CN115744994B - Preparation method of battery-grade manganous-manganic oxide - Google Patents
Preparation method of battery-grade manganous-manganic oxide Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 36
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 207
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 claims abstract description 78
- 238000006243 chemical reaction Methods 0.000 claims abstract description 62
- 229940099596 manganese sulfate Drugs 0.000 claims abstract description 54
- 239000011702 manganese sulphate Substances 0.000 claims abstract description 54
- 235000007079 manganese sulphate Nutrition 0.000 claims abstract description 54
- 239000000725 suspension Substances 0.000 claims abstract description 43
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 29
- 239000011572 manganese Substances 0.000 claims abstract description 25
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 24
- 238000001556 precipitation Methods 0.000 claims abstract description 24
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 16
- 239000011593 sulfur Substances 0.000 claims abstract description 16
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims abstract 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 34
- 238000001914 filtration Methods 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 23
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 22
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 20
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- 239000012298 atmosphere Substances 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- 230000001681 protective effect Effects 0.000 claims description 15
- 238000005406 washing Methods 0.000 claims description 11
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 6
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 31
- 239000002245 particle Substances 0.000 abstract description 22
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract description 17
- 230000003647 oxidation Effects 0.000 abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 12
- 238000009826 distribution Methods 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 11
- 229910052748 manganese Inorganic materials 0.000 abstract description 11
- 239000000463 material Substances 0.000 abstract description 8
- 239000002244 precipitate Substances 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 81
- ISPYRSDWRDQNSW-UHFFFAOYSA-L manganese(II) sulfate monohydrate Chemical compound O.[Mn+2].[O-]S([O-])(=O)=O ISPYRSDWRDQNSW-UHFFFAOYSA-L 0.000 description 58
- 239000008367 deionised water Substances 0.000 description 28
- 229910021641 deionized water Inorganic materials 0.000 description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000007787 solid Substances 0.000 description 14
- 238000005303 weighing Methods 0.000 description 14
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 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 description 10
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 239000002994 raw material Substances 0.000 description 9
- 238000001035 drying Methods 0.000 description 7
- 238000004537 pulping Methods 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 230000001105 regulatory effect Effects 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000012798 spherical particle Substances 0.000 description 5
- 239000010405 anode material Substances 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 230000002349 favourable effect Effects 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002696 manganese Chemical class 0.000 description 2
- 239000011565 manganese chloride Substances 0.000 description 2
- 235000002867 manganese chloride Nutrition 0.000 description 2
- 229940099607 manganese chloride Drugs 0.000 description 2
- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 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
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 150000002697 manganese compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
-
- 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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- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of battery-grade manganous-manganic oxide, which comprises the following steps: adding a manganese sulfate solution into a sodium hydroxide solution for precipitation reaction to obtain manganese hydroxide; preparing manganese hydroxide into manganese hydroxide suspension; and adding the manganese hydroxide suspension into a sodium hydroxide solution for oxidation reaction to obtain the battery-grade manganous-manganic oxide. According to the preparation method, firstly, manganese hydroxide precipitate is generated by reaction under the strong alkaline condition, and then oxidation is carried out, so that the generation of basic manganese sulfate is avoided, the sulfur content and other soluble impurity content in a trimanganese tetroxide product are greatly reduced, and the prepared trimanganese tetroxide has the advantages of low preparation cost, high purity, proper particle size distribution, small specific surface area, high density and the like, is a novel and high-quality manganese source material capable of remarkably improving the electrochemical performance of lithium manganate, and has the advantages of high use value, good application prospect, easiness in controlling the reaction condition, no pollution to the operating environment and the like.
Description
Technical Field
The invention belongs to the technical field of manganese compound preparation, relates to a preparation method of battery-grade manganous oxide, and in particular relates to a preparation method of battery-grade manganous oxide for lithium manganate.
Background
The lithium manganate serving as one of the lithium ion battery anode materials has the advantages of rich resources, simple production process, relatively low price, good low-temperature performance and safety, is one of the ideal lithium battery anode materials at present, and is widely applied to the fields of 3C numbers, electric tools, electric bicycles, electric automobiles and the like.
