CN105523587A - High-quality trimanganese tetraoxide preparation method and product prepared by same - Google Patents
High-quality trimanganese tetraoxide preparation method and product prepared by same Download PDFInfo
- Publication number
- CN105523587A CN105523587A CN201610105839.0A CN201610105839A CN105523587A CN 105523587 A CN105523587 A CN 105523587A CN 201610105839 A CN201610105839 A CN 201610105839A CN 105523587 A CN105523587 A CN 105523587A
- Authority
- CN
- China
- Prior art keywords
- preparation
- trimanganese tetroxide
- quality
- sheet
- electrolytic metal
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
Disclosed are a high-quality trimanganese tetraoxide preparation method and a product prepared by the same. According to the high-quality trimanganese tetraoxide preparation method, unpassivated electrolytic manganese metal sheets are taken as a raw material, electrolytic manganese metal slurry is prepared by a water atomization method, and the electrolytic manganese metal slurry is subjected to suspended oxidizing reaction to obtain low-selenium low-iron trace-chromium high-quality trimanganese tetraoxide. The high-quality trimanganese tetraoxide preparation method has the advantages that since a surface passivation technology is omitted, intake of harmful ions such as chromium ions can be avoided; proper technological parameters are arranged during smelting, so that low-boiling-point harmful elements such as selenium, sulfur and phosphorus contained in manganese metal sheets originally can be removed; the problem that the iron and the chromium are added severely during pulping by a traditional ball milling pulverization technology can be solved by the water atomization method for pulping, prepared slurry particle size distribution is more centralized, and accordingly the low-selenium low-iron trace-chromium high-quality trimanganese tetraoxide can be prepared. The invention further provides the trimanganese tetraoxide product prepared by the method and a lithium manganate material synthesized by the trimanganese tetraoxide product.
Description
Technical field
The present invention relates to a kind of preparation method of high-quality trimanganese tetroxide and the product of preparation, particularly relate to a kind of low selenium, lithium manganate material that low iron, the preparation method of trace chromium high-quality trimanganese tetroxide synthesize with the trimanganese tetroxide product of preparation and trimanganese tetroxide product.
Background technology
Trimanganese tetroxide is the four directions crystallization of a kind of black, another name brightness manganese, hausmannite, activity oxidation manganese, crystallization is become through calcination, belong to spinels, wherein divalence and Manganic ion are distributed on two kinds of different crystallographic sites, oxonium ion is that cubic close is piled up, and divalent manganesetion accounts for tetrahedron space, and Manganic ion accounts for octahedral interstices.The production technique of current high-quality trimanganese tetroxide mainly contains following several method:
(1) manganese sulfate solution oxidation style, by the manganese sulfate solution adopting manganese ore wet-leaching to obtain, by impurity and purification, add ammonium salt alkalization, filter, adopt air or oxygen oxidation, washing obtain trimanganese tetroxide crystal, dry trimanganese tetroxide crystal, cool, pack and to obtain product.Although this method technical maturity, due to manganese sulfate solution purification and impurity removal, particularly remove potassium sodium calcium magnesium addition ion and remain in technological difficulties, therefore, adopt this method to be difficult to the trimanganese tetroxide of obtained high-purity rank.
(2) manganous sulfate calcination method: manganous sulfate heating crystals is calcined, directly generates trimanganese tetroxide, obtain product through washing and drying.The key of this method is to obtain high-purity mangano-manganic oxide, first must ensure the purity of manganous sulfate crystal, because after manganous sulfate crystal high-temperature decomposes, impurity can continue to remain in trimanganese tetroxide, and has the problem of enrichment increase.
(3) electrolytic metal manganese powder suspension oxidation style: with electrolytic metal Mn sheet for raw material, first pulverized by manganese metal sheet and make manganese powder suspension, recycling air or oxygen makees oxygenant, in certain temperature with under the condition of adding ammonium salt, prepares trimanganese tetroxide.China is Mn3O4 major country of production, and production technique generally adopts electrolytic metal Mn wet oxidation method, and its typical process flow is: electrolytic metal Mn sheet → powder process (dry method, wet method) → oxidation → washing → drying → finished product.This preparation method has that technique is simple, easy to operate, unit output is large, manganese recovery ratio is high and pollute the advantages such as little, is adopted by most of manufacturer.Although this method technical maturity, simple, less investment, its outstanding shortcoming is not resolved for many years: 1) with low content of technology, production cost is high, and profit is very low; 2) various foreign matter content is generally higher, can only produce the product of common grade; 3) specific surface area is less, is generally 5m
2/ g-10m
2/ g, foreign customers general requirement is at 10m
2/ more than g; 4) impure selenium (Se) is higher.
