CN115180651A - Preparation method of manganous-manganic oxide material with controllable particle size for lithium manganate - Google Patents
Preparation method of manganous-manganic oxide material with controllable particle size for lithium manganate Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 74
- 239000002245 particle Substances 0.000 title claims abstract description 51
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 title claims abstract description 20
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 96
- AMWRITDGCCNYAT-UHFFFAOYSA-L manganese oxide Inorganic materials [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 claims abstract description 62
- 239000003513 alkali Substances 0.000 claims abstract description 57
- 238000000034 method Methods 0.000 claims abstract description 28
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims description 45
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 32
- 229910052748 manganese Inorganic materials 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 14
- 229940099596 manganese sulfate Drugs 0.000 claims description 13
- 239000011702 manganese sulphate Substances 0.000 claims description 13
- 235000007079 manganese sulphate Nutrition 0.000 claims description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- -1 polyoxyethylene Polymers 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- BXWNKGSJHAJOGX-UHFFFAOYSA-N hexadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCO BXWNKGSJHAJOGX-UHFFFAOYSA-N 0.000 claims description 4
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000001509 sodium citrate Substances 0.000 claims description 3
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 3
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 2
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 239000002585 base Substances 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 229960000541 cetyl alcohol Drugs 0.000 claims description 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- DDXLVDQZPFLQMZ-UHFFFAOYSA-M dodecyl(trimethyl)azanium;chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)C DDXLVDQZPFLQMZ-UHFFFAOYSA-M 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 239000011565 manganese chloride Substances 0.000 claims description 2
- 235000002867 manganese chloride Nutrition 0.000 claims description 2
- 229940099607 manganese chloride Drugs 0.000 claims description 2
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000012216 screening Methods 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims 1
- 150000004665 fatty acids Chemical class 0.000 claims 1
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 74
- 229910021529 ammonia Inorganic materials 0.000 abstract description 37
- 238000009826 distribution Methods 0.000 abstract description 10
- 239000012535 impurity Substances 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 51
- 230000001276 controlling effect Effects 0.000 description 19
- 230000001105 regulatory effect Effects 0.000 description 12
- 239000012071 phase Substances 0.000 description 11
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 10
- 239000012670 alkaline solution Substances 0.000 description 8
- 238000007873 sieving Methods 0.000 description 7
- 239000011734 sodium Substances 0.000 description 7
- 239000007787 solid Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- 229940113116 polyethylene glycol 1000 Drugs 0.000 description 4
- 239000000047 product Substances 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 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
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000007791 liquid phase Substances 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
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
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- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
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- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C01P2006/11—Powder tap density
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- C01P2006/80—Compositional purity
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Abstract
The invention provides a preparation method of a manganous-manganic oxide material for lithium manganate with controllable particle size. Preparing a product with tap density of more than 2.1g/cm 3 ，BET 0.5‑5m 2 The manganous manganic oxide material has the advantages of good sphericity, uniform particle size, high purity and low impurity content, and the method has the following characteristics: adding a surfactant to improve the dispersibility and sphericity of the mangano-manganic oxide material; by controlling the proportion of ammonia and alkali and the growth time of trimanganese tetroxide in a reaction kettle, the particle size uniformity and the high density of the trimanganese tetroxide material are improved; the manganous-manganic oxide produced by the method has low impurity content, wherein the content of Mn is more than or equal to 71.3 percent, na is less than 150ppm, S is less than 2000ppm, the particle size is uniform, and the particle size distribution is 0.6-1.0; the production process is simple and efficient, and the indexes are easy to control.
Description
Technical Field
The invention belongs to the technical field of lithium ion battery anode material precursors, and particularly relates to a preparation method of a trimanganese tetroxide material for lithium manganate with controllable particle size.