Physical and chemical indexes such as morphology, particle size distribution, purity and the like of the manganese source precursor seriously influence the electrochemical performance of lithium manganate. For example, lithium manganate produced by using electrolytic manganese dioxide as a precursor has the problems of low capacity, poor cycle performance, poor high-temperature performance and the like, which are mainly caused by irregular morphology, uneven particle size distribution, large specific surface area and high impurity content of the electrolytic manganese dioxide. The high-performance lithium manganate positive electrode material is prepared by a special precursor, and the trimanganese tetroxide is a high-quality manganese source material for preparing the lithium manganate positive electrode material due to a special crystal structure, because the trimanganese tetroxide synthesized by a liquid phase has regular spherical shape, small specific surface area and low impurity content, and the trimanganese tetroxide and the lithium manganate are of spinel structures, in the process of preparing spinel lithium manganate by using the trimanganese tetroxide, the phase structure change is small, the internal stress is less, the material structure is more stable, and the capacity and the cycle performance are greatly improved compared with those of lithium manganate produced by taking electrolytic manganese dioxide as a raw material.
At present, the method for producing the battery-grade manganous oxide in the industry mainly comprises a metal manganese oxidation method and a manganese sulfate solution oxidation method, wherein the metal manganese oxidation method takes electrolytic metal manganese sheets as raw materials, firstly, the metal manganese sheets are crushed into suspension, and air oxidation is utilized to prepare the manganous oxide. The method has the advantages of simple process, convenient operation, large yield and high yield, but the electrolytic manganese metal raw material is expensive, the obtained product has high content of manganous manganic oxide impurities, high magnetic substance and poor sphericity of particle morphology, and can not meet the requirements of high-end lithium manganate anode materials; in addition, the metal manganese contains selenium, and the prepared manganous-manganic oxide volatilizes out at high temperature in the process of synthesizing lithium manganate, so that certain influence is caused on the operation environment.
The manganese sulfate solution oxidation process to produce manganous oxide includes adding ammonia water, sodium hydroxide or other alkaline solution into manganese sulfate solution to react or adding manganese sulfate solution and alkaline solution into reactor to react to produce manganese hydroxide precipitate, and oxidizing manganese hydroxide precipitate into manganous oxide with air. In addition, ammonia water is required to be added in the oxidation reaction process to keep the pH stable, and the ammonia is discharged along with air in the reaction process, so that the pH stability is difficult to keep, the operation environment is influenced, and the problem of environmental pollution exists.
Therefore, a preparation method of battery-grade manganous-manganic oxide with low preparation cost, high purity, spherical particles, proper particle size distribution, small specific surface area and high density is developed, and has important significance for promoting wide application of the manganous-manganic oxide as a high-quality manganese source material of lithium manganate and remarkably improving electrochemical performance of the lithium manganate.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the preparation method of the battery-grade manganese tetraoxide, which has the advantages of low preparation cost, high purity, spherical particles, proper particle size distribution, small specific surface area and high density.
In order to solve the technical problems, the invention adopts the following technical scheme:
the preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
(1) Adding a manganese sulfate solution into a sodium hydroxide solution for precipitation reaction to obtain manganese hydroxide;
(2) Preparing manganese hydroxide into manganese hydroxide suspension;
(3) And adding the manganese hydroxide suspension into a sodium hydroxide solution for oxidation reaction to obtain the battery-grade manganous-manganic oxide.
The above-mentioned production method, further improved, wherein in the above (1), the Mn in the manganese sulfate solution 2+ With OH in sodium hydroxide solution - The mol ratio of (2) is 1:2.02-2.10.
The above-mentioned production method, further improved, wherein in the above (1), the Mn in the manganese sulfate solution 2+ The concentration of (2) is 0.5 mol/L-1.5 mol/L; the manganese sulfate solution is prepared by dissolving manganese sulfate in water; the purity of the manganese sulfate is more than 99.5%; the concentration of the sodium hydroxide solution is 0.5 mol/L-2.0 mol/L; the sodium hydroxide solution is prepared by dissolving sodium hydroxide in water; the purity of the sodium hydroxide is more than 99.5 percent.