In China's electrolytic manganese production process, most producer employs additive SeO
2, the thus Se of made electrolytic manganese generally containing 0.05-0.1%, correspondingly, domestic trimanganese tetroxide is usually containing higher impurity Se.For producing the trimanganese tetroxide of low Se, current way is, selects low Se electrolytic manganese, but price is high on the one hand to select low Se manganese sheet, and low Se manganese sheet is thick and fine and close on the other hand, is difficult to fragmentation, and tooling cost remains high.Certainly also can consider to adopt other without Se raw material as MnSO4 etc., but be difficult to purification due to other impurity such as silicon, calcium, magnesium, the technological process of production is partially long, and refuse is difficult to process and quantity discharged is large again, and its industrialization is still needed perfect.Therefore, how to have become with the Mn3O4 preparing low Se containing Se manganese sheet the problem be of practical significance very much.
Documents 1:CN103178256A discloses a kind of preparation method of mangano-manganic oxide for lithium-manganese battery, except after Na, Mg by the electrolytic metal Mn sheet hot water of low S, with Vertical Mill, electrolytic metal Mn sheet is milled to the manganese slurry that-200 μm are greater than 95%, drop in reactor and stir, pass into atmospheric oxidation simultaneously, and slowly inject ammoniacal liquor, react that within 15-25 hour, to obtain median size be 3-10 μm of trimanganese tetroxide manganese slurry.Again trimanganese tetroxide manganese slurry is dropped in another reactor and carry out secondary reaction, xitix and formaldehyde is added in reactor, stir, temperature of reaction controls at 50 DEG C-70 DEG C, reaction times is four hours, by the trimanganese tetroxide manganese plasm scouring obtained, after drying, obtaining median size is 15 ~ 20 μm, the heavy trimanganese tetroxide of jolt ramming.
Documents 2:CN104803419A discloses a kind of preparation method of trimanganese tetroxide, comprises the steps: (1) raw materials pretreatment; (2) slurrying; (3) acidleach: filter add 98% strong sulfuric acid response 40 ~ 60min in ore pulp after, the weight ratio of ore pulp and the vitriol oil is 3 ~ 4.5:1; (4) removal of impurities; (5) electrolysis; (6) passivation; (7) clean; (8) dry and peel off; (10) concentrated, washing, centrifugal, dehydration, dry trimanganese tetroxide powder.The present invention's low-grade manganese carbonate ore produces electrolytic metal manganese powder, trimanganese tetroxide is prepared again with electrolysis manganese powder, the trimanganese tetroxide specific surface area obtained is 15 ~ 20m2/g, and loose density is 0.6 ~ 0.8g/cm3, and the massfraction of trimanganese tetroxide is more than or equal to 71%.
Documents 3:CN103121723A discloses a kind of preparation method of low calcium and magnesium high-purity mangano-manganic oxide, by the manganese slurry of electrolytic metal Mn sheet vertical grinder wet grinding mill to 95% by-45 μm, pass into atmospheric oxidation in a kettle., stir, inject ammoniacal liquor and make catalyzer, be obtained by reacting trimanganese tetroxide.
The preparation method of trimanganese tetroxide disclosed in above documents belongs to electrolytic metal manganese powder suspension oxidation style to prepare trimanganese tetroxide, in its preparation method, documents 1 and documents 3 all adopt vertical grinder wet method (ball-milling technology) electrolytic metal Mn sheet to be worn into manganese slurry, the method of slurrying general at present is also adopt wet method slurrying (ball milling slurrying), the size-grade distribution of the slurry that wet method slurrying obtains is concentrated not, and easily increases the heavy metal element such as iron, chromium in pulping process.Carried out surface passivation to electrolytic manganese sheet in documents 2, passivation technology can make electrolytic metal Mn sheet top layer chromium content raise, the quality of the trimanganese tetroxide product of impact preparation and purity.
Summary of the invention
The technical problem to be solved in the present invention is to provide the having complete spinel structure and can apply the preparation method of the trimanganese tetroxide synthesizing lithium manganate having spinel structure material and the product of preparation of high-quality of a kind of low selenium (content of selenium element is lower than 0.0005%), low iron (content of ferro element is lower than 0.015%), trace chromium (content of chromium is 1,000,000/).