Background
In recent years, with the development of green industries such as new energy automobiles, lithium manganate (LiMn) has been used 2 O 4 ) As a positive electrode material of a power type lithium ion battery, the material has attracted more and more attention due to the advantages of low price, good safety performance, no environmental pollution and the like. Production of lithium manganate (LiMn) 2 O 4 ) The traditional method is mainly a high-temperature solid-phase method, electrolytic manganese dioxide is used as a manganese source in the method, adding lithium carbonate and corresponding additive, and sintering in solid phase. However, the battery material prepared from the lithium manganate produced by the method has the problems of low gram specific capacity, poor cycle performance, poor high-temperature performance and the like. Research shows that the manganese dioxide adopts quasi-spherical mangano-manganic oxide (Mn) compared with manganese dioxide 3 O 4 ) LiMn prepared as raw material 2 O 4 The performance is better. Mn 3 O 4 And LiMn 2 O 4 All of spinel type structure, using Mn 3 O 4 Preparation of LiMn 2 O 4 The violent structural change can not occur, and the material structure is more stable; prepared LiMn 2 O 4 The electrochemical performance is more excellent, and the gram specific capacity, the high-temperature performance, the cycle performance and the like are obviously improved: thus, with Mn 3 O 4 Production of LiMn instead of electrolytic manganese dioxide 2 O 4 Is the current development trend. Mn 3 O 4 The preparation method mainly comprises a roasting method, a reduction method, an oxidation method, an electrolysis method and the like, and at present, a metal manganese powder suspension oxidation method is mostly adopted, which is mature, but has high production cost, high impurity content, uneven granularity, larger grain diameter and wide grain size distribution. How to improve the preparation method to make the impurity content low, the particle size controllable and narrow the particle size distribution is the focus of the current research. In recent years, mn has been produced by direct oxidation of a manganese sulfate solution in an alkaline medium without electrolysis 3 O 4 The method has been a research hotspot due to easy operation, low cost and wide raw material sources.
In the method for directly preparing manganous-manganic oxide by using manganese sulfate solution, a plurality of research reports use ammonia as a precipitator, manganese ions are firstly precipitated, and then the precipitate is oxidized to prepare the manganous-manganic oxide. The method has low manganese recovery rate and high impurity content in the product, and in order to solve the problems, the research on the behavior of manganese sulfate for preparing trimanganese tetroxide in an alkaline medium is very necessary.
With Mn 3 O 4 Preparation of LiMn 2 O 4 ，Mn 3 O 4 The indexes of granularity, crystal morphology, tap density, impurity content and the like of LiMn 2 O 4
Has an important influence on the properties of (B), while Mn 3 O 4 The preparation method of (A) has a large influence on the index. Currently, mn 3 O 4 Mainly prepared by a manganese metal method, but the method has the problems of low specific surface area of the product, uneven granularity, larger grain diameter, wide grain size distribution and the like. The existing preparation process of manganous-manganic oxide comprises the following steps: (1) The two-stage oxidation method for preparing high-purity mangano-manganic oxide can not completely oxidize in liquid phase and needs 300 DEG o C, solid-phase oxidation conversion is carried out to mangano-manganic oxide; (2) Manganese sulfate is directly prepared into manganous manganic oxide by a high-temperature pyrolysis method, and sulfur dioxide and sulfur trioxide gas are generated in the roasting process; (3) The preparation of high-purity trimanganese tetroxide by a metal manganese air oxidation method has the problems that the heat control and the reaction conditions are difficult to control, a great deal of manganese dioxide and manganic oxide are mixed in the product, the conversion rate of trimanganese tetroxide is not high, the specific surface area is small, and the development requirements of the electronic industry and the new energy industry are difficult to meet.
Disclosure of Invention
The invention provides a preparation method of a manganous-manganic oxide material for lithium manganate with controllable particle size, which comprises the following steps:
preparing a manganese-containing solution, and adding a surfactant into the manganese-containing solution;
preparing reaction base solution from one or more of pure water, ammonia solution and alkali solution in a reaction kettle, wherein the pH value is 7.0-13.4, and the rotating speed and the temperature of the reaction kettle are kept within the required range;
step three, enabling the alkali solution, the ammonia solution, the manganese-containing solution and air to flow into a reaction kettle in a parallel mode to react, and controlling the pH value of the reaction to be 8.5-11.85;
step four, after the growth is carried out for a period of time, the particle size meets the requirement, the liquid feeding is stopped, the reaction materials enter a centrifugal machine for spin-drying, 0.1-1mol/L alkali solution is used for leaching, and the temperature of the alkali solution is 25 DEG o C~80 o And C, the weight ratio of the reaction materials to the alkali solution is 1.5 to 1 o C~60 o C, the weight ratio of the reaction materials to the pure water is 1;
step five, transferring the reaction material after centrifugation to 100 o C-200 o And C, drying in an oven until the moisture content is less than 3500ppm, cooling to room temperature, and screening the dried and cooled reaction material by using an ultrasonic vibration screen to obtain the trimanganese tetroxide material with a single crystal phase.