In the above preparation method, further improved, in the step (1), the precipitation reaction is carried out at a temperature of 10℃to 90 ℃.
In the above preparation method, further improvement, in the step (1), the precipitation reaction is performed under a protective atmosphere, and the protective atmosphere is a nitrogen atmosphere. The precipitation reaction further comprises the following treatment after completion: and filtering and washing the reaction product under a protective atmosphere to obtain manganese hydroxide, wherein the protective atmosphere is a nitrogen atmosphere.
In the preparation method, the concentration of the manganese hydroxide suspension in the step (2) is 20g/L to 120g/L; the preparation method of the manganese hydroxide suspension comprises the following steps: mixing manganese hydroxide with water, and stirring to obtain manganese hydroxide suspension; the preparation of the manganese hydroxide suspension is carried out under a protective atmosphere; the protective atmosphere is nitrogen atmosphere.
In the above preparation method, further improved, in the step (3), the oxidation reaction is performed at a temperature of 30 to 70 ℃; the oxidation reaction process also comprises the step of introducing air into the reaction system, wherein the flow rate of the air is 1L/min-5L/min.
In the above preparation method, further improved, in the step (3), the pH value of the sodium hydroxide solution is 7 to 9.
In the preparation method, further improved, in the step (3), the manganese hydroxide suspension is fed within 15-30 hours; the reaction was continued for 2 hours after the addition of the manganese hydroxide suspension was completed.
In the above preparation method, further improved, in the step (3), the battery grade manganous-manganic oxide is spherical; the specific surface area of the battery grade manganous oxide is less than 0.5m 2 /g; the mass content of Mn in the battery-level manganous-manganic oxide is more than 71%; the mass content of sulfur and sodium in the battery-grade manganous oxide is less than 50ppm.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the problems of high preparation cost and product in the existing technique for producing the manganous manganic oxide by using the manganese sulfate solution oxidation methodThe invention creatively provides a preparation method of battery-grade manganous oxide, which comprises the steps of adding a manganese sulfate solution into a sodium hydroxide solution, reacting under a strong alkaline condition to generate manganese hydroxide precipitate, avoiding the generation of basic manganese sulfate, greatly reducing the sulfur content in the product, washing and filtering, further reducing soluble impurities (such as sodium ions), thereby obtaining high-purity manganese hydroxide, further preparing the high-purity manganese hydroxide into suspension, adding the suspension into the sodium hydroxide solution, carrying out oxidation reaction under the alkaline condition, further avoiding the generation of basic manganese sulfate, further facilitating the generation of high-purity manganous oxide, and simultaneously facilitating the generation of compact spherical manganous oxide particles with proper particle size distribution by adjusting the reaction time and the reaction temperature, wherein the specific surface area of the battery-grade manganous oxide is smaller than 0.5m 2 And/g, mn content is more than 71% by mass, and sulfur and sodium content are both less than 50ppm by mass. In addition, manganese sulfate is used as a raw material, so that the manganese sulfate has the advantages of wide source, low price and the like, and impurities are easy to introduce when other manganese salts are used as raw materials, for example, when chloride ions contained in manganese chloride are introduced into a battery, the battery is adversely affected. Therefore, the preparation method of the invention firstly generates manganese hydroxide precipitate under the strong alkaline condition, and then oxidizes, thereby avoiding the generation of basic manganese sulfate, greatly reducing the sulfur content and other soluble impurity content in the manganous manganic oxide product, and the prepared manganous manganic oxide has the advantages of low preparation cost, high purity, spherical particles, proper particle size distribution, small specific surface area, high density and the like, and is a novel and high-quality manganese source material capable of obviously improving the electrochemical performance of lithium manganate, and has high use value and good application prospect.
