CN103700830B - A kind of manganese sesquioxide managnic oxide micro mist and its preparation method and application - Google Patents
A kind of manganese sesquioxide managnic oxide micro mist and its preparation method and application 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 40
- 239000003595 mist Substances 0.000 title claims abstract description 35
- 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
- 239000007788 liquid Substances 0.000 claims abstract description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 239000011572 manganese Substances 0.000 claims abstract description 16
- 239000012266 salt solution Substances 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
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 claims abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 7
- 229910000859 α-Fe Inorganic materials 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 56
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 20
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 20
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 20
- 239000001099 ammonium carbonate Substances 0.000 claims description 20
- 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
- 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
- 238000000034 method Methods 0.000 claims description 9
- 239000000470 constituent Substances 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 238000004062 sedimentation Methods 0.000 claims description 5
- 239000012535 impurity Substances 0.000 abstract description 11
- JJEJDZONIFQNHG-UHFFFAOYSA-N [C+4].N Chemical compound [C+4].N JJEJDZONIFQNHG-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007935 neutral effect Effects 0.000 abstract description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- 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
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 8
- 239000011777 magnesium Substances 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 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
- 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
- 235000006748 manganese carbonate Nutrition 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
- 239000000843 powder Substances 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
- 230000001276 controlling effect Effects 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
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 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
- 150000002696 manganese Chemical class 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 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
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 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
- 229910052744 lithium Inorganic materials 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
- 238000003701 mechanical milling Methods 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
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000001105 regulatory effect Effects 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
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
Landscapes
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a kind of manganese sesquioxide managnic oxide micro mist, its D50 is 3 ~ 30 μm, and apparent density is 0.5 ~ 1.5g/mL, tap density be 1.0 ~ 2.5g/mL, Mn content more than 68%, Ca, Mg content is all at below 100ppm, and sulfate radical content is at below 500ppm; Its preparation method is: under uniform temperature and stirring condition, simultaneously adds manganous salt solution and oxalic acid continuously, until pH value lower than 5.0 time add ammoniacal liquor or carbon ammonium continuously, make reaction system maintain faintly acid; Question response liquid adds complete and pH value and is increased to close to time neutral, and insulated and stirred is until react completely; Finally carry out Separation of Solid and Liquid to product, rinsing for several times, then roasting, cools, pulverizes and sieves and obtain product.Manganese sesquioxide managnic oxide micro mist fine uniform of the present invention, granularity is controlled, impurity content is low, purity is high, can be used as precursor power lithium ion battery LiMn2O4 or soft magnetic ferrite.
Description
Technical field
The invention belongs to new material technology field, relate to a kind of oxide micropowder material and preparation method thereof, particularly relate to a kind of lithium ion battery use or soft magnetic ferrite manganese sesquioxide managnic oxide micro mist and preparation method thereof.
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 electrokinetic cell.The production of current LiMn2O4 is generally raw material with electrolytic manganese dioxide, obtain by mixing rear roasting with lithium carbonate, and the production of electrolytic manganese dioxide to be first electrolyzing manganese sulfate solution obtain block on anode, then carry out the powder that sorting obtains suitable particle size after pulverizing with Raymond machine.Accordingly, when using electrolytic manganese dioxide as precursor power LiMn2O4, can there is the problem of following three aspects: 1) cost is high, the power consumption of such as electrolytic process just needs 8000 KWhs/ton, and the sorting after pulverizing can produce 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 affect the chemical property of lithium manganate material further; 3) impurity content is high, and the sulfate radical content such as, be mingled with in product generally up to 1.3%, and can bring fe in crushing process, and this can cause negative effect to the security performance of lithium ion battery product.
The oxide of manganese preparation field of magnetic material application mainly with the form of mangano-manganic oxide for the synthesis of soft magnetic ferrite, the production of magnetic material mangano-manganic oxide on negative electrode, obtains manganese metal sheet by electrolyzing manganese sulfate solution, after ball mill grinding, carry out wet oxidation again and obtain, similarly, owing to have passed through electrolytic process, the production cost of its product is higher, and product quality is difficult to be guaranteed equally.