In order to solve the problems of the technologies described above, the present invention by the following technical solutions:
The invention provides a kind of preparation method of high-quality trimanganese tetroxide, be specially:
One for raw material with not passivation electrolytic metal Mn sheet, adopts water atomization to prepare electrolytic metal Mn slurry, then electrolytic metal Mn slurry suspension oxidizing reaction is obtained the preparation method of low selenium, low iron, trace chromium high-quality trimanganese tetroxide.
Further, described preparation method specifically comprises the following steps:
The surface treatment of A, not passivation electrolytic metal Mn sheet:
Directly fresh not passivation electrolytic metal Mn sheet is cleaned, dry;
B, employing water atomization prepare electrolytic metal Mn slurry, comprise the steps:
B1, melting technology: dropped in intermediate frequency furnace by the not passivation electrolytic metal Mn sheet after steps A surface treatment and carry out melting, its melting duration is 35-40 minute, and smelting temperature is 1250-1350 DEG C;
B2, water atomization pulping: pour the manganese metal sheet turndown in intermediate frequency furnace after melting into water atomization plant and carry out water atomization process, regulate water atomization pressure to be 300-400 kilogram, turndown duration is 10-12min;
B3, to size mixing: according to the needs of rear end suspension oxidation reaction solution concentration, regulate slurry concentration to solid-liquid ratio to be 1.6-2.0;
C, suspension oxidation react:
Be placed in reactor by electrolytic metal Mn slurry obtained in step B and carry out suspension oxidation reaction, inject ammoniacal liquor and make catalyzer, pass into air, temperature of reaction is 50-70 DEG C; Stirring velocity is 220-260r/min; Blast volume is 1.8-2.2L/min; Reaction times is 20-24h;
D, centrifugal drying: obtain trimanganese tetroxide after suspension oxidation has reacted, through cleaning, after adopting centrifugal drying technique to dehydrate, get product.
Further,
In step B2, water atomization pulping is obtained is more than or equal to 95% by-150 object electrolytic metal Mn slurries.
Further,
Reactor described in step C is ceramic pipeline reactor.
Preferably, the reactor of described ceramic pipeline is the reactor on aluminum oxide abrasion resistant ceramic tube road.
Further,
The slag making also comprising melting in described step B1 melting technology with skim operation, described in skim in operation and adopt slagging agent to carry out slag hitting process, improve melting purity.
Slagging agent is also known as slag former, and slagging agent has adsorption and melting ability to slag body, and energy is refining molten metal fully, reduces slag to metallic pollution, and fully reclaiming has valency effective metal, and raising product direct yield, reduces costs, reduce slag rate.Slagging agent described in this programme can adopt the conventional slagging agent of industrial melting, such as: sodium aluminum fluoride.
Further,
Adopt protection of inert gas air ring to protect electrolytic metal Mn sheet in described step B1 melting technology, prevent it to be oxidized;
Described rare gas element preferably adopts nitrogen or argon gas.
Preferably,
Described intermediate frequency furnace is 500KG level intermediate frequency furnace.
Further,
In described not passive metal manganese sheet: Mn >=99.9%; C≤0.02%; S≤0.04%; P≤0.002%; Si≤0.004%; Se≤0.001%; Fe≤0.01%.
Preferred DJMnB is passive metal manganese sheet not.
The present invention also provides a kind of trimanganese tetroxide adopting above-mentioned preparation method to obtain, and described trimanganese tetroxide has complete spinel structure, in described trimanganese tetroxide:
Content≤0.0005% of Se element; Content≤0.015% of Fe element; The content of chromium element is trace, namely the content of chromium be less than 1,000,000/;
The content of S element is 8-12ppm, the content < 5ppm of P element, the content < 15ppm of C element.
The present invention also provides a kind of lithium manganate material of the trimanganese tetroxide synthesis adopting above-mentioned preparation method to obtain, and described lithium manganate material is lithium manganate having spinel structure (LiMn
2o
4) material.