(2) In the invention, the manganese hydroxide suspension is added into the sodium hydroxide solution with the pH value of 7-9, compared with the existing preparation method which takes ammonia water as an alkaline solvent, the preparation method has the following advantages: the pH value is stable and cannot change as the reaction continues to progress; no other auxiliary agent is needed, the process condition is simple and easy to control, the product quality is stable, and the operating environment is pollution-free. In addition, compared with potassium hydroxide solution, when sodium hydroxide solution is used as alkaline solution, the prepared manganous manganic oxide product is more suitable to be used as a raw material of lithium manganate anode material to obtain a battery with more excellent performance.
(3) In the invention, in the process of preparing manganese hydroxide, mn in the manganese sulfate solution is optimized 2+ With OH in sodium hydroxide solution - The molar ratio of (2) to (2.02) to (2.10) is 1:2, so that the Mn can be ensured by slightly excessive sodium hydroxide 2+ The precipitation reaction is always carried out under the strong alkaline condition, so that the generation of basic salt is effectively avoided, and excessive cost is not increased at the moment. In addition, the manganese sulfate and the sodium hydroxide with high purity (more than 99.5%) are used as raw materials, so that the introduction of impurities can be further avoided, the preparation of the manganese hydroxide with higher purity is facilitated, and the further improvement of the purity of the manganous-manganic oxide product is facilitated.
(4) In the process of preparing manganese hydroxide, nitrogen is used as a protective gas, and after the precipitation reaction is finished, the reaction product is continuously filtered and washed under the protective atmosphere, so that the manganese hydroxide can be prevented from being oxidized into manganese dioxide or other manganese oxides such as manganese sesquioxide, and the purity of the manganous oxide product is improved.
(5) In the invention, the concentration of the manganese hydroxide suspension is optimized to be 20 g/L-120 g/L, which is favorable for improving the utilization rate of manganese hydroxide reaction equipment and further favorable for obtaining compact spherical manganous manganic oxide particles with proper particle size distribution, because when the concentration of the suspension is too high, the material is sticky and difficult to disperse, not only is not favorable for conveying and metering, but also is difficult to obtain a manganous oxide product with ideal morphology and particle size distribution, and when the concentration is too low, the equipment utilization rate is low and the cost is increased. In addition, the preparation of the manganese hydroxide suspension is carried out under a protective atmosphere, so that manganese hydroxide can be prevented from being oxidized into manganese dioxide or other manganese oxides such as manganese sesquioxide, and the purity of the manganous manganic oxide product can be improved.
(6) In the process of preparing the manganous-manganic oxide, the temperature of the oxidation reaction is optimized to be 30-70 ℃, so that the spherical manganous-manganic oxide product with compact surface can be obtained. In addition, the oxidation reaction process also comprises the step of introducing air into the reaction system, and the flow rate of the air is optimized to be 1L/min-5L/min, so that the oxidation process is ensured to contain enough oxygen, namely, when the flow rate is too small, the oxidation is insufficient, and when the flow rate is too large, the energy consumption cost is increased. In addition, the manganese hydroxide suspension is fed within 15-30 hours, and the particle size of the manganese tetraoxide product can be adjusted, so that the manganese tetraoxide spherical particles with proper particle size can be obtained more easily, further, the reaction is continued for 2 hours after the feeding of the manganese hydroxide suspension is finished, the growth and the balling of small particles are facilitated, the sphericity of the manganese tetraoxide particles is improved, and the agglomeration of the small particles is avoided.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Fig. 1 is an SEM image of battery grade trimanganese tetroxide prepared in example 1 of the present invention at various magnifications.
Fig. 2 is a particle size distribution diagram of battery grade trimanganese tetroxide prepared in example 1 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
In the following examples, materials and instruments used are commercially available unless otherwise specified. The process adopted is a conventional process, the equipment adopted is a conventional equipment, and the obtained data are all average values of more than three repeated experiments.