No matter the electrolytic manganese dioxide as manganate precursor for lithium material or the mangano-manganic oxide for the preparation of magnetic material, all belong to the middle transition product preparing succeeding target finished product, its physical property and the quality of chemical property to succeeding target finished product have considerable influence, but as a kind of middle transition product, they neither synthesize unique feedstock candidate of respective succeeding target product.Such as, we can use mangano-manganic oxide, manganese sesquioxide managnic oxide, manganese carbonate etc. to replace electrolytic manganese dioxide manufacturing objective finished product LiMn2O4, similarly, manganese carbonate, manganese oxide, manganese sesquioxide managnic oxide etc. also can be used to replace mangano-manganic oxide manufacturing objective finished product soft magnetic ferrite.The investigation recent according to us, manganese sesquioxide managnic oxide is exactly a kind of substitutability middle transition product in synthesis cost, properties of product etc. with application prospect.
Mostly existing manganese sesquioxide managnic oxide is to be prepared after roasting by the manganese such as manganese oxalate, manganese carbonate salt, but commercially available manganese oxalate generally reacts obtained by manganese salt and sodium oxalate, and sodium content is high, and impurity is many; And manganese carbonate is generally directly react obtained by manganese sulfate and carbon ammonium etc., but obtained manganese carbonate product particle is fluffy and thicker, and not easily rinsed clean, is mingled with sulfate radical more; Visible, the manganese sesquioxide managnic oxide become with above-mentioned manganese salt roasting all can not meet the requirement of modern lithium ion battery material and magnetic material.Therefore, how to improve preparation technology and the condition of manganese sesquioxide managnic oxide further, 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 overcomes the deficiencies in the prior art, a kind of product particle fine uniform is provided, granularity is controlled, impurity content is low, manganese sesquioxide managnic oxide micro mist that purity is high, 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 3 μm ~ 30 μm and (is preferably 5 μm ~ 25 μm, most preferably be 9 μm ~ 22 μm), 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 (preferably more than 69%) more than 68%, Ca, Mg constituent content is all below 100ppm (more preferably at below 55ppm), sulfate radical content is below 500ppm (more preferably at below 250ppm).
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) manganous salt solution and oxalic acid solution is prepared; Preparation ammoniacal liquor or ammonium bicarbonate solution; In this step, select ammoniacal liquor or ammonium bicarbonate solution especially, and do not use other alkaline matters (as NaOH, potassium hydroxide, sodium acid carbonate etc.), being mixed into of other metal ion can be avoided so as far as possible, reduce the content of metal impurities ion in product as far as possible;
(2) add pure water in the reactor and do reaction end liquid, at the temperature of 40 DEG C ~ 90 DEG C and stirring condition, stoichiometrically (1:1) adds manganous salt solution and oxalic acid solution simultaneously continuously, the pH value of question response liquid lower than 5.0(more preferably less than 4.0) time starts to add ammoniacal liquor or ammonium bicarbonate solution continuously, and control the charging rate of ammoniacal liquor or ammonium bicarbonate solution, make the pH value of reaction system maintain within the scope of faintly acid; Until manganous salt solution and oxalic acid solution all add complete and the pH value of reaction system is increased to close to neutral range time, stop adding of ammoniacal liquor or ammonium bicarbonate solution, continue insulated and stirred (continue insulated and stirred time be generally no more than 1h) until react completely;
In the step (2) of the invention described above, when 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 the ammoniacal liquor of alkalescence or constantly adding of ammonium bicarbonate solution, start again the neutralization reaction as shown in the formula (2) or (3) occurs:
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 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) the oxalic acid hydrate manganese thorough roasting in the air furnace of 300 DEG C ~ 500 DEG C will obtained after step (3), and ensure that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverizes and sieves, and namely obtains manganese sesquioxide managnic oxide micropowder material; This step is by Roasting Decomposition and is oxidized manganese oxalate, and reaction of following formula (4) occurs for it:
4MnC
2O
4·2H
2O+3O
2＝2Mn
2O
3+8CO
2+8H
2O（4）；
This step requires it is carry out roasting under the atmosphere of air or logical oxygen, to make product for manganese sesquioxide managnic oxide micro mist, if the quantity not sufficient of starvation or oxygen, the product obtained after roasting is the Mn oxide of other form, as the mixture etc. of manganese monoxide or manganese monoxide and manganese sesquioxide managnic oxide.
Above-mentioned preparation method, preferably, 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.
Above-mentioned preparation method, preferably, 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.
For ensureing that solution can reach above-mentioned preferred concentration range, can heat when dissolving oxalic acid, carbon ammonium, then keeping necessary solution temperature to prevent crystallization.