Further, the manganese-containing solution is prepared from one or more of manganese sulfate, manganese nitrate and manganese chloride, and the concentration of the manganese-containing solution is 1.0-3.0mol/L.
Further, the surfactant is one or more of hexadecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, dodecyl trimethyl ammonium chloride, lauryl sodium sulfate, sodium dodecyl benzene sulfonate, polyethylene glycol, polyvinylpyrrolidone, ethanol, n-butyl alcohol, sodium citrate, ethylene diamine tetraacetic acid, urea, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine and palmityl alcohol, and the concentration of the surfactant is 0.5g/L-3.5g/L.
Further, the concentration of the ammonia solution is 0.9-10mol/L, the alkali solution is one or more of sodium hydroxide and potassium hydroxide, and the concentration of the alkali solution is 0.8-8mol/L.
Further, in the third step, the flow rate of the manganese-containing solution is 70-300mL/min, and the flow rate of the introduced air is 0-20mL/min.
Further, in the second step, the concentration of the ammonia solution is 0.9-10mol/L; the ammonia solution is a precipitator and a complexing agent in the reaction process; the concentration of the alkali solution is 0.8-8mol/L; the content of alkali solution in the reaction bottom liquid is 0-10g/L, the content of ammonia solution is 0-10g/L, and the rotating speed of the reaction kettle is 500-1000r/min, the reaction temperature is 30-80 DEG C o C。
Further, in the third step, the ratio of the alkali solution to the ammonia solution in the reaction process is 1.
Furthermore, in the fourth step, the growth time is 20-200h.
Further, the grain size of the trimanganese tetroxide material with a single crystal phase finally obtained in the fifth step is less than 10 microns.
The invention also provides a manganous-manganic oxide material for lithium manganate with controllable particle size, and the manganous-manganic oxide material prepared by the preparation method has the advantages of single crystalline phase, controllable particle size, uniform particle size, high purity, good dispersibility and tap density of more than 2.1g/cm 3 ，BET 0.5-5m 2 G, good sphericity.
Advantageous effects
The mangano-manganic oxide material prepared by the method has the advantages of single crystalline phase, controllable particle size, uniform particle size, high purity, good dispersibility and tap density of more than 2.1g/cm 3 ，BET 0.5-5m 2 G, good sphericity and the like. In order to improve the electrochemical performance of lithium manganate, bulk phase doping of one or more elements including but not limited to Al, B, W, mo, yb, Y, la, in, zr, mg, ti, C, N, etc. may also be performed during the preparation of trimanganese tetroxide by using the method of the present invention, and the doping amount is less than 1%.
Drawings
FIG. 1 XRD pattern of manganomanganic oxide prepared in example 1;
FIG. 2 SEM photograph of manganomanganic oxide prepared in example 1;
FIG. 3 is an SEM image of manganomanganic oxide prepared in comparative example 1;
FIG. 4 XRD pattern of manganomanganic oxide prepared in comparative example 2;
fig. 5 SEM image of trimanganese tetroxide prepared in comparative example 2.
Detailed Description
The present invention will be described in detail with reference to examples.
Example 1
Step one, preparing 2.5mol/L manganese sulfate solution, and adding 1.0g/L polyethylene glycol 1000.
Step two, adding 79.712kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 40 o And C, adding 0.092kg of 8mol/L sodium hydroxide to ensure that the alkali content is within the range of 0-0.3g/L, adding 0.196kg of 9mol/L ammonia to ensure that the ammonia content is within the range of 0.4-0.5g/L, and adjusting the pH to 11.75-11.85.
