CN112551588A - Preparation method of battery-grade manganese dioxide - Google Patents
Preparation method of battery-grade manganese dioxide Download PDFInfo
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- CN112551588A CN112551588A CN202011284227.5A CN202011284227A CN112551588A CN 112551588 A CN112551588 A CN 112551588A CN 202011284227 A CN202011284227 A CN 202011284227A CN 112551588 A CN112551588 A CN 112551588A
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract description 40
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 39
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 39
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000011656 manganese carbonate Substances 0.000 claims abstract description 26
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 claims abstract description 26
- 235000006748 manganese carbonate Nutrition 0.000 claims abstract description 25
- 229940093474 manganese carbonate Drugs 0.000 claims abstract description 25
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 claims abstract description 25
- 238000003756 stirring Methods 0.000 claims abstract description 25
- 238000001035 drying Methods 0.000 claims abstract description 23
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 16
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- 238000001914 filtration Methods 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000007800 oxidant agent Substances 0.000 claims abstract description 10
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 23
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 20
- 229910052748 manganese Inorganic materials 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- 239000012065 filter cake Substances 0.000 claims description 9
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000006864 oxidative decomposition reaction Methods 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000010000 carbonizing Methods 0.000 claims description 4
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 4
- 238000009776 industrial production Methods 0.000 abstract description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 7
- 229910052939 potassium sulfate Inorganic materials 0.000 description 7
- 238000005979 thermal decomposition reaction Methods 0.000 description 6
- 235000011151 potassium sulphates Nutrition 0.000 description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000003337 fertilizer Substances 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000010405 anode material Substances 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 229910000357 manganese(II) sulfate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05D—INORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C; FERTILISERS PRODUCING CARBON DIOXIDE
- C05D1/00—Fertilisers containing potassium
- C05D1/02—Manufacture from potassium chloride or sulfate or double or mixed salts thereof
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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 of battery-grade manganese dioxide, which comprises the following steps: respectively dissolving industrial manganese sulfate and potassium carbonate in water to prepare an industrial manganese sulfate solution and a potassium carbonate solution with certain concentrations for later use; mixing an industrial manganese sulfate solution and a potassium carbonate solution, heating, stirring to fully react, filtering and drying to obtain manganese carbonate; introducing oxygen into the manganese carbonate, and simultaneously heating until the manganese carbonate is decomposed to obtain a crude manganese dioxide product; dissolving manganese dioxide, adding sulfuric acid, adding a proper amount of oxidant, and fully mixing and reacting to obtain heavy manganese dioxide; and drying the manganese dioxide under a proper temperature condition to obtain the battery-grade chemical manganese dioxide. The process disclosed by the invention is suitable for preparing a chemical manganese dioxide product serving as a raw material of a power battery, is environment-friendly and clean, and is suitable for industrial production.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a preparation method of battery-grade manganese dioxide.
Background
The battery anode material is a key material of the lithium ion battery, the rapid increase of the output of the lithium ion battery drives the explosive increase of the demand of the lithium ion battery anode material, and the battery-grade Chemical Manganese Dioxide (CMD)) is a basic raw material applied to the lithium battery and is a preferential development direction for the development and utilization of manganese resources. At present, the main method for preparing battery-grade Chemical Manganese Dioxide (CMD) is to utilize low-valence manganese compounds to react with strong oxidant chlorine, hypochlorous acid or salts thereof and the like under certain chemical conditions to prepare manganese dioxide, and the preparation process of the method is mature, but has the obvious defects: the production cost is high, the generated waste liquid is difficult to treat, and the environmental protection problem is prominent; the other preparation method is to prepare Chemical Manganese Dioxide (CMD) by air oxidation roasting, the process has the disadvantages of overlong oxidation time, low efficiency, generally high impurity content of Fe, Ca, Na, S and the like in the product, low apparent density, irregular shape crystal form and incapability of preparing high-end manganese batteries. Therefore, it is important to develop a low-cost, high-efficiency battery-grade Chemical Manganese Dioxide (CMD) preparation method.
Disclosure of Invention
The invention aims to: aiming at the problems, the preparation method of the battery-grade manganese dioxide is provided. The method is suitable for preparing a Chemical Manganese Dioxide (CMD) product serving as a raw material of a power battery, is environment-friendly and clean in process, and is suitable for industrial production.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of battery-grade manganese dioxide comprises the following steps:
(1) liquid preparation: respectively dissolving industrial manganese sulfate and potassium carbonate in water to prepare an industrial manganese sulfate solution and a potassium carbonate solution with certain concentrations for later use;
(2) carbonizing and precipitating: mixing the industrial manganese sulfate solution obtained in the step (1) with a potassium carbonate solution, heating, stirring to fully react, filtering and drying to obtain manganese carbonate;
(3) oxidative decomposition: introducing oxygen into the manganese carbonate obtained in the step (2), and simultaneously heating until the manganese carbonate is decomposed to obtain crude manganese dioxide;
(4) and (3) weight conversion: dissolving the manganese dioxide obtained in the step (3), adding sulfuric acid, adding a proper amount of oxidant, and fully mixing and reacting to obtain heavy manganese dioxide;
(5) drying: and (4) drying the manganese dioxide obtained in the step (4) at a proper temperature to obtain the battery-grade chemical manganese dioxide.
Further, in the step (1), the manganese content of the industrial manganese sulfate solution is 50-120g/L, and the concentration of the potassium carbonate solution is 8-20%.
Further, in the step (2), the manganese sulfate solution is added into the potassium carbonate solution, the manganese sulfate liquid feeding speed is 50-100ml/min, the reaction temperature is 40-80 ℃, the stirring rotation number is 350r/min, after the feeding is finished, the stirring is continued for 1h, then the filter cake is obtained by filtering, and the filter cake is dried at the temperature of 100-105 ℃.
Further, in the step (3), the temperature of oxidative decomposition of the manganese carbonate is 400-.
Further, in the step (4), the manganese dioxide is dissolved and slurried according to a solid-to-liquid ratio of 1:2-3, the sulfuric acid is 50% sulfuric acid, and the acid addition is stopped when the pH value is 1.
Further, the reaction of adding the oxidant is to heat and stir for 1-3h at 50-80 ℃, measure the manganese content in the liquid, add potassium permanganate according to the manganese content, and stir for 3-4 h.
Further, in the step (6), the drying temperature is 100-.
The reaction principle is as follows: the invention prepares battery-grade manganese dioxide through multilayer reaction, and the reaction formula is as follows:
MnSO4+K2CO3＝MnCO3+K2SO4
2MnCO3+O2＝2MnO2+2CO2
2KMnO4+3MnSO4+2H2O＝5MnO2+2H2SO4+K2SO4
the reaction formula shows that: the industrial-grade manganese sulfate is extracted after being carbonized and precipitated through potassium carbonate, oxygen is introduced, the manganese carbonate is oxidized and decomposed at high temperature to form manganese oxide, manganese dioxide is dissolved through sulfuric acid, and then heavy manganese dioxide is oxidized through potassium permanganate to form battery-grade heavy manganese dioxide.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
according to the invention, industrial manganese sulfate is used as a raw material, potassium carbonate is used as a precipitator, the temperature of a reaction system is controlled, high-purity manganese carbonate is prepared, the thermal decomposition principle of manganese carbonate is utilized, pure oxygen is introduced for oxidizing roasting, so that crude manganese dioxide is generated by pyrolysis, and the efficiency and the conversion rate are obviously improved compared with those of air oxidation; finally, acidifying the crude manganese dioxide by using sulfuric acid, and carrying out weight conversion by using potassium permanganate to prepare high-quality Chemical Manganese Dioxide (CMD); the by-product tail liquid containing sulfuric acid and potassium sulfate can be circularly reused in the acidification section, and finally, the tail liquid is appropriately opened, and is combined with the carbonized potassium sulfate tail liquid, and alkali is adjusted to produce the high-quality potassium fertilizer.
Drawings
FIG. 1 is a process flow diagram of the present application.
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
130g of industrial manganese sulfate in a certain factory is dissolved until the manganese content is 80g/L, 500ml of manganese sulfate liquid is added into 10% potassium carbonate solution by mass, the feeding speed of the manganese sulfate is controlled to be 60ml/min, the temperature of carbonization precipitation is set to be 40 ℃, and the stirring speed is 300 r/min. After the manganese sulfate liquid is dripped, the reaction is continued for 1h, then the filtration is carried out, and a filter cake is taken and dried at the temperature of 105 ℃. And (3) placing the dried manganese carbonate into a muffle furnace, setting the temperature at 400 ℃, setting the oxygen flow at 0.1L/min, and carrying out thermal decomposition reaction for 6 hours to obtain a crude product of manganese dioxide. And (3) mixing the crude manganese dioxide according to the solid-to-liquid ratio of 1:2, dropwise adding 50% sulfuric acid until the pH of the slurry keeps 1, and then adding theoretical amount of potassium permanganate according to the total manganese content of the liquid. Stirring and reacting for 3h at 50 ℃, and filtering to obtain Chemical Manganese Dioxide (CMD), wherein a byproduct potassium sulfate is used as a potassium fertilizer.