Due to Mn
3o
4and LiMn
2o
4be all spinel structure, use Mn
3o
4synthesis LiMn
2o
4there is not violent structural changes, and use general electrolytic MnO
2for manganese source, adopt LiMn prepared by same process
2o
4compare, LiMn
2o
4formation relatively easy, therefore with Mn
3o
4synthesis LiMn
2o
4come into one's own gradually.With Mn
3o
4for manganese source, solid reaction process is adopted to prepare LiMn
2o
4technical process as follows:
With Mn
3o
4, Li
2o
3for raw material, dehydrated alcohol is dispersion agent ground and mixed, after 600 DEG C of pre-burning 6h, as in crucible, then crucible is placed in calcination reaction 30h at retort furnace 750 DEG C, and afterwards, 600 DEG C of annealing 6h, can obtain LiMn after furnace cooling
2o
4material.
Beneficial effect of the present invention:
1, prepared in the method for trimanganese tetroxide in the past, for guaranteeing appearance luster and the use properties of electrolytic metal Mn sheet, the manganese metal sheet that usually need go out electrolysis carries out chromating process, and before and after passivation technology process, electrolytic metal Mn sheet top layer chromium content can increase to about 80ppm by 20ppm.Method of the present invention is after the preparation of electrolytic metal Mn sheet, cancel surface passivation technology, adopt the electrolytic metal Mn sheet of unpassivated to directly apply to and prepare trimanganese tetroxide product, effectively can avoid the absorption of the harmful ions such as chromium ion, the increasing chromium problem in passivating process can be avoided.
In the metal smelting process of 2, the water atomization technique of the inventive method, smelting temperature is arranged on 1250-1350 DEG C, by adjusting process parameter, the lower boiling harmful element such as selenium, sulphur, phosphorus originally contained in electrolytic metal Mn sheet can be removed, make in the trimanganese tetroxide obtained: the content of selenium element is lower than 5ppm, the content of element sulphur is at about 10ppm, and the content of phosphoric is less than 5ppm, and the content of carbon is lower than 15ppm.The physical function parameter of part lower boiling harmful element is as follows:
Physical function parameter index table
| Mn | Se | S | P | Fe | Cr | |
| Fusing point DEG C | 1244 | 217 | 112.8 | 44.1 | 1535 | 1857 |
| Boiling point DEG C | 1962 | 684.9 | 444.674 | 280 | 2750 | 2672 |
3, adopt intermediate frequency furnace to carry out melting to manganese metal sheet in the inventive method, and adopt the slag making of melting and to skim operation, adopt slagging agent to carry out slag hitting process, improve melting purity, also can remove the wherein harmful element such as selenium, sulphur, phosphorus further.
4, in traditional technology, ball mill crushing technique is often adopted to obtain electrolytic metal Mn slurry, the phenomenon increasing the heavy metal element such as iron, chromium is serious, have a strong impact on the quality of product, method in the present invention prepares electrolytic metal Mn slurry by atomization, make the slurry size-grade distribution prepared more concentrated, and the content increasing the heavy metal element such as iron, chromium can be avoided, improve the quality of product.
5, ceramic pipeline is adopted in the suspension oxidation technique in the inventive method, the absorption of the harmful elements such as iron, chromium, selenium can be avoided, prepare the trimanganese tetroxide product of low selenium, low iron, trace chromium high-quality, in the trimanganese tetroxide that present method is obtained: the content of selenium element lower than 0.0005%, the content of ferro element lower than 0.015%, the content of chromium element is trace, namely the content of chromium be 1,000,000/.
6, the trimanganese tetroxide that method of the present invention is prepared has very high purity and complete spinel structure, can be good at being applied as synthetic spinel type lithium manganate.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is only some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the process flow sheet of preparation method of the present invention;
Fig. 2 be adopt the trimanganese tetroxide prepared of method of the present invention for the production of the X ray diffracting spectrum of lithium manganate product;
The spinel structure schematic diagram of the lithium manganate of the trimanganese tetroxide synthesis that Fig. 3 obtains for method described in employing embodiment 1.
Embodiment
Below in conjunction with drawings and Examples, invention is further illustrated, but be not used for limiting the scope of the invention.