And step three, regulating the flow of a manganese metering pump to be 100ml/min, regulating the flow of an ammonia metering pump and an alkaline solution metering pump, enabling the ammonia metering pump and the alkaline solution metering pump to flow into a reaction kettle in a parallel mode, controlling the ammonia content to be within the range of 0.4-0.5g/L and the alkaline content to be within the range of 0-0.3g/L, simultaneously introducing air with the flow of 10ml/min, stably controlling the pH to be 11.80 within 0-6h, reducing the reaction pH to 11.05 from 11.80 within 6-6.5h, reducing the reaction pH to 10.45 from 11.05 within 14-14.5h, and stably controlling the reaction pH until the reaction is finished. The initial particle size for 1h of the reaction was D50.40 μm.
Step four, after reacting for 76 hours, the particle size of the solid reaches 4.9 microns, the manganese metering pump, the ammonia metering pump and the alkali metering pump stop feeding liquid, the reaction materials enter a centrifuge for spin-drying, and are leached by 0.5mol/L alkali solution, and the temperature of the alkali solution is 80 DEG C o And C, washing the material and the alkali solution by using pure water at the weight ratio of 1.
Step five, transferring the centrifuged material to 130 o Drying in a C oven until the moisture content is less than 3500ppm, cooling to room temperature, sieving the dried and cooled material with a 325-mesh ultrasonic vibration sieve to obtain trimanganese tetroxide material with single crystal phase, wherein the Mn% is 71.35%, the Na 137ppm, the S1360ppm, and the tap density is 2.39g/cm 3 Specific surface area of 0.73m 2 (g), the particle size distribution was 0.68.
Example 2
Step one, preparing 2.1mol/L manganese sulfate solution, and adding 2.0g/L polyvinylpyrrolidone.
Step two, adding 79.712kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 40 o And C, adding 0.196kg of 9mol/L ammonia to ensure that the ammonia content is in the range of 0.4-0.5 g/L.
And step three, regulating the flow of a manganese metering pump to be 100ml/min, regulating the flow of an ammonia metering pump and an alkaline solution metering pump, enabling the ammonia metering pump and the alkaline solution metering pump to flow into a reaction kettle in a parallel mode, controlling the ammonia content to be within the range of 0.4-0.5g/L and the alkaline content to be within the range of 0-0.3g/L, simultaneously introducing air with the flow of 10ml/min, stably controlling the pH to be 11.80 within 0-8h, reducing the reaction pH to 11.05 from 11.80 within 8-8.5h, reducing the reaction pH to 10.45 from 11.05 within 54-54.5h, and stably controlling the reaction pH until the reaction is finished. The initial particle size for 1h of reaction was D50.62. Mu.m.
Step four, after the reaction is carried out for 100 hours, the particle size of the solid reaches 5.6 microns, the manganese metering pump, the ammonia metering pump and the alkali metering pump stop feeding liquid, the reaction materials enter a centrifugal machine for spin-drying, 0.5mol/L alkali solution is used for leaching, and the temperature of the alkali solution is 80 DEG o And C, washing the material and the alkali solution by using pure water at the weight ratio of 1.
Step five, transferring the centrifuged material to 130 o Drying in a C oven until the moisture content is less than 3500ppm, cooling to room temperature, sieving the dried and cooled material with a 325-mesh ultrasonic vibration sieve to obtain trimanganese tetroxide material with single crystal phase, wherein the Mn content is 71.51%, the Na content is 123ppm, the S content is 1270ppm, and the tap density is 2.46g/cm 3 The specific surface area is 0.61m 2 (g), the particle size distribution was 0.54.
Example 3
Step one, preparing 2.5mol/L manganese sulfate solution, and adding 2.0g/L polyethylene glycol 1000.
Step two, adding 35.0kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 70 o And C, adding 1.4kg of 8mol/L sodium hydroxide to ensure that the alkali content is within the range of 9-10g/L and the pH is 13.0-13.4.
And step three, regulating the flow of a manganese metering pump to be 100ml/min, regulating the flow of an ammonia metering pump and an alkali solution metering pump, enabling the ammonia metering pump and the alkali solution metering pump to flow into a reaction kettle in parallel, controlling the ammonia content to be within the range of 0.5-1.0g/L and the alkali content to be within the range of 0-0.3g/L, simultaneously introducing air with the flow of 10ml/min, and stably controlling the pH value of the reaction to be 8.5-9 until the reaction is finished. The initial particle size for 1h of reaction was D50 0.99. Mu.m.