Example 2
500g of industrial manganese sulfate is dissolved to ensure that the manganese content is 90g/L, 1500ml of manganese sulfate liquid is added into potassium carbonate solution with the mass fraction of 12%, the feeding speed of the manganese sulfate is controlled to be 70ml/min, the temperature of carbonization precipitation is set to be 50 ℃, and the stirring speed is 350 r/min. After the materials are added, the reaction is continued for 1h, then the filtration is carried out, and the filter cake is taken out and dried at the temperature of 105 ℃. And (3) placing the dried manganese carbonate into a muffle furnace, setting the temperature at 550 ℃, setting the oxygen flow at 0.1L/min, and carrying out thermal decomposition reaction for 5 hours to obtain a crude product of manganese dioxide. And (3) mixing the crude manganese dioxide according to the solid-to-liquid ratio of 1:2, dropwise adding 50% sulfuric acid until the pH of the slurry keeps 1, and then adding theoretical amount of potassium permanganate according to the total manganese content of the liquid. Stirring and reacting for 3h at 50 ℃, and filtering to obtain Chemical Manganese Dioxide (CMD), wherein a byproduct potassium sulfate is used as a potassium fertilizer.
Example 3
1kg of industrial manganese sulfate is dissolved until the manganese content is 100g/L, 3000ml of manganese sulfate liquid is added into potassium carbonate solution with the mass fraction of 15%, the feeding speed of the manganese sulfate is controlled to be 60ml/min, the temperature of carbonization precipitation is set to be 40 ℃, and the stirring speed is 300 r/min. After the materials are added, the reaction is continued for 1h, then the filtration is carried out, and the filter cake is taken out and dried at the temperature of 105 ℃. And (3) putting the dried manganese carbonate into a muffle furnace, setting the temperature at 500 ℃ and the oxygen flow at 0.15L/min, and carrying out thermal decomposition reaction for 4 hours to obtain a crude product of manganese dioxide. And (3) mixing the crude manganese dioxide according to the solid-to-liquid ratio of 1:2, dropwise adding 50% sulfuric acid until the pH of the slurry keeps 1, and then adding theoretical amount of potassium permanganate according to the total manganese content of the liquid. Stirring and reacting for 3h at 50 ℃, and filtering to obtain Chemical Manganese Dioxide (CMD), wherein a byproduct potassium sulfate is used as a potassium fertilizer.
Example 4
A preparation method of battery-grade manganese dioxide comprises the following steps:
(1) liquid preparation: respectively dissolving industrial manganese sulfate and potassium carbonate in water to prepare an industrial manganese sulfate solution and a potassium carbonate solution with certain concentrations for later use, wherein the manganese content of the industrial manganese sulfate solution is 50g/L, and the concentration of the potassium carbonate solution is 8%;
(2) carbonizing and precipitating: adding the manganese sulfate solution obtained in the step (1) into a potassium carbonate solution, mixing, heating, stirring to fully react, filtering and drying to obtain manganese carbonate, wherein the feeding speed of manganese sulfate liquid is 50ml/min, the reaction temperature is 40 ℃, the stirring revolution is 300r/min, after the manganese sulfate liquid is completely added, stirring for 1 hour is continued, filtering to obtain a filter cake, and drying at the temperature of 100 ℃;
(3) oxidative decomposition: introducing oxygen into the manganese carbonate obtained in the step (2), and simultaneously heating until the manganese carbonate is decomposed to obtain crude manganese dioxide, wherein the oxidative decomposition temperature of the manganese carbonate is 400 ℃, the flow of the introduced oxygen is 0.1L/min, and the thermal decomposition time is 2 h;
(4) and (3) weight conversion: dissolving the manganese dioxide obtained in the step (3), adding sulfuric acid, adding a proper amount of oxidant, fully mixing and reacting to obtain heavy manganese dioxide, wherein the manganese dioxide dissolution is realized by mixing slurry according to a solid-to-liquid ratio of 1:2, the sulfuric acid is sulfuric acid with a concentration of 50%, adding acid is stopped when the pH value is 1, the oxidant is added for reaction, the manganese content in the liquid is measured after heating and stirring for 1h at 50 ℃, potassium permanganate is added according to the manganese content, and stirring and reacting are carried out for 3 h;
(5) drying: and (4) drying the manganese dioxide obtained in the step (4) under a proper temperature condition to obtain battery-grade chemical manganese dioxide, wherein the drying temperature is 100 ℃, and the drying time is 3 hours.
