CN104393276A - Preparation method of doping-modified spinel-type lithium manganate - Google Patents
Preparation method of doping-modified spinel-type lithium manganate Download PDFInfo
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- CN104393276A CN104393276A CN201410532008.2A CN201410532008A CN104393276A CN 104393276 A CN104393276 A CN 104393276A CN 201410532008 A CN201410532008 A CN 201410532008A CN 104393276 A CN104393276 A CN 104393276A
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- acetate
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- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/12—Manganates manganites or permanganates
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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 preparation of lithium ion positive pole materials and especially relates to a preparation method of doping-modified spinel-type lithium manganate. The preparation method comprises the following steps of preparing a mixed solution of lithium acetate, chromium acetate, nickel acetate and manganese acetate, adding resorcinol into the mixed solution, carrying out stirring until resorcinol is completely dissolved, adding a formaldehyde solution into the obtained mixed solution, putting the mixed solution into a constant-temperature water bath, carrying out a reaction process to obtain gel, drying the gel by an oven, carrying out pre-sintering, grinding the pre-sintered product, carrying out secondary sintering, and grinding the re-sintered product to obtain the modified spinel-type lithium manganate. The preparation method utilizes lithium acetate, manganese acetate, chromium acetate, nickel acetate, resorcinol and formaldehyde as raw materials to prepare the doping-modified spinel-type lithium manganate, utilizes pre-sintering to improve product phase purity, utilizes secondary sintering to improve material crystallization performances, specific discharge capacity and energy density, and utilizes a reasonable raw material ratio to improve material electrochemical performances.
Description
Technical field
The present invention relates to the preparation field of lithium ion anode material, is the preparation method of doping vario-property lithium manganate having spinel structure 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.
Usually, the output voltage of dynamical lithium-ion battery packs is between 300-400V, a large amount of monocell is needed to connect, the number of series-connected cell depends on monocell operating voltage, single battery voltage is higher, and Series Sheet number of batteries is fewer, and relevant control circuit is simpler, reliability and the fail safe of integral battery door group are higher, and the operating voltage of lithium ion battery depends on the voltage of positive electrode.Thus the doping vario-property of lithium manganate having spinel structure positive electrode, significant to the positive electrode preparing high potential.
Summary of the invention
For above-mentioned technical problem, the invention provides a kind of doping vario-property lithium manganate having spinel structure with higher specific discharge capacity and energy density.
The present invention solves the problems of the technologies described above adopted technical scheme: the preparation method of doping vario-property lithium manganate having spinel structure, and it comprises the following steps:
(1) prepare lithium acetate, chromic acetate, nickel acetate, 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 mixing nickel chromium triangle modified spinelle manganic acid lithium.
As preferably, described lithium acetate: chromic acetate: nickel acetate, manganese acetate: resorcinol: the mol ratio of formaldehyde is 1:0.2:0.4:1.4:(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--950 DEG C.
As can be known from the above technical solutions, the present invention prepares modified spinelle type LiMn2O4 with lithium acetate, chromic acetate, manganese acetate, nickel 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 energy density 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, chromic acetate, nickel acetate, 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: chromic acetate: nickel acetate: manganese acetate: resorcinol: the mol ratio of formaldehyde is 1:0.2:0.4::1.4:(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--950 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, modified spinelle type LiMn2O4.
Embodiment 1
First, by 1mol lithium acetate, 0.2mol chromic acetate, 0.4mol nickel acetate, 1.4 manganese acetates 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 modified lithium manganate.Analyze after testing, the first discharge specific capacity of mixing chromium nickel modified lithium manganate prepared under above-mentioned condition is 109mAh/g, and the capability retention after 100 times that circulates is that the specific discharge capacity of material under 90%, 40C and mean voltage are respectively higher than 95mAh/g and 3.94V.
Embodiment 2
First, by 1mol lithium acetate, 0.2mol chromic acetate, 0.4mol nickel acetate, 1.4 manganese acetates 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 750 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 modified spinelle type LiMn2O4.Analyze after testing, the first discharge specific capacity of the modified lithium manganate prepared under above-mentioned condition is 132mAh/g, and the capability retention after 100 times that circulates is that the specific discharge capacity of material under 95%, 40C and mean voltage are respectively higher than 100mAh/g and 4.2V.
Embodiment 3
First, by 1mol lithium acetate, 0.2mol chromic acetate, 0.4mol nickel acetate, 1.4 manganese acetates 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 950 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 modified spinelle type LiMn2O4.Analyze after testing, the first discharge specific capacity of the modified lithium manganate prepared under above-mentioned condition is 121mAh/g, and the capability retention after 100 times that circulates is that the specific discharge capacity of material under 91%, 40C and mean voltage are respectively higher than 93mAh/g and 4.08V.
Visible, adopt this method can prepare the modified lithium manganate 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 doping vario-property lithium manganate having spinel structure, it comprises the following steps:
(1) prepare the mixed solution of lithium acetate, chromic acetate, nickel acetate, manganese acetate, 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 mixing nickel chromium triangle modified lithium manganate.
2. preparation method according to claim 1, is characterized in that: described lithium acetate: chromic acetate: nickel acetate: manganese acetate: resorcinol: the mol ratio of formaldehyde is 1:0.2:0.4:1.4:(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--950 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107845808A (en) * | 2017-11-06 | 2018-03-27 | 柳州光华科技有限公司 | A kind of preparation technology of lithium manganate battery material |
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| CN101859895A (en) * | 2010-05-20 | 2010-10-13 | 哈尔滨工业大学 | Method for improving electrochemical performance of positive material LiNi0.5Mn1.5O4 of lithium ion battery |
| 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 |
| CN103268937A (en) * | 2013-05-15 | 2013-08-28 | 陕西科技大学 | Preparation method of framework lithium manganate battery cathode material |
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2014
- 2014-10-11 CN CN201410532008.2A patent/CN104393276A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101859895A (en) * | 2010-05-20 | 2010-10-13 | 哈尔滨工业大学 | Method for improving electrochemical performance of positive material LiNi0.5Mn1.5O4 of lithium ion battery |
| 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 |
| CN103268937A (en) * | 2013-05-15 | 2013-08-28 | 陕西科技大学 | Preparation method of framework lithium manganate battery cathode material |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107845808A (en) * | 2017-11-06 | 2018-03-27 | 柳州光华科技有限公司 | A kind of preparation technology of lithium manganate battery material |
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