CN103700830A - Manganese sesquioxide micro powder and preparation method and application thereof - Google Patents
Manganese sesquioxide micro powder and preparation method and application 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 52
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 42
- 239000000843 powder Substances 0.000 title abstract description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 69
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 23
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 21
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 21
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 21
- 239000011572 manganese Substances 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 17
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- 230000007935 neutral effect Effects 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 56
- 239000003595 mist Substances 0.000 claims description 32
- 235000007079 manganese sulphate Nutrition 0.000 claims description 17
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 17
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 229940099596 manganese sulfate Drugs 0.000 claims description 16
- 239000011702 manganese sulphate Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 16
- ZWBLCEPTJRPNLP-UHFFFAOYSA-N manganese;oxalic acid;hydrate Chemical compound O.[Mn].OC(=O)C(O)=O ZWBLCEPTJRPNLP-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims description 8
- 239000000470 constituent Substances 0.000 claims description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- 229910001416 lithium ion Inorganic materials 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 5
- 238000013459 approach Methods 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 11
- 150000002696 manganese Chemical class 0.000 abstract description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052744 lithium Inorganic materials 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 7
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000000696 magnetic material Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 235000006748 manganese carbonate Nutrition 0.000 description 5
- XMWCXZJXESXBBY-UHFFFAOYSA-L manganese(ii) carbonate Chemical compound [Mn+2].[O-]C([O-])=O XMWCXZJXESXBBY-UHFFFAOYSA-L 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- 239000011656 manganese carbonate Substances 0.000 description 4
- 229940093474 manganese carbonate Drugs 0.000 description 4
- 229910000016 manganese(II) carbonate Inorganic materials 0.000 description 4
- VASIZKWUTCETSD-UHFFFAOYSA-N oxomanganese Chemical compound [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 4
- 238000010298 pulverizing process Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 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 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000035784 germination Effects 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 235000003642 hunger Nutrition 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 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
- IEBUJWPMONWWDM-UHFFFAOYSA-N manganese;oxalic acid Chemical compound [Mn].OC(=O)C(O)=O IEBUJWPMONWWDM-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 description 1
- 229940039790 sodium oxalate Drugs 0.000 description 1
- 230000037351 starvation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
-
- 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 manganese sesquioxide micro powder of which the D50 is 3-30 micrometer, the apparent density is 0.5-1.5 g/mL, the tap density is 1.0-2.5 g/mL, content of Mn is higher than 68%, contents of Ca and Mg are both lower than 100ppm, and content of sulfate radical is less than 500ppm. A preparation method comprises continuously adding a divalent manganese salt solution and oxalic acid at the same time at certain temperature under a stirring condition, then continuously adding ammonium hydroxide or ammonium bicarbonate when the pH value is lower than 5.0, to maintain a reaction system to be faintly acid, preserving heat and stirring until the reaction is finished after the reaction liquid is finished adding and the pH value is raised to about neutral, finally conducting solid liquid separation on a product, rinsing for multiple times, then roasting, cooling, crushing and sieving to obtain the product. The manganese sesquioxide micro powder is small and even, controllable in granularity, low in content of impurities and high in purity, and can be used as a precursor to prepare lithium manganate or soft magnetic ferrite for a lithium battery.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of oxide micropowder material and preparation method thereof, relate in particular to a kind of lithium ion battery use or manganese sesquioxide managnic oxide micro mist and preparation method thereof for soft magnetic ferrite.
Background technology
The oxide of manganese has a lot of purposes, and wherein, preparing lithium ion battery material and magnetic material is its important application in modern new forms of energy and novel electron Material Field.
LiMn2O4, due to aboundresources and low price, is one of candidate materials of new-energy automobile use electrokinetic cell.The production of LiMn2O4 at present generally be take electrolytic manganese dioxide as raw material, by roasting after mixing with lithium carbonate, make, and the production of electrolytic manganese dioxide to be first electrolyzing manganese sulfate solution obtain on anode block, then carry out the powder that sorting obtains suitable particle size after pulverizing with Raymond machine.Accordingly, when using electrolytic manganese dioxide to prepare LiMn2O4 as presoma, can have the problem of following three aspects: 1) cost is high, for example the power consumption of electrolytic process just needs 8000 KWhs/ton, and the sorting meeting after pulverizing produces the waste of raw materials of larger proportion; 2) pattern of powder body material, specific area, granularity and distribution etc. all can not be effectively controlled, and this can further affect the chemical property of lithium manganate material; 3) impurity content is high, and the sulfate radical content being for example mingled with in product is generally up to 1.3%, and can bring fe in crushing process, and this can cause negative effect to security performance of lithium ion battery product.
