CN111620379A - Preparation method of high-end lithium manganate raw material - Google Patents
Preparation method of high-end lithium manganate raw material Download PDFInfo
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- CN111620379A CN111620379A CN202010422594.0A CN202010422594A CN111620379A CN 111620379 A CN111620379 A CN 111620379A CN 202010422594 A CN202010422594 A CN 202010422594A CN 111620379 A CN111620379 A CN 111620379A
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 239000002994 raw material Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 78
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 55
- 238000003756 stirring Methods 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 238000001035 drying Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 239000002253 acid Substances 0.000 claims abstract description 21
- 239000007787 solid Substances 0.000 claims abstract description 20
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002002 slurry Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005303 weighing Methods 0.000 claims abstract description 10
- LQKOJSSIKZIEJC-UHFFFAOYSA-N manganese(2+) oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Mn+2].[Mn+2].[Mn+2].[Mn+2] LQKOJSSIKZIEJC-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 14
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 10
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- 239000012286 potassium permanganate Substances 0.000 claims description 5
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 13
- 229910052760 oxygen Inorganic materials 0.000 abstract description 13
- 239000001301 oxygen Substances 0.000 abstract description 13
- 230000008901 benefit Effects 0.000 abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 11
- 239000011572 manganese Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 7
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003837 high-temperature calcination Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 229910002983 Li2MnO3 Inorganic materials 0.000 description 1
- 229910002993 LiMnO2 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- 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
-
- 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
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/5825—Oxygenated metallic salts or polyanionic structures, e.g. borates, phosphates, silicates, olivines
-
- 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
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a high-end lithium manganate raw material, which comprises the following steps: weighing a certain amount of manganese tetraoxide and water according to a proportion, mixing to form slurry, and starting a stirring device to fully stir; proportionally adding acid into a certain amount of water to be diluted to a proper concentration for later use; slowly dripping the prepared acid solution into the slurry, and stirring at normal temperature to ensure that the diluted acid and the manganese tetraoxide fully react; filtering the mixed solution after reaction for the first time by using a vacuum circulating pump, and filtering out solid substances for later use; adding water into the solid matter according to a certain proportion, rinsing, and performing secondary filtration to obtain filter residue which is a manganese oxide raw material mixed by mangano-manganic oxide and manganese dioxide; and drying the filter residue to obtain the high-end lithium manganate raw material. The preparation method of the invention fully utilizes the advantage of good performance of the lithium manganate prepared by taking the manganous-manganic oxide as the raw material, and also fully utilizes the purpose of generating oxygen when the manganese dioxide is taken as the raw material to prepare the lithium manganate.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a preparation method of a high-end lithium manganate raw material.
Background
The lithium manganate positive electrode material comprises spinel-type LiMn2O4Layered LiMnO2And layered Li2MnO3Of spinel type LiMn2O4Has good charge-discharge cycle performance and is widely applied to high-capacity and high-power batteries.
Currently LiMn2O4The preparation method mainly uses electrolytic manganese dioxide and Li2CO3The lithium manganate is obtained by high-temperature calcination, but the obtained lithium manganate product has the advantages of non-uniform phase, irregular crystal grains, large shape grain boundary size, wide particle size distribution range and poor electrical property of the prepared lithium battery; and the manganese dioxide contains more impurities, so that the electrochemical performance of the lithium manganate is influenced to a certain extent. In order to further improve the comprehensive performance of lithium manganate, a large number of experimental researches are carried out by researchers at home and abroad, and research results prove that the capacity and the cycle performance of the battery adopting manganous-manganic oxide as a manganese source to synthesize the lithium manganate are greatly improved, and the electrical performance of the battery is obviously superior to that of the lithium manganate prepared by taking manganese dioxide as the manganese source. Therefore, it is a trend to produce high-end lithium manganate by using battery grade trimanganese tetroxide instead of manganese dioxide as a manganese source. However, when the manganous-manganic oxide is used as a manganese source to prepare the lithium manganate, external oxygen supply is needed, and the oxygen introducing time is longer in the whole sintering process, so that the production cost is increased, the market share of products is reduced, and the economic benefit is low. This is also why this process has not been widely spread. Therefore, the problem of oxygen supply in the process for preparing lithium manganate by manganous-manganic oxide needs to be solved by reducing the cost.