Above-mentioned preparation method, preferably, in described step (2), adds complete after described manganous salt solution and oxalic acid solution last 0.5h ~ 3h.By controlling the feed time of oxalic acid and manganous salt solution, the dense of manganese oxalate germination can be made, minimizing sulfate radical being mingled with in the product, being conducive to the impurity content reducing final manganese sesquioxide managnic oxide product.
Above-mentioned preparation method, preferably, in described step (2), described faintly acid scope refers to that pH value controls 2.0 ~ 5.0; Describedly refer to that pH value controls 6.0 ~ 8.0 close to neutral range.
Above-mentioned preparation method, preferably, in described step (3), the temperature of rinsing pure water controls at 40 DEG C ~ 90 DEG C.
Above-mentioned preparation method, preferably, in described step (4), the time controling of oxalic acid hydrate manganese thorough roasting in air furnace is at 1h ~ 6h.
Above-mentioned preparation method, preferably, in described step (4), roasting adopts revolution baking modes or suitably carry out stirring in roasting process, and the uniformity of product can be made so better.
In the preparation method of the invention described above, its technological principle first synthesizes the oxalic acid hydrate manganese that D50 is 3 μm ~ 30 μm, then decompose and oxidation through high-temperature roasting, obtained 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 the application in precursor power lithium ion battery LiMn2O4 or soft magnetic ferrite.
Compared with prior art, the invention has the advantages that:
1, product particle is tiny, even, and granularity is controlled: the present invention by first controlling the granularity of intermediate oxalic acid hydrate manganese, and then controls the granularity of product manganese sesquioxide managnic oxide; When oxalic manganese, controlled the granular size of manganese oxalate by control charging rate and pH value, ensure that the uniform particles of final products.And compare electrolytic manganese dioxide and magnetic material mangano-manganic oxide, these conventional methods are all 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 uniform, controllable more, and performance is better.
2, product impurity content is low, purity is high: preparation technology of the present invention effectively can reduce the Inclusion Problem of impurity, and when precipitating manganese oxalate, part metals impurity is retained in mother liquor and is discharged; Owing to controlling the speed of crystallization process, manganese oxalate particle can be made to grow densely, and pass through rinsing and remove sulfate radical foreign matter, decrease 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 at about 50ppm, sulfate radical content is at about 200ppm, iron content is at below 30ppm, product Fe content (the theoretical Fe content of pure manganese sesquioxide managnic oxide is 69.6%) more than 69.2% is amounted to manganese sesquioxide managnic oxide content and is reached more than 99% (by contrast, general electrolytic manganese dioxide, its calcium-magnesium content is at about 300ppm, sulfate radical content about 1.3%, total iron content is at about 50ppm, and manganese dioxide content is about 93%).
3, without the need to pulverizing, avoid being mixed into of exogenous impurity: the present invention first obtains manganese sesquioxide managnic oxide micro mist by Moist chemical synthesis manganese oxalate, again pyrolysis and oxidation, this does not wherein have mechanical milling processes, also extraneous metal impurity (and the pulverizing of the electrolytic manganese dioxide of routine and manganese metal, iron tramp problem can be brought) can not be introduced.
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 simplifies more, and eliminate the electrolytic process that energy consumption is high, reduce production cost greatly, economic benefit is obvious.
5, the manganese sesquioxide managnic oxide micro mist prepared with the present invention for raw material for the preparation of LiMn2O4 time, be conducive to the chemical property and the security performance that improve LiMn2O4 product, also can be soft magnetic ferrite industry simultaneously and a kind of candidate materials cheap for manufacturing cost is provided.
Accompanying drawing explanation
Fig. 1 is the SEM figure of manganese sesquioxide managnic oxide micro mist obtained in the embodiment of the present invention 3.
Fig. 2 is the particle size distribution figure of manganese sesquioxide managnic oxide micro mist obtained in the embodiment of the present invention 3.
Fig. 3 is the XRD figure of manganese sesquioxide managnic oxide micro mist obtained in the embodiment of the present invention 3.
Embodiment
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
If no special instructions, the raw material used in following examples and reagent etc. are and are commercially available or prepare by conventional method.
Embodiment 1:
A kind of manganese sesquioxide managnic oxide micro mist of the present invention, the size indicator D50 of manganese sesquioxide managnic oxide micro mist is 9.2 μm, and apparent density is 0.6g/mL, tap density is 1.2g/mL, Mn content is 52ppm, Mg constituent content at 69.2%, Ca constituent content is 48ppm, 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) preparing metal Fe content is the manganese sulfate solution 1L of 145g/L, and compound concentration is the oxalic acid solution 1L of 332g/L; Preparation mass fraction is the ammoniacal liquor of 15%;
(2) in the reactor of 8L, add 1L pure water make reaction end liquid, stirring is warming up to 60 DEG C, at the temperature of 60 DEG C and stirring condition, stoichiometrically 1:1 adds manganese sulfate solution and the oxalic acid solution of above-mentioned preparation simultaneously continuously, evenly, the pH value of question response mother liquor starts when being reduced to 4.0 to add ammoniacal liquor continuously, 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 all add complete and the pH value of reaction system is increased to 6.5 time, stop the adding of ammoniacal liquor, continue insulated and stirred 30min until react completely;
(3) product after step (2) is carried out Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use 50 DEG C of pure water rinsings for several times, then Separation of Solid and Liquid;
(4) the oxalic acid hydrate manganese crystal thorough roasting 3h in the air furnace of 400 DEG C will obtained after step (3), and ensure that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverizes and sieves, and namely obtains manganese sesquioxide managnic oxide micropowder material.
After testing, the size indicator D50 of this manganese sesquioxide managnic oxide micro mist is 9.2 μm, and apparent density is 0.6g/ml, and tap density is 1.2g/ml, and specific area is 15.4m
2/ g, Mn% are 69.2%, Ca content is only 52ppm, and Mg content is only 48ppm, SO
4 2-content is only 236ppm.
Embodiment 2:
A kind of manganese sesquioxide managnic oxide micro mist of the present invention, the size indicator D50 of manganese sesquioxide managnic oxide micro mist is 20.3 μm, and apparent density is 0.8g/mL, tap density is 1.3g/mL, Mn content is 39ppm, Mg constituent content at 68.9%, Ca constituent content is 43ppm, 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) preparing metal Fe content is the manganese sulfate solution 1L of 55g/L, and compound concentration is the oxalic acid solution 1L of 126g/L; The ammonium bicarbonate solution of preparation 200g/L;
(2) in the reactor of 8L, add 1L pure water make reaction end liquid, stirring is warming up to 40 DEG C, at the temperature of 40 DEG C and stirring condition, stoichiometrically 1:1 adds manganese sulfate solution and the oxalic acid solution of above-mentioned preparation simultaneously continuously, evenly, the pH value of question response mother liquor starts when being reduced to 3.0 to add ammonium bicarbonate solution continuously, 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 all add complete and the pH value of reaction system is increased to 7.0 time, stop the adding of ammonium bicarbonate solution, continue insulated and stirred 30min until react completely;
(3) product after step (2) is carried out Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use 50 DEG C of pure water rinsings for several times, then Separation of Solid and Liquid;
(4) the oxalic acid hydrate manganese crystal thorough roasting 3h in the air furnace of 500 DEG C will obtained after step (3), and ensure that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverizes and sieves, and namely obtains manganese sesquioxide managnic oxide micropowder material.
After testing, the size indicator D50 of this manganese sesquioxide managnic oxide micro mist is 20.3 μm, and apparent density is 0.8g/ml, and tap density is 1.3g/ml, and specific area is 11.3m
2/ g, Mn% are 68.9%, Ca content is only 39ppm, and Mg content is only 43ppm, SO
4 2-content is only 218ppm.
Embodiment 3:
A kind of manganese sesquioxide managnic oxide micro mist of the present invention, the size indicator D50 of manganese sesquioxide managnic oxide micro mist is 13.2 μm, and apparent density is 1.0g/mL, tap density is 1.4g/mL, Mn content is 47ppm, Mg constituent content at 69.4%, Ca constituent content is 42ppm, 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) preparing metal Fe content is the manganese sulfate solution of 110g/L, and compound concentration is the oxalic acid solution (being preheated to 60 DEG C) of 250g/L; The ammonium bicarbonate solution of preparation 240g/L;
(2) in the reactor of 200L, add about 30L pure water make reaction end liquid, stirring is warming up to 60 DEG C, at the temperature of 60 DEG C and stirring condition, stoichiometrically 1:1 adds manganese sulfate solution and the oxalic acid solution of above-mentioned preparation simultaneously continuously, evenly, the charging rate of manganese sulfate solution and oxalic acid solution is regulated to be 25L/h, the pH value of question response mother liquor starts when being reduced to 2.0 to add ammonium bicarbonate solution continuously, 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 all add complete and the pH value of reaction system is increased to 6.5 time, stop the adding of ammonium bicarbonate solution, continue insulated and stirred 15min until react completely;
(3) product after step (2) is carried out Separation of Solid and Liquid, obtain intermediate sedimentation thing oxalic acid hydrate manganese, then use 50 DEG C of pure water rinsings for several times, then Separation of Solid and Liquid;
(4) the oxalic acid hydrate manganese crystal thorough roasting 3h in the air furnace of 350 DEG C will obtained after step (3), and ensure that air or oxygen atmosphere in air furnace is sufficient, cooling after roasting completes, pulverizes and sieves, and namely obtains manganese sesquioxide managnic oxide micropowder material.
After testing, the size indicator D50 of this manganese sesquioxide managnic oxide micro mist is 13.2 μm, and apparent density is 1.0g/ml, and tap density is 1.4g/ml, and specific area is 20.6m
2/ g, Mn% are 69.4%, Ca content is only 47ppm, and 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 μm ~ 30 μm, 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 is all at below 100ppm, and sulfate radical content is at below 500ppm.
2. a preparation method for manganese sesquioxide managnic oxide micro mist, comprises the following steps:
(1) manganous salt solution and oxalic acid solution is prepared; Preparation ammoniacal liquor or ammonium bicarbonate solution;
(2) add pure water in the reactor and do reaction end liquid, at the temperature of 40 DEG C ~ 90 DEG C and stirring condition, stoichiometrically add manganous salt solution and oxalic acid solution continuously simultaneously, the pH value of question response liquid lower than 5.0 time start to add ammoniacal liquor or ammonium bicarbonate solution continuously, and control the charging rate of ammoniacal liquor or ammonium bicarbonate solution, make the pH value of reaction system maintain within the scope of faintly acid; Until manganous salt solution and oxalic acid solution all add complete and the pH value of reaction system is increased to 6.0 ~ 8.0 time, stop adding of ammoniacal liquor or ammonium bicarbonate solution, continue insulated and stirred until react completely;
(3) product after step (2) is carried out 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) the oxalic acid hydrate manganese roasting in the air furnace of 300 DEG C ~ 500 DEG C will obtained after step (3), cooling after roasting completes, pulverizes and sieves, and namely obtains manganese sesquioxide managnic oxide micropowder material.
3. preparation method according to claim 2, is characterized in that: in described step (1), and 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), and the concentration of described ammoniacal liquor is 5% ~ 30%, and the concentration of described ammonium bicarbonate solution is 150g/L ~ 350g/L.
5. the preparation method according to claim 2,3 or 4, is characterized in that: in described step (2), adds complete after described manganous salt solution and oxalic acid solution last 0.5h ~ 3h.
6. the preparation method according to claim 2,3 or 4, is characterized in that: in described step (2), and described faintly acid scope refers to that pH value controls 2.0 ~ 5.0.
7. the preparation method according to claim 2,3 or 4, is characterized in that: in described step (3), and the temperature of rinsing pure water controls at 40 DEG C ~ 90 DEG C.
8. the preparation method according to claim 2,3 or 4, is characterized in that: in described step (4), and the time controling of oxalic acid hydrate manganese thorough roasting in air furnace is at 1h ~ 6h.
9. the preparation method according to claim 2,3 or 4, is characterized in that: in described step (4), and roasting adopts revolution baking modes or carry out stirring in roasting process.
10. as claimed in claim 1 or preparation method obtains according to any one of claim 2 ~ 9 a manganese sesquioxide managnic oxide micro mist is as the application in precursor power lithium ion battery LiMn2O4 or soft magnetic ferrite.
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| CN105883924A (en) * | 2016-05-23 | 2016-08-24 | 渤海大学 | Preparation method of manganese sesquioxide hierarchical-structure material |
| CN106848295B (en) * | 2017-02-20 | 2020-05-05 | 北京理工大学 | Manganese oxide, preparation method thereof and aluminum ion battery |
| CN113120965A (en) * | 2021-03-23 | 2021-07-16 | 安徽博石高科新材料股份有限公司 | Preparation method for producing lithium manganate by mixing manganese oxide with manganese dioxide |
| 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 |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319373A (en) * | 2008-05-30 | 2008-12-10 | 哈尔滨工程大学 | Production method of orderly arranged manganese oxide |
| CN102070197A (en) * | 2011-01-26 | 2011-05-25 | 江苏方舟新能源股份有限公司 | Preparation method of spherical manganous oxide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101319373A (en) * | 2008-05-30 | 2008-12-10 | 哈尔滨工程大学 | Production method of orderly arranged manganese oxide |
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|---|---|---|---|---|
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