Example 1
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with main content of more than 99.5%, dissolving with deionized water to prepare 10L manganese sulfate solution with concentration of 0.5mol/L, standing, and passingFiltering to obtain pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare 10.1L sodium hydroxide solution with the concentration of 1.0mol/L, standing and filtering to obtain pure sodium hydroxide solution; adding a manganese sulfate solution into a sodium hydroxide solution under the condition of stirring in a nitrogen atmosphere for precipitation reaction at the reaction temperature of 50 ℃, and filtering and washing after the precipitation reaction is completed to obtain manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 50 g/L; under the nitrogen atmosphere, deionized water is firstly added into a reactor, the mixture is stirred and heated to 70 ℃, the pH value is regulated to 8.5 by a sodium hydroxide solution, the manganese hydroxide suspension is slowly added by a metering pump, meanwhile, air is introduced for oxidation, the reaction temperature is kept at 70 ℃, the charging time is 20 hours, the air flow is 3L/min, and the reaction is continued for 2 hours after the charging is completed; and rinsing, filtering and drying after the reaction is finished to obtain the battery-grade manganese tetraoxide product.
Tested: as shown in fig. 1 and 2, the battery grade trimanganese tetroxide product prepared in example 1 of the present invention has a regular spherical morphology, and the average particle size of the product is 9.37 μm. In addition, the specific surface area of the battery grade manganous-manganic oxide product is 0.46m 2 The mass content of Mn per gram was 71.35%, the mass content of sulfur was 42ppm, and the mass content of Na was 34ppm.
Example 2
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with the main content of more than 99.5%, dissolving the high-purity manganese sulfate monohydrate with deionized water to prepare a manganese sulfate solution with the concentration of 5L and 1.0mol/L, standing and filtering to obtain a pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare a sodium hydroxide solution with the concentration of 2.0mol/L and 5.25L, standing and filtering the solution to obtain a pure sodium hydroxide solution; adding manganese sulfate solution into sodium hydroxide solution under nitrogen atmosphere and stirring condition for precipitation reaction at 70deg.C, filtering and washing to obtain the final productTo manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 80 g/L; under the nitrogen atmosphere, deionized water is firstly added into a reactor, the mixture is stirred and heated to 50 ℃, the pH value is regulated to 7.5 by a sodium hydroxide solution, the manganese hydroxide suspension is slowly added by a metering pump, meanwhile, air is introduced for oxidation, the reaction temperature is kept at 50 ℃, the charging time is 18 hours, the air flow is 2L/min, and the reaction is continued for 2 hours after the charging is completed; and rinsing, filtering and drying after the reaction is finished to obtain the battery-grade manganese tetraoxide product. The test shows that the average grain diameter of the product is 9.81 mu m, the appearance is regular sphere, and the specific surface area is 0.42m 2 Per g, mn content was 71.23% by mass, sulfur content was 46ppm by mass, na content was 21ppm by mass.
Example 3
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with the main content of more than 99.5%, dissolving the high-purity manganese sulfate monohydrate with deionized water to prepare a manganese sulfate solution with the concentration of 3.33L and 1.5mol/L, standing and filtering to obtain a pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare 8.46L sodium hydroxide solution with the concentration of 1.2mol/L, standing and filtering to obtain pure sodium hydroxide solution; adding a manganese sulfate solution into a sodium hydroxide solution under the condition of stirring in a nitrogen atmosphere for precipitation reaction at the reaction temperature of 10 ℃, and filtering and washing after the precipitation reaction is completed to obtain manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 20g/L; under the nitrogen atmosphere, deionized water is firstly added into a reactor, the mixture is stirred and heated to 65 ℃, the pH value is regulated to 7.0 by a sodium hydroxide solution, the manganese hydroxide suspension is slowly added by a metering pump, air is simultaneously introduced for oxidation, the reaction temperature is kept at 65 ℃, the charging time is 15 hours, the air flow is 5L/min, and the reaction is continued for 2 hours after the charging is completed; rinsing, filtering and drying after the reaction is completed to obtain a battery level fourA manganese oxide product. The test shows that the average grain diameter of the product is 9.68 mu m, the appearance is regular sphere, and the specific surface area is 0.37m 2 The mass content of Mn per gram was 71.60%, the mass content of sulfur was 45ppm, and the mass content of Na was 35ppm.