Disclosure of Invention
The invention aims to: aiming at the problems, the preparation method of the manganese oxide raw material mixed by manganomanganic oxide and manganese dioxide is provided. The method comprises the steps of reacting trimanganese tetroxide with sulfuric acid to prepare manganese dioxide, adjusting the amount of sulfuric acid to obtain a trimanganese tetroxide and manganese dioxide mixed manganese oxide raw material, using the characteristics that manganese dioxide in the manganese oxide raw material generates oxygen and trimanganese tetroxide needs the oxygen, and preparing high-end lithium manganate by taking advantages and disadvantages and taking synergistic effects.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a high-end lithium manganate raw material comprises the following steps:
(1) slurry preparation: weighing a certain amount of manganese tetraoxide and water according to a proportion, mixing to form slurry, and starting a stirring device to fully stir;
(2) acid preparation: proportionally adding acid into a certain amount of water to be diluted to a proper concentration for later use;
(3) reaction: slowly dripping the acid solution prepared in the step (2) into the slurry, and stirring at normal temperature to ensure that the diluted acid and the manganese tetraoxide fully react;
(4) and (3) filtering: performing primary filtration on the mixed solution after the reaction in the step (3) by using a vacuum circulating pump, and filtering out solid substances for later use;
(5) rinsing: adding water into the solid matter obtained in the step (4) according to a certain proportion, rinsing, and performing secondary filtration to obtain filter residue which is a manganese oxide raw material mixed by manganous-manganic oxide and manganese dioxide;
(6) drying: and (5) drying the filter residue in the step (5) to obtain the high-end lithium manganate raw material.
Further, in the step (1), the weight ratio of the trimanganese tetroxide to the water is 1: (1-3), wherein the stirring speed of the stirring is 250-500 r/min.
Further, in the step (2), the acid is sulfuric acid, and the concentration after dilution is 10-50%.
Further, in the step (3), the dropping speed of the acid solution is 5-20ml/min, and the stirring reaction time is 3-6 h.
Further, in the step (4), the filter screen used for filtering is a micron-grade filter screen, so that suspended matters in the mixed liquor are completely filtered out.
Further, in the step (5), the ratio of the solid matter to water is 1: (2-5), and the rinsing is to add water into the solid matters and then fully stir the solid matters evenly to dissolve impurities on the solid matters into the water and filter the impurities out.
Further, in the step (6), the drying temperature is 150-.
And (3) further, mixing the potassium permanganate raw material obtained in the step (6) with a lithium source, and performing high-temperature calcination to prepare high-end lithium manganate.
The reaction principle is as follows: the invention prepares manganous manganic oxide and manganese dioxide mixed manganese oxide raw material according to liquid phase reaction, and the reaction formula is as follows:
Mn3O4+H2SO4→MnO2+MnSO4+H2O
manganese dioxide generates oxygen, and the reaction formula of oxygen required by trimanganese tetroxide is as follows:
the overall reaction formula is:
the reaction formula shows that: properly adjusting the dosage of the sulfuric acid to enable part of the mangano-manganic oxide to generate manganese dioxide, stopping adding the sulfuric acid after the required manganese dioxide is obtained, stopping the reaction, and finally obtaining the mangano-manganic oxide and manganese dioxide mixed manganese oxide raw material. After the manganese oxide raw material is obtained, the materials are mixed according to the proportion of a manganese source and a lithium source, and are subjected to high-temperature calcination and powder grinding to obtain the high-end lithium manganate.