Step four, after the reaction for 20 hours, the particle size of the solid reaches 2.6 microns, and a manganese metering pump and ammonia are usedStopping feeding liquid into the metering pump and the alkali metering pump, allowing the reaction materials to enter a centrifugal machine for spin-drying, leaching with 1.0mol/L alkali solution, and allowing the temperature of the alkali solution to be 80% o And C, washing the material and the alkali solution by using pure water at the weight ratio of 1.
Step five, transferring the centrifuged material to 130 o Drying in a C drying oven until the moisture content is less than 3500ppm, cooling to room temperature, sieving the dried and cooled material with a 325-mesh ultrasonic vibration sieve to obtain the trimanganese tetroxide material with single crystal phase, wherein the Mn content is 71.21 percent, the Na content is 96ppm, the S content is 1568ppm, and the tap density is 2.28g/cm 3 Specific surface area of 1.42m 2 (g), the particle size distribution was 0.61.
Example 4
Step one, preparing 2.1mol/L manganese sulfate solution, and adding 1.0g/L sodium citrate.
Step two, adding 80.0kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 40 DEG o C。
And step three, regulating the flow of a manganese metering pump to be 100ml/min, regulating the flow of an ammonia metering pump and an alkaline solution metering pump, enabling the ammonia metering pump and the alkaline solution metering pump to flow into a reaction kettle in a parallel mode, controlling the ammonia content to be within the range of 0.4-0.5g/L and the alkaline content to be within the range of 0-0.3g/L, simultaneously introducing air with the flow of 10ml/min, stably controlling the pH to be 12.50 within 0-10h, reducing the reaction pH to 11.50 from 12.50 within 10-12h, reducing the reaction pH to 9.50 from 11.50 within 140-150h, and stably controlling the reaction pH until the reaction is finished. The initial particle size for 1h of reaction was D50.04. Mu.m.
Step four, after the reaction is carried out for 200 hours, the particle size of the solid reaches 7.9 micrometers, the manganese metering pump, the ammonia metering pump and the alkali metering pump stop feeding liquid, the reaction materials enter a centrifuge for spin-drying, 0.5mol/L alkali solution is used for leaching, and the temperature of the alkali solution is 80 DEG o And C, washing the material and the alkali solution at a weight ratio of 1.
Step five, transferring the centrifuged material to 100 o C, drying in an oven until the moisture content is less than 3500ppm, cooling to room temperature, and sieving the dried and cooled material with a 325-mesh ultrasonic vibration sieveScreening to obtain the trimanganese tetroxide material with single crystal phase, wherein the Mn content is 71.43 percent, the Na 113ppm and the S1014ppm are contained, and the tap density is 2.57g/cm 3 Specific surface area of 0.32m 2 (g), the particle size distribution was 0.57.
Example 5
Step one, preparing 2.5mol/L manganese sulfate solution, and adding 1.0g/L polyethylene glycol 1000. Adding a certain amount of sodium metaaluminate into 8mol/L potassium hydroxide solution.
Step two, adding 79.712kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 40 o And C, adding 0.092kg of 8mol/L sodium hydroxide to ensure that the alkali content is within the range of 0-0.3g/L, adding 0.196kg of 9mol/L ammonia to ensure that the ammonia content is within the range of 0.4-0.5g/L, and adjusting the pH to 11.75-11.85.
Step three, regulating the flow of a manganese metering pump to be 100ml/min, adjusting the flow of an ammonia metering pump and an aluminum alkaline solution metering pump, enabling the ammonia metering pump and the aluminum alkaline solution metering pump to flow into a reaction kettle in a parallel mode, controlling the ammonia content to be within the range of 0.4-0.5g/L and the alkaline content to be within the range of 0-0.3g/L, simultaneously introducing air with the flow of 10ml/min, stably controlling the pH to be 11.80 within 0-6h, reducing the reaction pH to 11.05 within 6-6.5h, reducing the reaction pH to 10.45 from 11.05 within 14-14.5h, and stably controlling the reaction pH until the reaction is finished. The initial particle size of the reaction was D50.40 μm for 1 h.
Step four, after reacting for 76 hours, the particle size of the solid reaches 4.9 microns, the manganese metering pump, the ammonia metering pump and the aluminum alkali metering pump stop feeding liquid, the reaction materials enter a centrifuge for spin-drying, and are leached by 0.5mol/L alkali solution, and the temperature of the alkali solution is 80 DEG C o And C, washing the material and the alkali solution at a weight ratio of 1.