Example 4
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with the main content of more than 99.5%, dissolving the high-purity manganese sulfate monohydrate with deionized water to prepare a manganese sulfate solution with the concentration of 4.17L and 1.2mol/L, standing and filtering the solution to obtain a pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare a sodium hydroxide solution with the concentration of 6.27L and 1.5mol/L, standing and filtering to obtain a pure sodium hydroxide solution; adding a manganese sulfate solution into a sodium hydroxide solution under the condition of stirring in a nitrogen atmosphere for precipitation reaction at the reaction temperature of 60 ℃, and filtering and washing after the precipitation reaction is completed to obtain manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 70 g/L; under the nitrogen atmosphere, deionized water is firstly added into a reactor, the mixture is stirred and heated to 30 ℃, the pH value is regulated to 9.0 by a sodium hydroxide solution, the manganese hydroxide suspension is slowly added by a metering pump, meanwhile, air is introduced for oxidation, the reaction temperature is kept at 30 ℃, the charging time is 30 hours, the air flow is 1L/min, and the reaction is continued for 2 hours after the charging is completed; and rinsing, filtering and drying after the reaction is finished to obtain the battery-grade manganese tetraoxide product. The test shows that the average grain diameter of the product is 12.61 mu m, the appearance is regular sphere, and the specific surface area is 0.39m 2 Per g, mn content was 71.28% by mass, sulfur content was 38ppm by mass, na content was 41ppm by mass.
Example 5
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with the main content of more than 99.5%, dissolving with deionized water to prepare 6.25L manganese sulfate solution with the concentration of 0.8mol/L, standing, and filteringObtaining pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare a sodium hydroxide solution with the concentration of 0.5mol/L and 20.8L, standing and filtering the solution to obtain a pure sodium hydroxide solution; adding a manganese sulfate solution into a sodium hydroxide solution under the condition of stirring in a nitrogen atmosphere for precipitation reaction at the reaction temperature of 80 ℃, and filtering and washing after the precipitation reaction is completed to obtain manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 120g/L; firstly adding deionized water into a reactor, stirring, heating to 40 ℃, adjusting the pH value to 8.5 by using a sodium hydroxide solution, slowly adding the manganese hydroxide suspension by using a metering pump, simultaneously introducing air for oxidation, keeping the reaction temperature at 40 ℃, adding for 26 hours, and continuing to react for 2 hours after the addition is completed, wherein the air flow is 3L/min; and rinsing, filtering and drying after the reaction is finished to obtain the battery-grade manganese tetraoxide product. The test shows that the average grain diameter of the product is 11.24 mu m, the appearance is regular sphere, and the specific surface area is 0.31m 2 Per g, mn is 71.38% by mass, sulfur is 35ppm by mass, na is 37ppm by mass.
Example 6
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with the main content of more than 99.5%, dissolving the high-purity manganese sulfate monohydrate with deionized water to prepare a manganese sulfate solution with the concentration of 5L and 1.0mol/L, standing and filtering to obtain a pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare 12.7L sodium hydroxide solution with the concentration of 0.8mol/L, standing and filtering to obtain pure sodium hydroxide solution; adding a manganese sulfate solution into a sodium hydroxide solution under the condition of stirring in a nitrogen atmosphere for precipitation reaction at the reaction temperature of 90 ℃, and filtering and washing after the precipitation reaction is completed to obtain manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 100 g/L; under nitrogen atmosphereUnder the atmosphere, deionized water is firstly added into a reactor, the mixture is stirred and heated to 60 ℃, the pH value is regulated to 8.0 by a sodium hydroxide solution, the manganese hydroxide suspension is slowly added by a metering pump, air is simultaneously introduced for oxidation, the reaction temperature is kept at 60 ℃, the charging time is 24 hours, the air flow is 2L/min, and the reaction is continued for 2 hours after the charging is completed; and rinsing, filtering and drying after the reaction is finished to obtain the battery-grade manganese tetraoxide product. The test shows that the average grain diameter of the product is 9.53 mu m, the appearance is regular sphere, and the specific surface area is 0.48m 2 Per g, mn content was 71.40% by mass, sulfur content was 47ppm by mass, na content was 28ppm by mass.
Example 7
The preparation method of the battery-grade manganous-manganic oxide comprises the following steps:
weighing high-purity manganese sulfate monohydrate with the main content of more than 99.5%, dissolving the high-purity manganese sulfate monohydrate with deionized water to prepare 10L of manganese sulfate solution with the concentration of 0.5mol/L, standing and filtering to obtain pure manganese sulfate solution; weighing solid sodium hydroxide with the main content of more than 99.5%, dissolving the solid sodium hydroxide with deionized water to prepare 8.54L sodium hydroxide solution with the concentration of 1.2mol/L, standing and filtering to obtain pure sodium hydroxide solution; adding a manganese sulfate solution into a sodium hydroxide solution under the condition of stirring in a nitrogen atmosphere for precipitation reaction at the reaction temperature of 30 ℃, and filtering and washing after the precipitation reaction is completed to obtain manganese hydroxide; stirring and pulping the filtered and washed manganese hydroxide by deionized water in a closed container filled with nitrogen to prepare Mn (OH) 2 A manganese hydroxide suspension having a concentration of 40 g/L; under the nitrogen atmosphere, deionized water is firstly added into a reactor, the mixture is stirred and heated to 50 ℃, the pH value is regulated to 8.5 by a sodium hydroxide solution, the manganese hydroxide suspension is slowly added by a metering pump, meanwhile, air is introduced for oxidation, the reaction temperature is kept at 50 ℃, the charging time is 22 hours, the air flow is 3L/min, and the reaction is continued for 2 hours after the charging is completed; and rinsing, filtering and drying after the reaction is finished to obtain the battery-grade manganese tetraoxide product. The test shows that the product has average grain size of 9.07 μm, regular sphere shape and specific surface area of 0.35m 2 Per g, mn content of 71.43% by mass, sulfur content of 39ppm by mass, naThe mass content of (2) was 45ppm.
From the above results, it is apparent that the preparation method of the battery grade manganous oxide according to the present invention can prevent the generation of basic manganese sulfate by adding a manganese sulfate solution into a sodium hydroxide solution to react under a strong alkaline condition to generate a manganese hydroxide precipitate, thereby greatly reducing the sulfur content in the product, further reducing soluble impurities (such as sodium ions) after washing and filtering, thereby obtaining high purity manganous hydroxide, further, preparing the high purity manganous hydroxide into a suspension and adding the suspension into a sodium hydroxide solution, performing an oxidation reaction under the alkaline condition, further preventing the generation of basic manganese sulfate, thereby facilitating the obtaining of high purity manganous oxide, and simultaneously performing an oxidation reaction under the alkaline condition, and facilitating the obtaining of compact spherical manganous oxide particles with proper particle size distribution by adjusting the reaction time and the reaction temperature, wherein the specific surface area of the battery grade manganous oxide is less than 0.5m 2 And/g, mn content is more than 71% by mass, and sulfur and sodium content are both less than 50ppm by mass. In addition, manganese sulfate is used as a raw material, so that the manganese sulfate has the advantages of wide source, low price and the like, and impurities are easy to introduce when other manganese salts are used as raw materials, for example, when chloride ions contained in manganese chloride are introduced into a battery, the battery is adversely affected. Therefore, the preparation method of the invention firstly generates manganese hydroxide precipitate under the strong alkaline condition, and then oxidizes, thereby avoiding the generation of basic manganese sulfate, greatly reducing the sulfur content and other soluble impurity content in the manganous manganic oxide product, and the prepared manganous manganic oxide has the advantages of low preparation cost, high purity, spherical particles, proper particle size distribution, small specific surface area, high density and the like, and is a novel and high-quality manganese source material capable of obviously improving the electrochemical performance of lithium manganate, and has high use value and good application prospect.
The present invention is disclosed in the preferred embodiments, but is not limited thereto. Many variations and modifications of the present invention will be apparent to those skilled in the art, using the methods and techniques disclosed above. Therefore, any simple modification of the above embodiments according to the technical substance of the present invention is still within the scope of the technical solution of the present invention, without departing from the technical solution of the present invention.
Claims (5)
1. The preparation method of the battery-grade manganous-manganic oxide is characterized by comprising the following steps of:
(1) Adding a manganese sulfate solution into a sodium hydroxide solution for precipitation reaction to obtain manganese hydroxide; mn in the manganese sulfate solution 2+ With OH in sodium hydroxide solution - The mol ratio of (2) is 1:2.02-2.10; the precipitation reaction is carried out at a temperature of 10-90 ℃; the precipitation reaction is carried out under a protective atmosphere;
(2) Preparing manganese hydroxide into manganese hydroxide suspension; the concentration of the manganese hydroxide suspension is 20 g/L-120 g/L;
(3) Adding the manganese hydroxide suspension into a sodium hydroxide solution with the pH value of 7-9 for oxidation reaction to obtain battery-grade manganous-manganic oxide; the oxidation reaction is carried out at a temperature of 30-70 ℃; the oxidation reaction process also comprises the step of introducing air into the reaction system, wherein the flow rate of the air is 1L/min-5L/min; the manganese hydroxide suspension is fed within 15-30 hours; continuing to react for 2 hours after the addition of the manganese hydroxide suspension is completed; the battery-level manganous-manganic oxide is spherical; the specific surface area of the battery grade manganous oxide is less than 0.5m 2 /g。
2. The method according to claim 1, wherein in (1), mn in the manganese sulfate solution 2+ The concentration of (2) is 0.5 mol/L-1.5 mol/L; the manganese sulfate solution is prepared by dissolving manganese sulfate in water; the purity of the manganese sulfate is more than 99.5%; the concentration of the sodium hydroxide solution is 0.5 mol/L-2.0 mol/L; the sodium hydroxide solution is prepared by dissolving sodium hydroxide in water; the purity of the sodium hydroxide is more than 99.5 percent.
3. The production method according to claim 2, wherein in (1), the protective atmosphere is a nitrogen atmosphere; the precipitation reaction further comprises the following treatment after completion: and filtering and washing the reaction product under a protective atmosphere to obtain manganese hydroxide, wherein the protective atmosphere is a nitrogen atmosphere.
4. A production method according to any one of claims 1 to 3, wherein in (2), the production method of the manganese hydroxide suspension comprises the steps of: mixing manganese hydroxide with water, and stirring to obtain manganese hydroxide suspension; the preparation of the manganese hydroxide suspension is carried out under a protective atmosphere; the protective atmosphere is nitrogen atmosphere.
5. The production method according to claim 1, wherein in (3), the mass content of Mn in the battery-grade trimanganese tetroxide is more than 71%; the mass content of sulfur and sodium in the battery-grade manganous oxide is less than 50ppm.
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| JP2001114521A (en) * | 1999-08-10 | 2001-04-24 | Tanaka Chemical Corp | Trimanganese tetraoxide and method for its production |
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| CN101898797A (en) * | 2010-08-04 | 2010-12-01 | 湖南汇通科技有限责任公司 | High-purity trimanganese tetroxide and preparation method thereof |
| CN103172117A (en) * | 2013-03-15 | 2013-06-26 | 英德佳纳金属科技有限公司 | Method for preparing mangano-manganic oxide by liquid phase oxidation |
| CN105417585A (en) * | 2015-12-24 | 2016-03-23 | 湖南海利高新技术产业集团有限公司 | Preparation method of heavy manganous manganic oxide |
| CN107709243A (en) * | 2015-06-22 | 2018-02-16 | 普瑞斯伊诺康私人有限责任公司 | High-purity birnessite and preparation method thereof |
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| JP2001114521A (en) * | 1999-08-10 | 2001-04-24 | Tanaka Chemical Corp | Trimanganese tetraoxide and method for its production |
| CN101700911A (en) * | 2009-07-23 | 2010-05-05 | 深圳市东江环保股份有限公司 | Method for preparing manganous-manganic oxide by manganese sulphate solution |
| CN101898797A (en) * | 2010-08-04 | 2010-12-01 | 湖南汇通科技有限责任公司 | High-purity trimanganese tetroxide and preparation method thereof |
| CN103172117A (en) * | 2013-03-15 | 2013-06-26 | 英德佳纳金属科技有限公司 | Method for preparing mangano-manganic oxide by liquid phase oxidation |
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