The raw material for producing the lithium manganate material is mainly manganese dioxide, and the morphology, specific surface area, granularity and distribution of the manganese dioxide, and the content of impurities such as iron, sulfate radical, sodium ions and the like cannot be effectively controlled, so that the high-performance lithium manganate material is difficult to produce, and the requirements of a lithium ion power battery are difficult to meet. In order to further improve the comprehensive performance, particularly the electrical performance, of the lithium manganate, the battery capacity and the cycle performance of the lithium manganate synthesized by adopting the trimanganese tetroxide as a manganese source are greatly improved, and the electrical performance is obviously superior to that of the lithium manganate taking electrolytic manganese dioxide as a manganese source. The main reason for improving the electrical property is that the manganous-manganic oxide and the lithium manganate have a spinel structure, and the structure change is relatively small in the sintering process, so that the caused internal stress is smaller, and the material structure is more stable. Therefore, it has become a trend to replace a portion of the electrolytic manganese dioxide with battery grade trimanganese tetroxide as a manganese source to produce high-end lithium manganate.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
in order to fully utilize the advantages of good performance of the lithium manganate prepared by taking manganous manganic oxide as a raw material and fully utilize the oxygen generated in the process of preparing the lithium manganate by taking manganese dioxide as a raw material, the invention prepares high-end lithium manganate by using a mixture of the manganous manganic oxide and the manganese dioxide, controls the mass ratio of the manganese dioxide to be 60-75% by controlling the dosage of sulfuric acid, fully utilizes the oxygen generated inside the lithium manganate prepared by taking the manganese dioxide as the raw material, and greatly saves the production cost of the lithium manganate.
The lithium manganate produced by the technology has good performance and low cost, a sample is subjected to a power-on test, the 1C first discharge capacity reaches 125.38mAh/g, and after 50 times of charge-discharge circulation, the capacity retention rate is 96.03%, so that the performance of the lithium manganate prepared by taking manganese dioxide as a raw material is greatly superior to that of the lithium manganate prepared by taking manganese dioxide as a raw material.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in further detail below with reference to preferred embodiments. It should be noted, however, that the numerous details set forth in the description are merely for the purpose of providing the reader with a thorough understanding of one or more aspects of the present invention, which may be practiced without these specific details.
Example 1
A preparation method of a high-end lithium manganate raw material comprises the following steps:
(1) slurry preparation: weighing a certain amount of manganous oxide and water according to a proportion, mixing to form slurry, starting a stirring device to fully stir, wherein the weight of the manganous oxide and the weight of the water are respectively 1000g and 1000 ml, and the stirring speed of stirring is 250 r/min;
(2) acid preparation: proportionally adding sulfuric acid into a certain amount of water to be diluted to a concentration of 10%;
(3) reaction: slowly dripping 5000ml of sulfuric acid solution prepared in the step (2) into the slurry at the dripping speed of 20ml/min, stirring at normal temperature, and reacting for 3 hours to ensure that diluted acid and manganese tetraoxide fully react;
(4) and (3) filtering: performing primary filtration on the mixed solution reacted in the step (3) by using a vacuum circulating pump to filter out solid substances for later use, wherein the filter screen used for filtration is a micron-level filter screen, so that suspended matters in the mixed solution are all filtered out;
(5) rinsing: adding the solid substance obtained in the step (4) into a reactor with the weight ratio of 1: 2, adding water in the proportion, rinsing, and performing secondary filtration to obtain filter residue which is a manganese oxide raw material mixed by manganous-manganic oxide and manganese dioxide;
(6) drying: and (5) drying the filter residue in the step (5) to obtain a high-end lithium manganate raw material, wherein the drying temperature is 150 ℃, and the drying time is 1 h.
(7) Calcining the mixture of the potassium permanganate raw material obtained in the step (6) and a lithium source to prepare high-end lithium manganate by high-temperature calcination;
(8) and testing the electrical property of the lithium manganate.