Step five, transferring the centrifuged material to 130 o Drying in a C drying oven until the moisture content is less than 3500ppm, cooling to room temperature, sieving the dried and cooled material by using a 325-mesh ultrasonic vibration sieve to obtain the manganous-manganic oxide material with the aluminum doping amount of 0.3 percent, wherein the Mn content is 71.15 percent, the Na content is 124ppm, the S content is 1254ppm, and the tap density is 2.35g/cm 3 The specific surface area is 0.93m 2 (g), the particle size distribution was 0.56.
Comparative example 1
Step one, preparing 2.5mol/L manganese sulfate solution, and adding 1.0g/L sodium dodecyl benzene sulfonate.
Step two, adding 35.0kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 70 o And C, adding 1.4kg of 8mol/L sodium hydroxide to ensure that the pH value is 13.4-14.0.
And step three, regulating the flow of the ammonia metering pump when the flow of the manganese metering pump is 100ml/min, enabling the manganese metering pump to flow into the reaction kettle in a parallel mode, controlling the ammonia content to be within the range of 5-6g/L, simultaneously introducing air with the flow of 20ml/min, and stably controlling the pH value of the reaction to be 9.0-9.5 until the reaction is finished. The initial particle size of the reaction was D50.56 μm for 1 h.
Step four, after 10 hours of reaction, the particle size of the solid reaches 4.3 microns, the manganese metering pump and the ammonia metering pump stop feeding liquid, the reaction materials enter a centrifuge for spin-drying, 0.5mol/L alkali solution is used for leaching, and the temperature of the alkali solution is 80 DEG o And C, washing the material and the alkali solution at a weight ratio of 1.
Step five, transferring the centrifuged material to 130 o Drying in a C oven until the moisture content is less than 3500ppm, cooling to room temperature, sieving the dried and cooled material with a 325 mesh ultrasonic vibration sieve to obtain trimanganese tetroxide material with single crystal phase, wherein Mn% is 69.75%, na 61ppm, S5891ppm, and tap density is 1.40g/cm 3 Specific surface area of 14.94m 2 (g), the particle size distribution was 1.62.
Comparative example 2
Step one, preparing 2.5mol/L manganese sulfate solution, and adding 1.0g/L polyethylene glycol 1000.
Step two, adding 35.0kg of pure water into the reaction kettle, wherein the stirring speed of the reaction kettle is 745r/min, and the temperature is 70 o And C, adding 0.14kg of 8mol/L sodium hydroxide to ensure that the alkali content is within the range of 0.8-1.0g/L, adding 0.062kg of 9mol/L ammonia to ensure that the ammonia content is within the range of 0-0.3g/L, and ensuring that the pH is 12.0-13.0.
And step three, regulating the flow of a manganese metering pump to be 100ml/min, regulating the flow of an ammonia metering pump and an alkali solution metering pump, enabling the ammonia metering pump and the alkali solution metering pump to flow into a reaction kettle in parallel, controlling the ammonia content to be within the range of 0-0.3g/L, simultaneously introducing air with the flow of 10ml/min, and stably controlling the pH value of the reaction to be 6.0-7.0 until the reaction is finished. The initial particle size of the reaction was D50 0.98. Mu.m for 1 h.
Step four, after the reaction is carried out for 17 hours, the particle size of the solid reaches 1.5 micrometers, the manganese metering pump, the ammonia metering pump and the alkali metering pump stop feeding liquid, the reaction materials enter a centrifugal machine for spin-drying, 0.5mol/L alkali solution is used for leaching, and the temperature of the alkali solution is 80 DEG o And C, washing the material and the alkali solution by using pure water at the weight ratio of 1.
Step five, transferring the centrifuged material to 130 o And (3) drying in a C drying oven until the moisture content is less than 3500ppm, cooling to room temperature, and sieving the dried and cooled material by using a 325-mesh ultrasonic vibration sieve to obtain the manganous manganic oxide material which has impurity phases and is not spherical particles, wherein the Mn content is 69.11%, the Na content is 721ppm, and the S content is 2739ppm.
Claims (10)
1. The preparation method of the trimanganese tetroxide material for the lithium manganate with controllable particle size is characterized by comprising the following steps:
preparing a manganese-containing solution, and adding a surfactant into the manganese-containing solution;
preparing reaction base solution from one or more of pure water, ammonia solution and alkali solution in a reaction kettle, wherein the pH value is 7.0-13.4, and keeping the rotating speed and the temperature of the reaction kettle within the required range;
step three, enabling the alkali solution, the ammonia solution, the manganese-containing solution and air to flow into a reaction kettle in a parallel mode to react, and controlling the pH value of the reaction to be 8.5-11.85;
step four, after the growth is carried out for a period of time, the particle size meets the requirement, the liquid feeding is stopped, the reaction materials enter a centrifugal machine for spin-drying, 0.1-1mol/L alkali solution is used for leaching, and the temperature of the alkali solution is 25 DEG o C~80 o And C, the weight ratio of the reaction materials to the alkali solution is 1.5 to 1 o C~60 o C, the weight ratio of the reaction materials to the pure water is 1;
step five, transferring the centrifuged reaction material to 100 o C-200 o And C, drying in an oven until the moisture content is less than 3500ppm, cooling to room temperature, and screening the dried and cooled reaction material by using an ultrasonic vibration screen to obtain the trimanganese tetroxide material with a single crystal phase.
2. The method for preparing a trimanganese tetroxide material for lithium manganate with controllable particle size according to claim 1, wherein the manganese-containing solution is prepared from one or more of manganese sulfate, manganese nitrate and manganese chloride, and the concentration of the manganese-containing solution is 1.0-3.0mol/L.
3. The method for preparing the manganous manganic oxide material for lithium manganate with controllable particle size according to claim 1, wherein the surfactant is one or more of cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, dodecyltrimethylammonium chloride, sodium dodecylsulfate, sodium dodecylbenzenesulfonate, polyethylene glycol, polyvinylpyrrolidone, ethanol, n-butanol, sodium citrate, ethylenediamine tetraacetic acid, urea, polyoxyethylene fatty acid, polyoxyethylene alkylamine, and palmityl alcohol, and the concentration of the surfactant is 0.5g/L-3.5g/L.
4. The method for preparing a trimanganese tetroxide material for lithium manganate with controllable particle size according to claim 1, wherein the concentration of the ammonia solution is 0.9-10mol/L, the alkali solution is one or more of sodium hydroxide and potassium hydroxide, and the concentration of the alkali solution is 0.8-8mol/L.
5. The method for preparing a trimanganese tetroxide material for lithium manganate with controllable particle size according to claim 1, wherein in the third step, the flow rate of the manganese-containing solution is 70-300mL/min, and the flow rate of the introduced air is 0-20mL/min.
6. The method for preparing a manganomanganic oxide material for lithium manganate with controllable particle size according to claim 1, wherein in the second step, the ammonia solution isThe concentration is 0.9-10mol/L; the ammonia solution is a precipitator and a complexing agent in the reaction process; the concentration of the alkali solution is 0.8-8mol/L; the content of alkali solution in the reaction bottom liquid is 0-10g/L, the content of ammonia solution is 0-10g/L, the rotating speed of the reaction kettle is 500-1000r/min, and the reaction temperature is 30-80 o C。
7. The method for preparing a trimanganese tetroxide material for lithium manganate with controllable particle size according to claim 1, wherein in the third step, the ratio of alkali solution to ammonia solution in the reaction process is 1.
8. The method for preparing a trimanganese tetroxide material for lithium manganate with controllable particle size according to claim 1, wherein in the fourth step, the growth time is 20-200h.
9. The method for preparing a trimanganese tetroxide material for lithium manganate with controllable particle size according to claim 1, wherein the particle size of the trimanganese tetroxide material with single crystal phase finally obtained in the fifth step is less than 10 μm.
10. A trimanganese tetroxide material for lithium manganate with controllable particle size, which is characterized in that the trimanganese tetroxide material prepared by the preparation method of any one of claims 1 to 8 has the advantages of single crystal phase, controllable particle size, uniform particle size, high purity, good dispersibility and tap density of more than 2.1g/cm 3 ，BET 0.5-5m 2 G, good sphericity.
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