Embodiment 1
As shown in Figure 1, the preparation method of a kind of high-quality trimanganese tetroxide in the present embodiment, specifically comprises the following steps:
The surface treatment of A, not passivation electrolytic metal Mn sheet:
Directly fresh not passivation electrolytic metal Mn sheet is cleaned, dry;
B, employing water atomization prepare electrolytic metal Mn slurry, comprise the steps:
B1, melting technology: the not passivation electrolytic metal Mn sheet after steps A surface treatment is dropped into 500KG level intermediate frequency furnace and carry out melting, its melting duration is 35 minutes, and smelting temperature is 1250 DEG C;
Adopt slag making in fusion process and to skim operation, described in skim in operation and adopt slagging agent sodium aluminum fluoride to carry out slag hitting process, improve melting purity;
Also adopt nitrogen protection air ring to protect electrolytic metal Mn sheet in fusion process, prevent it to be oxidized;
B2, water atomization pulping: pour the manganese metal sheet turndown in intermediate frequency furnace after melting into water atomization plant and carry out water atomization process, water atomization pressure is regulated to be 300 kilograms, obtain and be more than or equal to 95% by-150 object electrolytic metal Mn slurries, turndown duration is 10min;
B3, to size mixing: according to the needs of rear end suspension oxidation reaction solution concentration, regulate slurry concentration to solid-liquid ratio to be 1.6;
C, suspension oxidation react:
Carry out suspension oxidation reaction in reactor electrolytic metal Mn slurry obtained in step B being placed in aluminum oxide abrasion resistant ceramic tube road, temperature of reaction is 50 DEG C; Stirring velocity is 220r/min; Blast volume is 1.8L/min; Reaction times is 20h;
D, centrifugal drying: obtain trimanganese tetroxide after suspension oxidation has reacted, through cleaning, after adopting centrifugal drying technique to dehydrate, get product, packaging of being tested by finished product.
Not passive metal manganese sheet in the present embodiment adopts DJMnB not passive metal manganese sheet, and DJMnB is the one in electrolytic metal Mn sheet industry standard, and the constituent content in its raw material requires as follows:
Table 1.1DJMnB is the content requirement of each element in passive metal manganese sheet not
After measured, in the trimanganese tetroxide that in the trimanganese tetroxide that obtains of the present embodiment method, the content of selenium, iron, chromium and common art methods obtain, the content balance situation of selenium, iron, chromium is as following table:
The content balance information slip of selenium, iron, chromium in the trimanganese tetroxide product that table 1.2 embodiment 1 is obtained
| Sequence number | Element type | Ordinary skill preparation (unit/%) | Prepared by new technology |
| 1 | Selenium | 0.0015 | 0.0005 |
| 2 | Iron | 0.5 | 0.015 |
| 3 | Chromium | 0.001 | Trace |
After measured, in the trimanganese tetroxide that obtains of the present embodiment method, the content of sulphur, phosphorus, carbon is as follows:
The content of sulphur, phosphorus, carbon in the trimanganese tetroxide product that table 1.3 embodiment 1 is obtained
| Sequence number | Element type | Content (unit/ppm) |
| 1 | Sulphur | 10 |
| 2 | Phosphorus | 5 |
| 3 | Carbon | 15 |
Embodiment 2
The difference of the present embodiment and embodiment 1 is:
Its melting duration is 40 minutes, and smelting temperature is 1350 DEG C;
Also adopt argon shield air ring to protect electrolytic metal Mn sheet in fusion process, prevent it to be oxidized;
Water atomization pressure is regulated to be 400 kilograms; Turndown duration is 12min;
Slurry concentration to solid-liquid ratio is regulated to be 2.0;
The temperature of reaction of suspension oxidation reaction is 70 DEG C; Stirring velocity is 260r/min; Blast volume is 2.2L/min; Reaction times is 24h;
After measured, in the trimanganese tetroxide that in the trimanganese tetroxide that obtains of the present embodiment method, the content of selenium, iron, chromium and common art methods obtain, the content balance situation of selenium, iron, chromium is as following table:
The content balance information slip of selenium, iron, chromium in table 2.1 embodiment 2 trimanganese tetroxide product
| Sequence number | Element type | Ordinary skill preparation (unit/%) | Prepared by new technology |
| 1 | Selenium | 0.0015 | 0.0004 |
| 2 | Iron | 0.5 | 0.015 |
| 3 | Chromium | 0.001 | Trace |
After measured, in the trimanganese tetroxide that obtains of the present embodiment method, the content of sulphur, phosphorus, carbon is as follows:
The content of sulphur, phosphorus, carbon in the trimanganese tetroxide product that table 2.2 embodiment 2 is obtained
| Sequence number | Element type | Content (unit/ppm) |
| 1 | Sulphur | 9 |
| 2 | Phosphorus | 4 |
| 3 | Carbon | 15 |
Embodiment 3
