CN115959710A - Preparation method of battery-grade manganese sesquioxide and product thereof - Google Patents
Preparation method of battery-grade manganese sesquioxide and product thereof Download PDFInfo
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- TYTHZVVGVFAQHF-UHFFFAOYSA-N manganese(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Mn+3].[Mn+3] TYTHZVVGVFAQHF-UHFFFAOYSA-N 0.000 title claims abstract description 53
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 77
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 53
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002002 slurry Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 239000012670 alkaline solution Substances 0.000 claims abstract description 17
- 230000001590 oxidative effect Effects 0.000 claims abstract description 17
- 230000033116 oxidation-reduction process Effects 0.000 claims abstract description 16
- 239000000725 suspension Substances 0.000 claims abstract description 16
- 239000007800 oxidant agent Substances 0.000 claims abstract description 15
- 239000003054 catalyst Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims abstract description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 33
- 239000011572 manganese Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 10
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000012752 auxiliary agent Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 5
- 229920000058 polyacrylate Polymers 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 4
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims description 4
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 claims description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 229920002125 Sokalan® Polymers 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- XYXNTHIYBIDHGM-UHFFFAOYSA-N ammonium thiosulfate Chemical compound [NH4+].[NH4+].[O-]S([O-])(=O)=S XYXNTHIYBIDHGM-UHFFFAOYSA-N 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004584 polyacrylic acid Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- 238000009826 distribution Methods 0.000 abstract description 5
- 230000007547 defect Effects 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 9
- 238000005086 pumping Methods 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 238000006555 catalytic reaction Methods 0.000 description 5
- 239000007774 positive electrode material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003301 hydrolyzing effect Effects 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 239000002912 waste gas Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 150000002696 manganese Chemical class 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of battery-grade manganese sesquioxide and a product thereof, relates to the technical field of manganese sesquioxide preparation, and aims to solve the problems that the existing preparation method of battery-grade manganese sesquioxide has more defects; the invention comprises using electrolytic manganese metal as raw material, acid as catalyst, adopting manganese metal suspension to hydrolyze and oxidize to prepare manganese sesquioxide; adding an oxidant in the reaction process, and controlling the oxidation-reduction potential of the reaction; adding an alkaline solution in the reaction process, and controlling the reaction pH; manganese sesquioxide slurry is prepared after reaction, and a manganese sesquioxide product is obtained after washing and drying, wherein the purity of the prepared product is more than 99 percent, the median particle size of the manganese sesquioxide is 3-20um, and the tap density is 1.8-2.8g/cm 3 (ii) a The method has the advantages of simple and easily controlled process, easy industrial implementation, and the manganese sesquioxide product obtained by production has the advantages of high purity, regular appearance, good dispersibility, uniform particle size distribution, high tap density and good product consistency.
Description
Technical Field
The invention relates to the technical field of manganese sesquioxide preparation, in particular to a preparation method of battery-grade manganese sesquioxide and a product thereof.
Background
Oxides of manganese are an important class of transition metal oxide materials, generally have variable valence states, and have very wide application in the fields of magnetism, catalysis, environmental protection and electrochemistry. The manganese sesquioxide is used as an important inorganic functional material, has the characteristics of low price, environmental friendliness and the like, plays an important role in modern industry, and can be used for removing carbon monoxide and nitrogen oxide in waste gas in the field of environmental protection due to high catalytic activity; in the preparation of semiconductors, manganese sesquioxide is used to remove organic matter from waste gas; can also be used for improving the thermal stability of the piezoelectric ceramics; in addition, the manganese-based positive electrode material can be synthesized with lithium salt through a solid-phase reaction, and is one of the materials with application prospects in the positive electrode active material of the lithium ion battery.
Lithium manganate is used as one of four commercial positive electrode materials, has the advantages of rich resources, low cost, no pollution, good safety, high multiplying power and the like, and is widely applied to the fields of 3C digital codes, electric tools, electric bicycles, electric automobile batteries and the like. After the new national standard ' safety technical specification ' of electric bicycles is implemented, the process of changing lead into lithium ' in the electric bicycle market can be greatly accelerated, and the application ratio of the lithium manganate material to the electric bicycle can be increased year by virtue of the cost performance advantage of the lithium manganate material, so that the market demand of the lithium manganate material is greatly increased, and meanwhile, higher requirements are brought to the performance of the lithium manganate material.
The manganese source used in the mass production of lithium manganate in the center of the prior art is mainly Electrolytic Manganese Dioxide (EMD), but the EMD is irregular in appearance, so that the lithium manganate is difficult to dope or coat and modify in the preparation process, and the synthesized lithium manganate is low in performance and difficult to meet the medium-high-end market demands of electric tools, electric bicycles, electric automobiles and the like. The spherical manganese sesquioxide has the advantages of high purity, good reaction activity, low raw material cost and the like, and is a good manganese source for synthesizing a high-performance lithium manganate positive electrode material. In addition, as novel manganese-based positive electrode materials such as lithium iron manganese phosphate, lithium nickel manganese oxide, lithium-rich manganese base and sodium ion battery layered oxide gradually enter the industrial development stage, the market demand of battery-grade manganese sesquioxide will be greatly increased.
At present, manganese sesquioxide is mostly prepared by roasting manganese salt, and the method has the defects of high calcination temperature, high energy consumption, high impurity content, poor reaction activity of products and the like. Other methods such as sol-gel method, hydrothermal method, solvothermal method, etc. have the problems of more additives, complex process conditions or the need of special reaction equipment, etc., and are not beneficial to industrial implementation. Therefore, a method for preparing battery grade manganese sesquioxide and a product thereof are needed to solve the problem.
Disclosure of Invention
The invention aims to provide a preparation method of battery-grade manganese sesquioxide and a product thereof, and aims to solve the problem that the existing preparation method of the battery-grade manganese sesquioxide has more defects.
In order to achieve the purpose, the invention provides the following technical scheme: a preparation method of battery-grade manganese sesquioxide comprises the steps of taking electrolytic manganese metal as a raw material, taking acid as a catalyst, and preparing manganese sesquioxide by hydrolyzing and oxidizing manganese metal suspension; adding an oxidant in the reaction process, and controlling the oxidation-reduction potential of the reaction; adding an alkaline solution in the reaction process, and controlling the reaction pH; and (3) preparing manganese sesquioxide slurry after reaction, and washing and drying to obtain a manganese sesquioxide product.
Preferably, the preparation method comprises the following specific steps:
s1, preparing electrolytic manganese metal with the purity of more than 99wt.% into manganese powder or manganese slurry with a certain granularity by using crushing equipment;
s2, adding deionized water, a catalyst and a reaction auxiliary agent into a reaction kettle, adding the prepared manganese powder or manganese slurry into the reaction kettle, adding deionized water to prepare a suspension, and reacting under the stirring condition;
s3, in the reaction process, adding an oxidant into the reaction kettle to control the oxidation-reduction potential of the reaction, and adding an alkaline solution to control the pH of the reaction to obtain manganese sesquioxide slurry;
and S4, washing and drying the manganese sesquioxide slurry to obtain a manganese sesquioxide product.
Preferably, the median diameter D50 of the manganese particles in the manganese powder or the manganese slurry is 5-15 um.
Preferably, the mass percentage of manganese in the suspension is 15-25%.
Preferably, the catalyst is at least one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid and amino acid; the adding mass of the catalyst is 0.4-1.0% of the mass of manganese in the suspension.
Preferably, the reaction auxiliary agent is at least one of polyacrylic acid, ammonium polyacrylate, polyethylene glycol, polyvinyl alcohol and polyacrylamide; the adding mass of the reaction auxiliary agent is 0.2-1 per mill of the mass of manganese in the suspension.
Preferably, the oxidant is at least one of hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium persulfate, sodium persulfate, ammonium persulfate, sodium thiosulfate and ammonium thiosulfate, and the oxidant is added to control the oxidation-reduction potential of the reaction to be 400 mV-600 mV.
Preferably, the alkaline solution is at least one of sodium hydroxide solution, potassium hydroxide solution, ammonia water solution and tetramethylammonium hydroxide solution, the concentration of the alkaline solution is 4-8%, the alkaline solution is added, and the reaction pH is controlled to be 6.5-8.
Preferably, in step S2, the rotation speed of the stirring impeller of the reaction kettle is 300 to 500rpm during the reaction.
The invention provides another technical scheme that: the battery grade manganese sesquioxide product prepared by the preparation method has the purity of more than 99 percent, the manganese sesquioxide is spherical or quasi-spherical, the median particle size is 3-20 mu m, and the tap density is 1.8-2.8g/cm 3 。
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages of simple and easily controlled process, mild process, no need of high-temperature calcination, no large energy consumption, low impurity content of the product, less used additives, no need of special equipment, no need of purification and impurity removal of the product, only need of controlling the addition of the oxidant and the alkaline solution in the reaction process, regulation and control of the synthesis conditions and the reaction process through the granularity of manganese, the catalyst, the surfactant and the type of the oxidant, effective control and improvement of the micro-morphology and the structure of the product, easy industrial implementation, high manganese sesquioxide product obtained by production, high purity, regular morphology, good dispersibility, uniform granularity distribution, high tap density and good product consistency, and can meet the application requirements of high-end industries.
Drawings
FIG. 1 is an SEM photograph of a sample prepared in example 1;
FIG. 2 is a graph of particle size distribution for the sample prepared in example 1;
FIG. 3 is a comparison of the XRD patterns and standard XRD patterns of samples from example 1 and comparative example 1.
Detailed Description
A preparation method of battery-grade manganese sesquioxide comprises the steps of taking electrolytic manganese metal as a raw material, taking acid as a catalyst, and preparing manganese sesquioxide by hydrolyzing and oxidizing manganese metal suspension; adding an oxidant in the reaction process, and controlling the oxidation-reduction potential of the reaction; adding an alkaline solution in the reaction process, and controlling the reaction pH; and (3) preparing manganese sesquioxide slurry after reaction, and washing and drying to obtain a manganese sesquioxide product.
The preparation method comprises the following specific steps:
s1, preparing electrolytic manganese metal with the purity of more than 99wt.% into manganese powder or manganese slurry with a certain granularity by using crushing equipment, namely the crushing equipment can be dry method or wet method, preferably, the median diameter D50 of manganese particles in the manganese powder or manganese slurry is 5-15 um;
s2, adding deionized water, a catalyst and a reaction auxiliary agent into a reaction kettle, adding the prepared manganese powder or manganese slurry into the reaction kettle, adding the deionized water to prepare a suspension, wherein the mass percentage of manganese in the suspension is controlled to be 15-25%, and reacting under a stirring condition, wherein optionally, the rotating speed of a stirring impeller of the reaction kettle can be 300-500 rpm in the reaction process;
s3, adding an oxidant into the reaction kettle in the reaction process to control the oxidation-reduction potential of the reaction; adding an alkaline solution to control the pH of the reaction, specifically, controlling the adding speed to effectively control the hydrolysis reaction process of manganese; obtaining manganese sesquioxide slurry after the reaction is finished;
s4, washing and drying the manganous oxide slurry to obtain a manganous oxide product.
The catalyst can be at least one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid and amino acid; the mass of the catalyst added is preferably 0.4-1.0% of the mass of manganese in the suspension.
The reaction auxiliary agent can be at least one of polyacrylic acid, ammonium polyacrylate, polyethylene glycol, polyvinyl alcohol and polyacrylamide, and mainly plays a role in dispersion; the addition mass of the reaction auxiliary agent is preferably 0.2-1 per mill of the mass of manganese in the suspension.
The oxidant can be at least one of hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium persulfate, sodium persulfate, ammonium persulfate, sodium thiosulfate and ammonium thiosulfate, and in order to obtain a high-purity product, the oxidant is added, the oxidation-reduction potential of the reaction is controlled to be 400 mV-600 mV, and the oxidation-reduction potential can be monitored in real time through an online oxidation-reduction potential detector.
The alkaline solution may be at least one of sodium hydroxide solution, potassium hydroxide solution, ammonia water solution and tetramethylammonium hydroxide solution, the concentration of the alkaline solution may be 4-8%, and the reaction pH is preferably controlled to 6.5-8 by adding the alkaline solution.
The purity of the battery-grade manganese sesquioxide product prepared by the preparation method is more than 99 percent, the purity can reach 99.5 to 99.9 percent if the control is reasonable, the manganese sesquioxide particle has good dispersibility, the appearance is spherical or quasi-spherical, the median particle diameter is 3 to 20um, preferably 5 to 15um, and the tap density is 1.8 to 2.8g/cm 3 Can be easily controlled to 2.0g/cm in general 3 The above.
The first embodiment,
Crushing 1000Kg of high-purity metal manganese sheets to a median diameter D by using a vertical stirring mill 50 About 5um, added to the mixture with 4m 3 Carrying out catalytic reaction in a reactor of pure water, 10L of nitric acid with the concentration of 50 percent and 0.6kg of polyacrylamide under the stirring condition, controlling the stirring speed at 400r/min, pumping in sodium hydroxide solution with the concentration of 4 percent to control the pH value of the reaction at 7 +/-0.1, and pumping in ammonium persulfate solution with the concentration of 5 percentControlling the oxidation-reduction potential of the reaction to be 450mV, finishing the reaction after 15 hours, washing and drying the slurry to obtain the manganese sesquioxide powder, wherein the prepared manganese sesquioxide product has good particle dispersibility, spherical or quasi-spherical appearance, 6.1um median diameter and 2.1g/cm tap density 3 。
FIG. 1 is an SEM image of a sample prepared in this example. As shown in the figure, the sample has regular appearance and is spherical or quasi-spherical. FIG. 2 is a laser particle size distribution diagram of the sample prepared in this example, wherein the particle size distribution of the sample is normal and narrow, indicating that the particle size is concentrated and the consistency of the product is good. In FIG. 3, the XRD diffraction peaks of the samples prepared in this example were compared with the standard spectrum (JCPDS # 65-1798) of manganese sesquioxide, and were found to be substantially identical, visually indicating that the samples were high purity manganese sesquioxide, with a manganese content of 69.7% as measured.
Example II,
Crushing 1000Kg of high-purity metal manganese sheet to a middle diameter D by using a double-roller machine 50 About 10um, mixed for 2 hours by a double cone mixer, and then put into a mixer with 4m added 3 Carrying out catalytic reaction in a reactor of pure water, 25L of hydrochloric acid with the concentration of 31 percent and 0.8kg of ammonium polyacrylate under the stirring condition, controlling the stirring speed at 350r/min, pumping in ammonia water solution with the concentration of 6 percent to control the pH value of the reaction at 7.2 +/-0.1, pumping in hydrogen peroxide with the concentration of 27 percent to control the oxidation-reduction potential of the reaction at 450mV, finishing the reaction after 15 hours, washing and drying the slurry to obtain the manganese sesquioxide powder, wherein the prepared manganese sesquioxide product has good particle dispersibility, spherical or quasi-spherical shape, the median particle diameter of 10.8um and the tap density of 2.5g/cm 3 。
Example III,
Crushing 1000Kg of high-purity metal manganese sheet to a middle diameter D by using a double-roller machine 50 About 15um, mixed for 2 hours by a double cone mixer, and then put into a mixer with 4m 3 Carrying out catalytic reaction in a reactor of pure water, 15L of 98 percent sulfuric acid and 0.8kg of polyvinyl alcohol under the stirring condition, controlling the stirring speed at 300r/min, pumping in 6 percent ammonia water solution to control the pH value of the reaction to be 7.5 +/-0.1, pumping in 5 percent ammonium persulfate solution to react with oxygenControlling the reduction potential at 450mV, finishing the reaction after 15 hours, washing and drying the slurry to obtain the manganese sesquioxide powder, wherein the prepared manganese sesquioxide product has good particle dispersibility, spherical or quasi-spherical appearance, a median particle diameter of 14.7um and a tap density of 2.8g/cm 3 。
Comparative examples 1,
Crushing 1000Kg of high-purity metal manganese sheet to a middle diameter D by using a double-roller machine 50 About 10um, mixed for 2 hours by a double cone mixer, and then put into a mixer with 4m added 3 Carrying out catalytic reaction in a reactor of pure water, 25L of hydrochloric acid with the concentration of 31 percent and 0.8kg of ammonium polyacrylate under the stirring condition, controlling the stirring speed at 350r/min, pumping in ammonia water solution with the concentration of 6 percent to control the pH value of the reaction at 7 +/-0.1, pumping in hydrogen peroxide with the concentration of 27 percent to control the oxidation-reduction potential of the reaction at 300mV, finishing the reaction after 15 hours, and washing and drying the slurry to obtain the product powder.
FIG. 3 is XRD patterns of samples prepared in example 1 and comparative example 1. From FIG. 3, it can be seen that when the oxidation-reduction potential of the reaction is lower than 400mV, a large amount of trimanganese tetroxide is formed in the product, and the trimanganese trioxide is difficult to obtain.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are also within the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope defined by the claims.
The details of the present invention are not described in detail, but are known to those skilled in the art.
Claims (10)
1. A preparation method of battery-grade manganese sesquioxide is characterized by comprising the following steps: the method comprises the steps of preparing manganese sesquioxide by using electrolytic manganese metal as a raw material and acid as a catalyst and adopting manganese metal suspension for hydrolysis and oxidation; adding an oxidant in the reaction process, and controlling the oxidation-reduction potential of the reaction; adding an alkaline solution in the reaction process, and controlling the reaction pH; and (3) preparing manganese sesquioxide slurry after reaction, and washing and drying to obtain a manganese sesquioxide product.
2. The method for preparing battery grade manganese sesquioxide according to claim 1, characterized by comprising the following specific steps:
s1, preparing electrolytic manganese metal with the purity of more than 99wt.% into manganese powder or manganese slurry with a certain granularity by using crushing equipment;
s2, adding deionized water, a catalyst and a reaction auxiliary agent into a reaction kettle, adding the prepared manganese powder or manganese slurry into the reaction kettle, adding deionized water to prepare a suspension, and reacting under the stirring condition;
s3, in the reaction process, adding an oxidant into the reaction kettle to control the oxidation-reduction potential of the reaction, and adding an alkaline solution to control the pH of the reaction to obtain manganese sesquioxide slurry;
s4, washing and drying the manganous oxide slurry to obtain a manganous oxide product.
3. The method of claim 2, wherein the method comprises the steps of: the median diameter D50 of the manganese particles in the manganese powder or the manganese slurry is 5-15 um.
4. The method of claim 1 or 2, wherein the method comprises the following steps: the mass percentage of manganese in the suspension is 15-25%.
5. The method of claim 1 or 2, wherein the method comprises the following steps: the catalyst is at least one of hydrochloric acid, sulfuric acid, nitric acid, formic acid, acetic acid and amino acid; the adding mass of the catalyst is 0.4-1.0% of the mass of the manganese in the suspension.
6. The method of claim 2, wherein the method comprises the steps of: the reaction auxiliary agent is at least one of polyacrylic acid, ammonium polyacrylate, polyethylene glycol, polyvinyl alcohol and polyacrylamide; the adding mass of the reaction auxiliary agent is 0.2-1 per mill of the mass of manganese in the suspension.
7. The method of claim 1 or 2, wherein the method comprises the following steps: the oxidant is at least one of hydrogen peroxide, hypochlorous acid, sodium hypochlorite, potassium persulfate, sodium persulfate, ammonium persulfate, sodium thiosulfate and ammonium thiosulfate, and the oxidant is added to control the oxidation-reduction potential of the reaction to be 400 mV-600 mV.
8. The method of claim 1 or 2, wherein the method comprises the following steps: the alkaline solution is at least one of sodium hydroxide solution, potassium hydroxide solution, ammonia water solution and tetramethylammonium hydroxide solution, the concentration of the alkaline solution is 4-8%, the alkaline solution is added, and the reaction pH is controlled to be 6.5-8.
9. The method of claim 2, wherein the method comprises the steps of: in the step S2, the rotating speed of the stirring impeller of the reaction kettle is 300-500 rpm in the reaction process.
10. A battery grade manganese oxide product prepared by the method of any one of claims 1 to 9, wherein: the purity of the manganese sesquioxide product is more than 99 percent, the manganese sesquioxide product is spherical or quasi-spherical, the median particle size is 3-20um, and the tap density is 1.8-2.8g/cm 3 。
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