Example 2
1) Slurry preparation: weighing a certain amount of manganous oxide and water according to a proportion, mixing to form slurry, starting a stirring device to fully stir, wherein the weight ratio of the manganous oxide to the water is 1: 3, the stirring speed of the stirring is 500 r/min;
(2) acid preparation: proportionally adding sulfuric acid into a certain amount of water to be diluted to the concentration of 50%;
(3) reaction: slowly dripping 900ml of the sulfuric acid solution prepared in the step (2) into the slurry at a dripping speed of 5ml/min, stirring at normal temperature, and reacting for 6 hours to ensure that the diluted acid and the manganese tetraoxide fully react;
(4) and (3) filtering: performing primary filtration on the mixed solution reacted in the step (3) by using a vacuum circulating pump to filter out solid substances for later use, wherein the filter screen used for filtration is a micron-level filter screen, so that suspended matters in the mixed solution are all filtered out;
(5) rinsing: adding the solid substance obtained in the step (4) into a reactor with the weight ratio of 1: 5, adding water in the proportion, rinsing, and filtering for the second time to obtain filter residue which is a manganese oxide raw material mixed by manganomanganic oxide and manganese dioxide;
(6) drying: and (5) drying the filter residue in the step (5) to obtain a high-end lithium manganate raw material, wherein the drying temperature is 230 ℃, and the drying time is 2.5 h.
(7) Calcining the mixture of the potassium permanganate raw material obtained in the step (6) and a lithium source to prepare high-end lithium manganate by high-temperature calcination;
(8) and testing the electrical property of the lithium manganate.
Example 3
(1) Slurry preparation: weighing a certain amount of manganous oxide and water according to a proportion, mixing to form slurry, starting a stirring device to fully stir, wherein the weight ratio of the manganous oxide to the water is 1: 2, the stirring speed of the stirring is 350 r/min;
(2) acid preparation: proportionally adding sulfuric acid into a certain amount of water to be diluted to the concentration of 25%;
(3) reaction: slowly dripping 3000ml of the sulfuric acid solution prepared in the step (2) into the slurry at a dripping speed of 15ml/min, stirring at normal temperature, and reacting for 4 hours to ensure that the diluted acid and the manganese tetraoxide fully react;
(4) and (3) filtering: performing primary filtration on the mixed solution reacted in the step (3) by using a vacuum circulating pump to filter out solid substances for later use, wherein the filter screen used for filtration is a micron-level filter screen, so that suspended matters in the mixed solution are all filtered out;
(5) rinsing: adding the solid substance obtained in the step (4) into a reactor with the weight ratio of 1: 3, adding water in the proportion, rinsing, and performing secondary filtration to obtain filter residue which is a manganese oxide raw material mixed by manganous-manganic oxide and manganese dioxide;
(6) drying: and (5) drying the filter residue in the step (5) to obtain a high-end lithium manganate raw material, wherein the drying temperature is 200 ℃, and the drying time is 2 hours.
(7) Calcining the mixture of the potassium permanganate raw material obtained in the step (6) and a lithium source, and calcining at the high temperature of 810 ℃ to prepare high-end lithium manganate;
(8) and testing the electrical property of the lithium manganate.
Example 4
900g of mangano-manganic oxide is weighed, 900mL of water is added, the stirring speed is set to be 300r/min, 1200mL of 30% sulfuric acid is slowly added, the addition speed of dilute sulfuric acid is 10mL/min, and the mixture is stirred for 4h at normal temperature. And after the reaction is finished, filtering, rinsing the filter residue by adding 900mL of water, and after rinsing the filter residue, drying the filter residue in an oven at the drying temperature of 200 ℃ for 1h to obtain 420g of the manganese oxide raw material mixed by manganous manganic oxide and manganese dioxide, wherein the mass ratio of the manganese dioxide is 70%. Weighing 90g of lithium carbonate according to the proportion of a manganese source and a lithium source of lithium manganate, mixing, grinding, putting into a muffle furnace, and sintering at 800 ℃ for 10 h. And cooling to obtain high-end lithium manganate, and making a test sample into a power-on test.
Example 5
Weighing 2kg of mangano-manganic oxide, adding 2.5L of water, setting the stirring speed to be 400r/min, slowly adding 2700mL of 30% sulfuric acid, adding 30mL/min of dilute sulfuric acid, and stirring for 3h at normal temperature. And after the reaction is finished, filtering, rinsing the filter residue by adding 2.5L of water, and after rinsing the filter residue, drying the filter residue in a drying oven at the drying temperature of 200 ℃ for 1h to obtain 900g of the manganese oxide raw material mixed by manganous manganic oxide and manganese dioxide, wherein the mass ratio of the manganese dioxide is 65%. Weighing 200g of lithium carbonate according to the proportion of a manganese source and a lithium source of lithium manganate, mixing, grinding, putting into a muffle furnace, and sintering at 800 ℃ for 11 h. And cooling to obtain high-end lithium manganate, and making a test sample into a power-on test.