The difference of the present embodiment and embodiment 1 is:
Its melting duration is 38 minutes, and smelting temperature is 1300 DEG C;
Water atomization pressure is regulated to be 350 kilograms; Turndown duration is 11min;
Slurry concentration to solid-liquid ratio is regulated to be 1.8;
The temperature of reaction of suspension oxidation reaction is 60 DEG C; Stirring velocity is 240r/min; Blast volume is 2.0L/min; Reaction times is 22h;
The content balance information slip of selenium, iron, chromium in table 3.1 embodiment 3 trimanganese tetroxide product
| Sequence number | Element type | Ordinary skill preparation (unit/%) | Prepared by new technology |
| 1 | Selenium | 0.0015 | 0.0003 |
| 2 | Iron | 0.5 | 0.012 |
| 3 | Chromium | 0.001 | Trace |
After measured, in the trimanganese tetroxide that obtains of the present embodiment method, the content of sulphur, phosphorus, carbon is as follows:
The content of sulphur, phosphorus, carbon in the trimanganese tetroxide product that table 3.2 embodiment 3 is obtained
| Sequence number | Element type | Content (unit/ppm) |
| 1 | Sulphur | 8 |
| 2 | Phosphorus | 4 |
| 3 | Carbon | 12 |
Embodiment 4
The present embodiment is for adopting the Mn that described in embodiment 1, method is obtained
3o
4for manganese source, solid reaction process is adopted to prepare LiMn
2o
4material, technical process is as follows:
With Mn obtained in above-described embodiment 1
3o
4, Li
2o
3for raw material, take dehydrated alcohol as dispersion agent ground and mixed, after 600 DEG C of pre-burning 6h, as in crucible, then crucible is placed in calcination reaction 30h at retort furnace 750 DEG C, afterwards, 600 DEG C of annealing 6h, can obtain LiM after furnace cooling
n2o
4material.
After measured: obtained LiMn
2o
4material, its D50 is 4.80 μm, and specific surface area is 1.0 ㎡/g, and its crystal grain is regular octahedron and size uniformity, concentrates on about 2.1 μm, with the LiMn prepared with electrolytic manganese dioxide
2o
4compare, its crystal grain is less but size is more homogeneous.
Gained lithium manganate initial discharge specific storage at 25 DEG C and 50 DEG C is 135mAh/g and 136mAh/g, and after 10 circulations, capability retention is 97.8%, 94.9%.
As shown in Figure 2, the characteristic peak of the lithium manganate having spinel structure material of the trimanganese tetroxide synthesis adopting method described in embodiment 1 to obtain is consistent with the standard diagram JCPDS35-0782 of lithium manganate, does not show any impurity peaks.
As shown in Figure 3, the well-regulated spinel structure of lithium manganate material tool of the trimanganese tetroxide synthesis adopting method described in embodiment 1 to obtain.
Above-described embodiment further illustrates of the present invention, instead of limit the scope of the invention.Do not depart from whole technical scope of the present invention, can various amendment and change be carried out.
Claims (10)
1. a preparation method for high-quality trimanganese tetroxide, is characterized in that,
For one with not passivation electrolytic metal Mn sheet for raw material, adopt water atomization prepare electrolytic metal Mn slurry, then electrolytic metal Mn slurry suspension oxidizing reaction is obtained the preparation method of low selenium, low iron, trace chromium high-quality trimanganese tetroxide.
2. the preparation method of a kind of high-quality trimanganese tetroxide according to claim 1, is characterized in that,
Described preparation method specifically comprises the following steps:
The surface treatment of A, not passivation electrolytic metal Mn sheet:
Directly fresh not passivation electrolytic metal Mn sheet is cleaned, dry;
B, employing water atomization prepare electrolytic metal Mn slurry, comprise the steps:
B1, melting technology: dropped in intermediate frequency furnace by the not passivation electrolytic metal Mn sheet after steps A surface treatment and carry out melting, its melting duration is 35-40 minute, and smelting temperature is 1250-1350 DEG C;
B2, water atomization pulping: pour the manganese metal sheet turndown in intermediate frequency furnace after melting into water atomization plant and carry out water atomization process, regulate water atomization pressure to be 300-400 kilogram, turndown duration is 10-12min;
B3, to size mixing: according to the needs of rear end suspension oxidation reaction solution concentration, regulate slurry concentration to solid-liquid ratio to be 1.6-2.0;
C, suspension oxidation react:
Be placed in reactor by electrolytic metal Mn slurry obtained in step B and carry out suspension oxidation reaction, inject ammoniacal liquor and make catalyzer, pass into air, temperature of reaction is 50-70 DEG C; Stirring velocity is 220-260r/min; Blast volume is 1.8-2.2L/min; Reaction times is 20-24h;
D, centrifugal drying: obtain trimanganese tetroxide after suspension oxidation has reacted, through cleaning, after adopting centrifugal drying technique to dehydrate, get product.