The oxide of manganese is mainly that form with mangano-manganic oxide is for the synthesis of soft magnetic ferrite in the application of preparation field of magnetic material, the production of magnetic material mangano-manganic oxide is by electrolyzing manganese sulfate solution, on negative electrode, to obtain manganese metal sheet, after ball mill grinding, carry out wet oxidation again and make, similarly, owing to having passed through electrolytic process, the production cost of its product is higher, and product quality is difficult to be guaranteed equally.
No matter as the electrolytic manganese dioxide of manganate precursor for lithium material or for the preparation of the mangano-manganic oxide of magnetic material, all belong to the middle transition product of preparing succeeding target finished product, its physical property and chemical property have considerable influence to the quality of succeeding target finished product, but as a kind of middle transition product, they neither synthesize unique feedstock candidate of succeeding target product separately.For example, we can replace electrolytic manganese dioxide manufacturing objective finished product LiMn2O4 with mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese carbonate etc., similarly, also can replace mangano-manganic oxide manufacturing objective finished product soft magnetic ferrite with manganese carbonate, manganese oxide, manganese sesquioxide managnic oxide etc.The investigation recent according to us, manganese sesquioxide managnic oxide is exactly a kind of substitutability middle transition product at aspects such as synthetic cost, properties of product with application prospect.
Mostly existing manganese sesquioxide managnic oxide is to be prepared after roasting by manganese salt such as manganese oxalate, manganese carbonates, but commercially available manganese oxalate generally reacts and make with sodium oxalate by manganese salt, and sodium content is high, and impurity is many; And manganese carbonate is generally directly to be reacted and make with carbon ammonium etc. by manganese sulfate, but the manganese carbonate product particle making is fluffy and thicker, is difficult for rinsing clean, is mingled with sulfate radical more; Visible, the manganese sesquioxide managnic oxide becoming with above-mentioned manganese salt roasting all can not meet the requirement of modern lithium ion battery material and magnetic material.Therefore, how further to improve preparation technology and the condition of manganese sesquioxide managnic oxide, become the difficult problem that those skilled in the art face.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, the manganese sesquioxide managnic oxide micro mist that a kind of product particle is tiny evenly, granularity is controlled, impurity content is low, purity is high is provided, also correspondingly provide that a kind of step is simple, cost is low, energy consumption is low, the preparation method of the manganese sesquioxide managnic oxide micro mist of good product performance, the also corresponding application that a kind of manganese sesquioxide managnic oxide micro mist of the present invention is provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of manganese sesquioxide managnic oxide micro mist, the size indicator D50 of described manganese sesquioxide managnic oxide micro mist is that 3 μ m～30 μ m(are preferably 5 μ m～25 μ m, most preferably be 9 μ m～22 μ m), apparent density is that 0.5g/mL～1.5g/mL(is preferably 0.6g/mL～1.0g/mL), tap density is that 1.0g/mL～2.5g/mL(is preferably 1.2g/mL～2.0g/mL), Mn content is at more than 68% (preferably more than 69%), Ca, Mg constituent content is below 100ppm (more preferably below 55ppm) all, sulfate radical content is (more preferably below 250ppm) below 500ppm.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned manganese sesquioxide managnic oxide micro mist, comprises the following steps:
(1) preparation manganous salt solution and oxalic acid solution; Preparation ammoniacal liquor or ammonium bicarbonate solution; In this step, select especially ammoniacal liquor or ammonium bicarbonate solution, and do not use other alkaline matters (as NaOH, potassium hydroxide, sodium acid carbonate etc.), can avoid like this sneaking into of other metal ion as far as possible, reduce as far as possible the content of metal impurities ion in product;
(2) in reactor, add pure water to do reaction end liquid, at the temperature and stirring condition of 40 ℃～90 ℃, by stoichiometric proportion (1:1), add continuously manganous salt solution and oxalic acid solution simultaneously, the pH value of question response liquid lower than 5.0(more preferably less than 4.0) time start to add continuously ammoniacal liquor or ammonium bicarbonate solution, and control the charging rate of ammoniacal liquor or ammonium bicarbonate solution, the pH value of reaction system is maintained within the scope of faintly acid; Until manganous salt solution and oxalic acid solution, all add pH value complete and reaction system and be increased to while approaching neutral range, stop adding of ammoniacal liquor or ammonium bicarbonate solution, continue insulated and stirred (the continuation insulated and stirred time is generally no more than 1h) until react completely;
In the step (2) of the invention described above, while starting to start reaction, the precipitation reaction principle of generation is as shown in the formula (1):
2MnSO
4+H
2C
2O
4+2H
2O＝MnC
2O
4·2H
2O↓+Mn(HSO
4)
2 （1）；
Along with being constantly adding of alkaline ammoniacal liquor or ammonium bicarbonate solution, start again to occur the neutralization reaction as shown in the formula (2) or (3):
Mn(HSO
4)
2+2NH
3·H
2O＝MnSO
4+(NH
4)
2SO
4+2H
2O（2）；
Mn(HSO
4)
2+2NH
4HCO
3＝MnSO
4+(NH
4)
2SO
4+2CO
2↑+2H
2O（3）；
(3) product after step (2) is carried out to Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use pure water rinsing for several times, to reduce sulfate radical content, then Separation of Solid and Liquid;
(4) by the oxalic acid hydrate manganese obtaining after step (3) thorough roasting in the air furnace of 300 ℃～500 ℃, and guarantee that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverize and sieve, obtain manganese sesquioxide managnic oxide micropowder material; This step is by Roasting Decomposition and is oxidized manganese oxalate, the reaction of its generation following formula (4):
4MnC
2O
4·2H
2O+3O
2＝2Mn
2O
3+8CO
2+8H
2O（4）；
It is under the atmosphere of air or logical oxygen, to carry out roasting that this step requires, so that product is manganese sesquioxide managnic oxide micro mist, if the quantity not sufficient of starvation or oxygen, the product obtaining after roasting is the Mn oxide of other form, as mixture of manganese monoxide or manganese monoxide and manganese sesquioxide managnic oxide etc.
Above-mentioned preparation method, preferred, in described step (1), manganous salt solution refers to that manganese metal content is the manganese sulfate solution of 20g/L～150g/L, the concentration of described oxalic acid solution is 100g/L～600g/L.
Above-mentioned preparation method, preferred, in described step (1), the concentration of described ammoniacal liquor is 5%～30%, the concentration of described ammonium bicarbonate solution is 150g/L～350g/L.
For guaranteeing that solution can reach above-mentioned preferred concentration range, when dissolving oxalic acid, carbon ammonium, can heat, then keep necessary solution temperature to prevent crystallization.
Above-mentioned preparation method, preferred, in described step (2), described manganous salt solution and oxalic acid solution last add after 0.5h～3h complete.By controlling the feed time of oxalic acid and manganous salt solution, can make the dense of manganese oxalate germination, reduce sulfate radical being mingled with in product, be conducive to reduce the impurity content of final manganese sesquioxide managnic oxide product.
Above-mentioned preparation method, preferred, in described step (2), described faintly acid scope refers to that pH value is controlled at 2.0～5.0; The described neutral range that approaches refers to that pH value is controlled at 6.0～8.0.
Above-mentioned preparation method, preferred, in described step (3), rinsing is controlled at 40 ℃～90 ℃ by the temperature of pure water.
Above-mentioned preparation method, preferred, in described step (4), oxalic acid hydrate manganese time of thorough roasting in air furnace is controlled at 1h～6h.
Above-mentioned preparation method, preferred, in described step (4), roasting adopts revolution baking modes or in roasting process, suitably carries out stirring, can make like this uniformity of product better.
In the preparation method of the invention described above, its technological principle is first to synthesize the oxalic acid hydrate manganese that D50 is 3 μ m～30 μ m, then decomposes and oxidation through high-temperature roasting, makes manganese sesquioxide managnic oxide micro mist.
As a total technical conceive, the present invention also provides a kind of above-mentioned manganese sesquioxide managnic oxide micro mist as presoma, preparing the application in LiMn2O4 or soft magnetic ferrite for lithium ion battery.
Compared with prior art, the invention has the advantages that:
1, product particle is tiny, even, and granularity is controlled: the present invention is by first controlling the granularity of intermediate oxalic acid hydrate manganese, and then the granularity of control product manganese sesquioxide managnic oxide; When oxalic manganese, by controlling charging rate and pH value, control the granular size of manganese oxalate, guaranteed the uniform particles of final products.And compare electrolytic manganese dioxide and magnetic material mangano-manganic oxide, these conventional methods are all to obtain powder by mechanical crushing, its granule size heterogeneity, in crushing process, unwanted micropowders also needs sorting to reject, the present invention compares conventional method, not only the utilization of resources is more abundant, and product granularity is more evenly controlled, and performance is better.
2, product impurity content is low, purity is high: preparation technology of the present invention can effectively reduce the Inclusion Problem of impurity, and when precipitation manganese oxalate, part metals impurity is retained in mother liquor and is discharged from; Owing to having controlled the speed of crystallization process, can make manganese oxalate particle grow densely, and remove sulfate radical foreign matter by rinsing, reduced being mingled with of sulfate radical.From detection case, in the manganese sesquioxide managnic oxide micro powder product of manufacture of the present invention, calcium-magnesium content is in 50ppm left and right, sulfate radical content is in 200ppm left and right, iron content is below 30ppm, product manganese content is amounted to manganese sesquioxide managnic oxide content more than 69.2% (the theoretical manganese content of pure manganese sesquioxide managnic oxide is 69.6%) and is reached more than 99% (by contrast, general electrolytic manganese dioxide, its calcium-magnesium content is in 300ppm left and right, sulfate radical content approximately 1.3%, total iron content is in 50ppm left and right, and manganese dioxide content is in 93% left and right).
3, without pulverizing, avoid sneaking into of exogenous impurity: the present invention is first by wet method synthesis of oxalic acid manganese, pyrolysis and oxidation obtain manganese sesquioxide managnic oxide micro mist again, this does not wherein have mechanical crushing process, can not introduce external metal impurities (and conventional electrolytic manganese dioxide and the pulverizing of manganese metal can bring iron tramp problem) yet.
4, cost is low: no matter be electrolytic manganese dioxide or mangano-manganic oxide, its source material is all manganese sulfates; And the present invention directly makes raw material with manganese sulfate, technological process is simplified more, has saved the high electrolytic process of energy consumption, has reduced greatly production cost, and economic benefit is obvious.
5, take manganese sesquioxide managnic oxide micro mist prepared by the present invention as raw material is during for the preparation of LiMn2O4, be conducive to improve chemical property and the security performance of LiMn2O4 product, also can be soft magnetic ferrite industry simultaneously a kind of candidate materials cheap for manufacturing cost is provided.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the manganese sesquioxide managnic oxide micro mist that makes in the embodiment of the present invention 3.
Fig. 2 is the particle size distribution figure of the manganese sesquioxide managnic oxide micro mist that makes in the embodiment of the present invention 3.
Fig. 3 is the XRD figure of the manganese sesquioxide managnic oxide micro mist that makes in the embodiment of the present invention 3.
Embodiment
For the ease of understanding the present invention, below in connection with Figure of description and preferred embodiment, the present invention is done more comprehensively, described meticulously, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, all technical terms of hereinafter using are identical with the implication that those skilled in the art understand conventionally.Technical term used herein, just in order to describe the object of specific embodiment, is not to be intended to limit the scope of the invention.
If no special instructions, the raw material of using in following examples and reagent etc. are and are commercially available maybe and can prepare by conventional method.
Embodiment 1:
A manganese sesquioxide managnic oxide micro mist of the present invention, the size indicator D50 of manganese sesquioxide managnic oxide micro mist is 9.2 μ m, apparent density is 0.6g/mL, tap density is 1.2g/mL, Mn content is that 52ppm, Mg constituent content are 48ppm at 69.2%, Ca constituent content, and sulfate radical content is 236ppm.
The preparation method of above-mentioned manganese sesquioxide managnic oxide micro mist in the present embodiment, specifically comprises the following steps:
(1) the manganese sulfate solution 1L that preparing metal manganese content is 145g/L, the oxalic acid solution 1L that compound concentration is 332g/L; The ammoniacal liquor that preparation mass fraction is 15%;
(2) in the reactor of 8L, add 1L pure water to make reaction end liquid, stirring is warming up to 60 ℃, at the temperature and stirring condition of 60 ℃, the manganese sulfate solution and the oxalic acid solution that by stoichiometric proportion 1:1, add continuously, evenly above-mentioned preparation simultaneously, the pH value of question response mother liquor is reduced at 4.0 o'clock and starts to add continuously ammoniacal liquor, and regulates the charging rate of ammoniacal liquor to make the pH of mother liquor maintain 4.0 ± 0.5; Until manganese sulfate solution and oxalic acid solution, last 1h and all add pH value complete and reaction system and be increased at 6.5 o'clock, stop adding of ammoniacal liquor, insulated and stirred 30min is until react completely in continuation;
(3) product after step (2) is carried out to Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use 50 ℃ of pure water rinsings for several times, then Separation of Solid and Liquid;
(4) by the oxalic acid hydrate manganese crystal thorough roasting 3h in the air furnace of 400 ℃ obtaining after step (3), and guarantee that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverize and sieve, obtain manganese sesquioxide managnic oxide micropowder material.