Example 5
A preparation method of battery-grade manganese dioxide comprises the following steps:
(1) liquid preparation: respectively dissolving industrial manganese sulfate and potassium carbonate in water to prepare an industrial manganese sulfate solution and a potassium carbonate solution with certain concentrations for later use, wherein the manganese content of the industrial manganese sulfate solution is 120g/L, and the concentration of the potassium carbonate solution is 20%;
(2) carbonizing and precipitating: adding the manganese sulfate solution obtained in the step (1) into a potassium carbonate solution, mixing, heating, stirring to fully react, filtering and drying to obtain manganese carbonate, wherein the feeding speed of manganese sulfate liquid is 100ml/min, the reaction temperature is 80 ℃, the stirring revolution is 350r/min, after the manganese sulfate liquid is completely added, stirring for 1 hour is continued, filtering to obtain a filter cake, and drying at the temperature of 105 ℃;
(3) oxidative decomposition: introducing oxygen into the manganese carbonate obtained in the step (2), and simultaneously heating until the manganese carbonate is decomposed to obtain crude manganese dioxide, wherein the oxidative decomposition temperature of the manganese carbonate is 600 ℃, the flow of the introduced oxygen is 0.15L/min, and the thermal decomposition time is 8 h;
(4) and (3) weight conversion: dissolving the manganese dioxide obtained in the step (3), adding sulfuric acid, adding a proper amount of oxidant, fully mixing and reacting to obtain heavy manganese dioxide, wherein the manganese dioxide dissolution is realized by mixing slurry according to a solid-to-liquid ratio of 1:3, the sulfuric acid is sulfuric acid with a concentration of 50%, adding acid is stopped when the pH value is 1, the oxidant is added for reaction, the temperature is increased and stirred at 80 ℃ for 3 hours, the manganese content in the liquid is measured, potassium permanganate is added according to the manganese content, and the stirring reaction is carried out for 4 hours;
(5) drying: and (4) drying the manganese dioxide obtained in the step (4) under a proper temperature condition to obtain battery-grade chemical manganese dioxide, wherein the drying temperature is 150 ℃, and the drying time is 8 hours.
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 (7)
1. A preparation method of battery-grade manganese dioxide is characterized by comprising the following steps: the method comprises the following steps:
(1) liquid preparation: respectively dissolving industrial manganese sulfate and potassium carbonate in water to prepare an industrial manganese sulfate solution and a potassium carbonate solution with certain concentrations for later use;
(2) carbonizing and precipitating: mixing the industrial manganese sulfate solution obtained in the step (1) with a potassium carbonate solution, heating, stirring to fully react, filtering and drying to obtain manganese carbonate;
(3) oxidative decomposition: introducing oxygen into the manganese carbonate obtained in the step (2), and simultaneously heating until the manganese carbonate is decomposed to obtain crude manganese dioxide;
(4) and (3) weight conversion: dissolving the manganese dioxide obtained in the step (3), adding sulfuric acid, adding a proper amount of oxidant, and fully mixing and reacting to obtain heavy manganese dioxide;
(5) drying: and (4) drying the manganese dioxide obtained in the step (4) at a proper temperature to obtain the battery-grade chemical manganese dioxide.
2. The method of claim 1, wherein the step of preparing the battery grade manganese dioxide comprises: in the step (1), the manganese content of the industrial manganese sulfate solution is 50-120g/L, and the concentration of the potassium carbonate solution is 8-20%.
3. The method of claim 1, wherein the step of preparing the battery grade manganese dioxide comprises: in the step (2), the manganese sulfate solution is added into the potassium carbonate solution, the manganese sulfate liquid feeding speed is 50-100ml/min, the reaction temperature is 40-80 ℃, the stirring revolution is 300-350r/min, after the material is added, the mixture is continuously stirred for 1h, then the filter cake is obtained by filtering, and the filter cake is dried at the temperature of 100-105 ℃.
4. The method of claim 1, wherein the step of preparing the battery grade manganese dioxide comprises: in the step (3), the temperature of oxidative decomposition of the manganese carbonate is 400-.
5. The method of claim 1, wherein the step of preparing the battery grade manganese dioxide comprises: in the step (4), the manganese dioxide dissolution is slurry mixing according to the solid-to-liquid ratio of 1:2-3, the sulfuric acid is 50% sulfuric acid, and the acid addition is stopped when the pH value is 1.
6. The method of claim 5, wherein the step of preparing the battery grade manganese dioxide comprises: the reaction of adding oxidant is to heat and stir for 1-3h at 50-80 ℃, measure the manganese content in the liquid, add potassium permanganate according to the manganese content, stir and react for 3-4 h.
7. The method of claim 1, wherein the step of preparing the battery grade manganese dioxide comprises: in the step (6), the drying temperature is 100-150 ℃, and the drying time is 3-8 h.
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| WO2023088393A1 (en) * | 2021-11-18 | 2023-05-25 | 瑞海泊(青岛)能源科技有限公司 | Positive electrode material, and preparation method therefor and use thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2023088393A1 (en) * | 2021-11-18 | 2023-05-25 | 瑞海泊(青岛)能源科技有限公司 | Positive electrode material, and preparation method therefor and use thereof |
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