3. a kind of preparation method according to claim 2, is characterized in that,
In step B2, water atomization pulping is obtained is more than or equal to 95% by-150 object electrolytic metal Mn slurries.
4. the preparation method of a kind of high-quality trimanganese tetroxide according to claim 2-3 any one, is characterized in that,
Reactor described in step C is ceramic pipeline reactor.
5. the preparation method of a kind of high-quality trimanganese tetroxide according to claim 2-3 any one, is characterized in that,
The slag making also comprising melting in described step B1 melting technology with skim operation, described in skim in operation and adopt slagging agent to carry out slag hitting process, improve melting purity.
6. the preparation method of a kind of high-quality trimanganese tetroxide according to claim 2-3 any one, is characterized in that,
Adopt protection of inert gas air ring to protect electrolytic metal Mn sheet in described step B1 melting technology, prevent it to be oxidized;
Described rare gas element adopts nitrogen or argon gas.
7. the preparation method of a kind of high-quality trimanganese tetroxide according to claim 2-3 any one, is characterized in that,
Described intermediate frequency furnace is 500KG level intermediate frequency furnace.
8. the preparation method of a kind of high-quality trimanganese tetroxide according to claim 2-3 any one, is characterized in that,
In described not passive metal manganese sheet: Mn >=99.9%; C≤0.02%; S≤0.04%; P≤0.002%; Si≤0.004%; Se≤0.001%; Fe≤0.01%.
9. adopt the trimanganese tetroxide that described in claim 1-3 any one, preparation method obtains, it is characterized in that,
Described trimanganese tetroxide product has complete spinel structure, in described trimanganese tetroxide:
Content≤0.0005% of Se element; Content≤0.015% of Fe element; The content of chromium element is trace;
The content of S element is 8-12ppm, the content < 5ppm of P element, the content < 15ppm of C element.
10. one kind adopts the lithium manganate material of the trimanganese tetroxide synthesis that described in claim 1-3 any one, preparation method obtains.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610105839.0A CN105523587B (en) | 2016-02-26 | 2016-02-26 | A kind of preparation method of high-quality mangano-manganic oxide and the product for preparing |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610105839.0A CN105523587B (en) | 2016-02-26 | 2016-02-26 | A kind of preparation method of high-quality mangano-manganic oxide and the product for preparing |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105523587A true CN105523587A (en) | 2016-04-27 |
| CN105523587B CN105523587B (en) | 2017-06-16 |
Family
ID=55766169
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610105839.0A Active CN105523587B (en) | 2016-02-26 | 2016-02-26 | A kind of preparation method of high-quality mangano-manganic oxide and the product for preparing |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105523587B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167584A (en) * | 2019-12-30 | 2020-05-19 | 贵州武陵锰业有限公司 | Manganese ore industrialization wet ball milling method based on electrolytic manganese anolyte |
| CN114772649A (en) * | 2022-04-13 | 2022-07-22 | 贵州大龙汇成新材料有限公司 | Method for preparing mangano-manganic oxide by using lean manganese ore |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445276A (en) * | 2009-01-04 | 2009-06-03 | 上海大学 | Method of producing low selenium and high specific surface area manganomanganic oxide by using carbon-manganese alloy one-step method |
| CN101734723A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Method for preparing nano mangano-manganic oxide micropowder with high specific surface area |
| CN102336441A (en) * | 2011-06-29 | 2012-02-01 | 金瑞新材料科技股份有限公司 | Method for preparing lithium manganate used as lithium ion battery anode material by using trimanganese tetroxide |
| CN103121723A (en) * | 2011-11-21 | 2013-05-29 | 伍宏斌 | Low-calcium-magnesium high-purity manganous-manganic oxide and preparation method for same |
| CN103178256A (en) * | 2011-12-26 | 2013-06-26 | 伍宏斌 | Preparation method of mangano-manganic oxide for lithium-manganese battery |
| CN104803419A (en) * | 2015-02-28 | 2015-07-29 | 四川中哲新材料科技有限公司 | Preparation method of manganous-manganic oxide |
-
2016