Example 6
Weighing 5kg of mangano-manganic oxide, adding 6.5L of water, setting the stirring speed to be 400r/min, slowly adding 5L of 40% sulfuric acid, setting the adding speed of dilute sulfuric acid to be 30mL/min, and stirring for 2h at normal temperature. And after the reaction is finished, filtering, rinsing the filter residue by adding 6.5L of water, and after rinsing the filter residue, drying the filter residue in a drying oven at the drying temperature of 200 ℃ for 1h to obtain 2300g of the manganese oxide raw material mixed by manganous manganic oxide and manganese dioxide, wherein the mass ratio of the manganese dioxide is 65%. According to the proportion of a manganese source and a lithium source of lithium manganate, 500g of lithium carbonate is weighed, mixed and grinded, and then placed into a muffle furnace to be sintered for 11 hours at 800 ℃. And cooling to obtain high-end lithium manganate, and making a test sample into a power-on test.
TABLE 1 test data for various examples
By integrating the above embodiments, the lithium manganate produced by the production method of the present invention has good performance in all aspects, and the whole production method has the following advantages:
1. in order to achieve the purposes of fully utilizing the advantages of good performance of the lithium manganate prepared by taking manganous-manganic oxide as a raw material and fully utilizing oxygen generated in the process of preparing the lithium manganate by taking manganese dioxide as a raw material, MnO is added into the lithium manganate2The molar ratio of the component (A) is 81-90%.
2. The kiln is not communicated with oxygen, so that oxygen generated inside the kiln when manganese dioxide is used as a raw material for preparing lithium manganate is fully utilized, and the production cost of the lithium manganate is greatly saved.
3. The whole preparation method is simple to operate, practical, high in economical efficiency and universal.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (8)
1. A preparation method of a high-end lithium manganate raw material is characterized by comprising the following steps: the method comprises the following steps:
(1) slurry preparation: weighing a certain amount of manganese tetraoxide and water according to a proportion, mixing to form slurry, and starting a stirring device to fully stir;
(2) acid preparation: proportionally adding acid into a certain amount of water to be diluted to a proper concentration for later use;
(3) reaction: slowly dripping the acid solution prepared in the step (2) into the slurry, and stirring at normal temperature to ensure that the diluted acid and the manganese tetraoxide fully react;
(4) and (3) filtering: performing primary filtration on the mixed solution after the reaction in the step (3) by using a vacuum circulating pump, and filtering out solid substances for later use;
(5) rinsing: adding water into the solid matter obtained in the step (4) according to a certain proportion, rinsing, and performing secondary filtration to obtain filter residue which is a manganese oxide raw material mixed by manganous-manganic oxide and manganese dioxide;
(6) drying: and (5) drying the filter residue in the step (5) to obtain the high-end lithium manganate raw material.
2. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: in the step (1), the weight ratio of the manganous-manganic oxide to the water is 1: (1-3), wherein the stirring speed of the stirring is 250-500 r/min.
3. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: in the step (2), the acid is sulfuric acid, and the concentration after dilution is 10-50%.
4. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: in the step (3), the dropping speed of the acid solution is 5-20ml/min, and the stirring reaction time is 3-6 h.
5. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: in the step (4), the filter screen used for filtering is a micron-grade filter screen, so that suspended matters in the mixed solution are completely filtered out.
6. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: in step (5), the ratio of the solid matter to water is 1: (2-5), and the rinsing is to add water into the solid matters and then fully stir the solid matters evenly to dissolve impurities on the solid matters into the water and filter the impurities out.
7. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: in the step (6), the drying temperature is 150-230 ℃, and the drying time is 1-2.5 h.
8. The method for preparing a high-end lithium manganate raw material according to claim 1, characterized in that: and (4) mixing the potassium permanganate raw material obtained in the step (6) with a lithium source, and calcining at high temperature to prepare the high-end lithium manganate.
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