After testing, the size indicator D50 of this manganese sesquioxide managnic oxide micro mist is 9.2 μ m, and apparent density is 0.6g/ml, and tap density is 1.2g/ml, and specific area is 15.4m
2/ g, Mn% is 69.2%, Ca content is only 52ppm, Mg content is only 48ppm, SO
4 2-content is only 236ppm.
Embodiment 2:
A manganese sesquioxide managnic oxide micro mist of the present invention, the size indicator D50 of manganese sesquioxide managnic oxide micro mist is 20.3 μ m, apparent density is 0.8g/mL, tap density is 1.3g/mL, Mn content is that 39ppm, Mg constituent content are 43ppm at 68.9%, Ca constituent content, and sulfate radical content is 218ppm.
The preparation method of above-mentioned manganese sesquioxide managnic oxide micro mist in the present embodiment, specifically comprises the following steps:
(1) the manganese sulfate solution 1L that preparing metal manganese content is 55g/L, the oxalic acid solution 1L that compound concentration is 126g/L; The ammonium bicarbonate solution of preparation 200g/L;
(2) in the reactor of 8L, add 1L pure water to make reaction end liquid, stirring is warming up to 40 ℃, at the temperature and stirring condition of 40 ℃, the manganese sulfate solution and the oxalic acid solution that by stoichiometric proportion 1:1, add continuously, evenly above-mentioned preparation simultaneously, the pH value of question response mother liquor is reduced at 3.0 o'clock and starts to add continuously ammonium bicarbonate solution, and regulates the charging rate of ammonium bicarbonate solution to make the pH of mother liquor maintain 3.5 ± 0.5; Until manganese sulfate solution and oxalic acid solution, last 1h and all add pH value complete and reaction system and be increased at 7.0 o'clock, stop adding of ammonium bicarbonate solution, insulated and stirred 30min is until react completely in continuation;
(3) product after step (2) is carried out to Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use 50 ℃ of pure water rinsings for several times, then Separation of Solid and Liquid;
(4) by the oxalic acid hydrate manganese crystal thorough roasting 3h in the air furnace of 500 ℃ obtaining after step (3), and guarantee that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverize and sieve, obtain manganese sesquioxide managnic oxide micropowder material.
After testing, the size indicator D50 of this manganese sesquioxide managnic oxide micro mist is 20.3 μ m, and apparent density is 0.8g/ml, and tap density is 1.3g/ml, and specific area is 11.3m
2/ g, Mn% is 68.9%, Ca content is only 39ppm, Mg content is only 43ppm, SO
4 2-content is only 218ppm.
Embodiment 3:
A manganese sesquioxide managnic oxide micro mist of the present invention, the size indicator D50 of manganese sesquioxide managnic oxide micro mist is 13.2 μ m, apparent density is 1.0g/mL, tap density is 1.4g/mL, Mn content is that 47ppm, Mg constituent content are 42ppm at 69.4%, Ca constituent content, and sulfate radical content is 208ppm.
The preparation method of above-mentioned manganese sesquioxide managnic oxide micro mist in the present embodiment, specifically comprises the following steps:
(1) manganese sulfate solution that preparing metal manganese content is 110g/L, the oxalic acid solution that compound concentration is 250g/L (being preheated to 60 ℃); The ammonium bicarbonate solution of preparation 240g/L;
(2) in the reactor of 200L, add about 30L pure water to make reaction end liquid, stirring is warming up to 60 ℃, at the temperature and stirring condition of 60 ℃, the manganese sulfate solution and the oxalic acid solution that by stoichiometric proportion 1:1, add continuously, evenly above-mentioned preparation simultaneously, regulate the charging rate of manganese sulfate solution and oxalic acid solution to be 25L/h, the pH value of question response mother liquor is reduced at 2.0 o'clock and starts to add continuously ammonium bicarbonate solution, and regulates the charging rate of ammonium bicarbonate solution to make the pH of mother liquor maintain 4.5 ± 0.5; Until manganese sulfate solution and oxalic acid solution, last 2h and all add pH value complete and reaction system and be increased at 6.5 o'clock, stop adding of ammonium bicarbonate solution, insulated and stirred 15min is until react completely in continuation;
(3) product after step (2) is carried out to Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use 50 ℃ of pure water rinsings for several times, then Separation of Solid and Liquid;
(4) by the oxalic acid hydrate manganese crystal thorough roasting 3h in the air furnace of 350 ℃ obtaining after step (3), and guarantee that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverize and sieve, obtain manganese sesquioxide managnic oxide micropowder material.
After testing, the size indicator D50 of this manganese sesquioxide managnic oxide micro mist is 13.2 μ m, and apparent density is 1.0g/ml, and tap density is 1.4g/ml, and specific area is 20.6m
2/ g, Mn% is 69.4%, Ca content is only 47ppm, Mg content is only 42ppm, SO
4 2-content is only 208ppm.
Claims (10)
1. a manganese sesquioxide managnic oxide micro mist, it is characterized in that: the size indicator D50 of described manganese sesquioxide managnic oxide micro mist is 3 μ m～30 μ m, apparent density is 0.5g/mL～1.5g/mL, tap density is 1.0g/mL～2.5g/mL, Mn content is more than 68%, Ca, Mg constituent content are all below 100ppm, and sulfate radical content is below 500ppm.
2. a preparation method for manganese sesquioxide managnic oxide micro mist, comprises the following steps:
(1) preparation manganous salt solution and oxalic acid solution; Preparation ammoniacal liquor or ammonium bicarbonate solution;
(2) in reactor, add pure water to do reaction end liquid, at the temperature and stirring condition of 40 ℃～90 ℃, by stoichiometric proportion, add continuously manganous salt solution and oxalic acid solution simultaneously, the pH value of question response liquid is lower than starting to add continuously ammoniacal liquor or ammonium bicarbonate solution at 5.0 o'clock, and control the charging rate of ammoniacal liquor or ammonium bicarbonate solution, the pH value of reaction system is maintained within the scope of faintly acid; Until manganous salt solution and oxalic acid solution, all add pH value complete and reaction system and be increased to while approaching neutral range, stop adding of ammoniacal liquor or ammonium bicarbonate solution, continuation insulated and stirred is until react completely;
(3) product after step (2) is carried out to Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use pure water rinsing for several times, then Separation of Solid and Liquid;
(4) by the oxalic acid hydrate manganese obtaining after step (3) roasting in the air furnace of 300 ℃～500 ℃, cooling after roasting completes, pulverize and sieve, obtain manganese sesquioxide managnic oxide micropowder material.
3. preparation method according to claim 2, is characterized in that: in described step (1), manganous salt solution refers to that manganese metal content is the manganese sulfate solution of 20g/L～150g/L, and the concentration of described oxalic acid solution is 100g/L～600g/L.
4. preparation method according to claim 2, is characterized in that: in described step (1), the concentration of described ammoniacal liquor is 5%～30%, and the concentration of described ammonium bicarbonate solution is 150g/L～350g/L.
5. according to the preparation method described in claim 2,3 or 4, it is characterized in that: in described step (2), described manganous salt solution and oxalic acid solution last add after 0.5h～3h complete.
6. according to the preparation method described in claim 2,3 or 4, it is characterized in that: in described step (2), described faintly acid scope refers to that pH value is controlled at 2.0～5.0; The described neutral range that approaches refers to that pH value is controlled at 6.0～8.0.
7. according to the preparation method described in claim 2,3 or 4, it is characterized in that: in described step (3), rinsing is controlled at 40 ℃～90 ℃ by the temperature of pure water.
8. according to the preparation method described in claim 2,3 or 4, it is characterized in that: in described step (4), oxalic acid hydrate manganese time of thorough roasting in air furnace is controlled at 1h～6h.
9. according to the preparation method described in claim 2,3 or 4, it is characterized in that: in described step (4), roasting adopts revolution baking modes or in roasting process, suitably carries out stirring.
10. a manganese sesquioxide managnic oxide micro mist as claimed in claim 1 or that preparation method makes as described in any one in claim 2～9 is being prepared the application in LiMn2O4 or soft magnetic ferrite for lithium ion battery as presoma.
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| CN105883924A (en) * | 2016-05-23 | 2016-08-24 | 渤海大学 | Preparation method of manganese sesquioxide hierarchical-structure material |
| CN106848295A (en) * | 2017-02-20 | 2017-06-13 | 北京理工大学 | Mn oxide and preparation method thereof and aluminium ion battery |
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| CN115959710A (en) * | 2022-12-06 | 2023-04-14 | 中钢天源股份有限公司 | Preparation method of battery-grade manganese sesquioxide and product thereof |
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