- 2016-02-26 CN CN201610105839.0A patent/CN105523587B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101445276A (en) * | 2009-01-04 | 2009-06-03 | 上海大学 | Method of producing low selenium and high specific surface area manganomanganic oxide by using carbon-manganese alloy one-step method |
| CN101734723A (en) * | 2009-12-22 | 2010-06-16 | 上海大学 | Method for preparing nano mangano-manganic oxide micropowder with high specific surface area |
| CN102336441A (en) * | 2011-06-29 | 2012-02-01 | 金瑞新材料科技股份有限公司 | Method for preparing lithium manganate used as lithium ion battery anode material by using trimanganese tetroxide |
| CN103121723A (en) * | 2011-11-21 | 2013-05-29 | 伍宏斌 | Low-calcium-magnesium high-purity manganous-manganic oxide and preparation method for same |
| CN103178256A (en) * | 2011-12-26 | 2013-06-26 | 伍宏斌 | Preparation method of mangano-manganic oxide for lithium-manganese battery |
| CN104803419A (en) * | 2015-02-28 | 2015-07-29 | 四川中哲新材料科技有限公司 | Preparation method of manganous-manganic oxide |
Non-Patent Citations (1)
| Title |
|---|
| 李元元等: "《新型材料科学与技术》", 30 September 2012, 华南理工大学出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111167584A (en) * | 2019-12-30 | 2020-05-19 | 贵州武陵锰业有限公司 | Manganese ore industrialization wet ball milling method based on electrolytic manganese anolyte |
| CN114772649A (en) * | 2022-04-13 | 2022-07-22 | 贵州大龙汇成新材料有限公司 | Method for preparing mangano-manganic oxide by using lean manganese ore |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105523587B (en) | 2017-06-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113912032B (en) | Method for recycling and preparing battery-grade lithium carbonate and ferric phosphate from waste lithium iron phosphate battery positive electrode powder | |
| CN101418370B (en) | Novel industrialization method for comprehensive utilization of vanadium ferrotitanium ore concentrate | |
| CN110482511B (en) | Method for recovering anode material of waste lithium iron phosphate battery | |
| CN102903985A (en) | Method for recycling lithium carbonate from lithium iron phosphate waste material | |
| CN101514395A (en) | Method for recovering lead oxide by waste lead-acid storage battery | |
| CN107082429A (en) | A kind of method that utilization Dust of Iron And Steel Works prepares cementite | |
| CN102534209B (en) | Reduction leaching method of manganese oxide ores | |
| CN109052492A (en) | A method of tertiary cathode material is prepared by lateritic nickel ore leaching solution | |
| CN115583641B (en) | Method for preparing battery-grade ferric phosphate by cooperation of pyrite cinder and waste lithium iron phosphate battery cell | |
| CN113772650B (en) | Preparation method and application of lithium iron phosphate | |
| CN113184821B (en) | Method for preparing ferric phosphate from iron-containing slag | |
| CN103193272B (en) | Method for preparing ammonium paratungstate | |
| CN103911514A (en) | Waste hard alloy grinding material recovery treatment method | |
| CN107090551A (en) | A kind of method of the direct vanadium extraction of vanadium titano-magnetite | |
| CN115849415B (en) | Method for preparing battery grade lithium carbonate | |
| CN102842708A (en) | Manganous-manganic oxide preparation method for battery positive pole material lithium manganate and product thereof | |
| CN114132909A (en) | Method for recycling pure metal salt from retired manganese iron phosphate lithium battery waste | |
| CN105523587A (en) | High-quality trimanganese tetraoxide preparation method and product prepared by same | |
| CN113387387A (en) | Method for preparing sodium tungstate solution by utilizing tungsten-containing waste in short process | |
| CN101698513A (en) | Method for preparing high-purity trimanganese tetroxide | |
| CN108275714B (en) | Method for producing feed-grade zinc oxide by sodium chloride-ammonia combined leaching | |
| CN106350680B (en) | A method of sodium roasting extracts valuable metal from oil burnning ash | |
| CN115744851A (en) | Method for recycling and preparing battery-grade iron phosphate | |
| CN116216797A (en) | Method for preparing lithium ion battery anode material by recycling waste lithium battery dismantling black powder and anode powder | |
| CN114204021B (en) | Preparation method of low-cost lithium iron manganese phosphate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |