CN115353160A - Preparation method of battery-grade nickel-cobalt-manganese ternary sulfate solution - Google Patents
Preparation method of battery-grade nickel-cobalt-manganese ternary sulfate solution Download PDFInfo
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- CN115353160A CN115353160A CN202211155269.8A CN202211155269A CN115353160A CN 115353160 A CN115353160 A CN 115353160A CN 202211155269 A CN202211155269 A CN 202211155269A CN 115353160 A CN115353160 A CN 115353160A
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- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 29
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 32
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 19
- 239000010941 cobalt Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 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 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 239000011572 manganese Substances 0.000 claims description 9
- 238000003825 pressing Methods 0.000 claims description 5
- 230000005587 bubbling Effects 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 8
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 16
- 244000046052 Phaseolus vulgaris Species 0.000 description 16
- 239000002994 raw material Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000002243 precursor Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000007788 liquid Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000003513 alkali Substances 0.000 description 7
- 238000003860 storage Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229940099596 manganese sulfate Drugs 0.000 description 5
- 239000011702 manganese sulphate Substances 0.000 description 5
- 235000007079 manganese sulphate Nutrition 0.000 description 5
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 239000012535 impurity Substances 0.000 description 4
- 238000005070 sampling Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- VNTQORJESGFLAZ-UHFFFAOYSA-H cobalt(2+) manganese(2+) nickel(2+) trisulfate Chemical compound [Mn++].[Co++].[Ni++].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VNTQORJESGFLAZ-UHFFFAOYSA-H 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- -1 manganese metals Chemical class 0.000 description 1
- 229940053662 nickel sulfate Drugs 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G45/00—Compounds of manganese
- C01G45/10—Sulfates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G51/00—Compounds of cobalt
- C01G51/10—Sulfates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of a battery-grade nickel-cobalt-manganese ternary sulfate solution, which comprises the following steps: s1, uniformly mixing concentrated sulfuric acid and pure water to obtain a sulfuric acid solution; s2, adding nickel and cobalt into the sulfuric acid solution, continuously stirring, introducing steam, heating and keeping the temperature at 80-90 ℃ for reacting for 6-8h; and S3, slowly adding manganese, adjusting the pH to 5-5.5 after the reaction is finished, filtering, and demagnetizing to obtain the battery-grade nickel-cobalt-manganese ternary sulfate solution. The method has short time consumption and accurate material preparation.
Description
Technical Field
The invention relates to a preparation method of a battery-grade nickel-cobalt-manganese ternary sulfate solution, belonging to the field of material science.
Background
The raw material used for preparing the precursor material of the anode of the nickel-cobalt-manganese ternary battery is mainly sulfate or sulfate solution. The preparation of sulfate (nickel sulfate, cobalt sulfate, manganese sulfate) solution is mainly prepared by dissolving sulfate and fine filtering. However, the process of this preparation method is time-consuming, or inaccurate in dosing due to variations in the water content of the sulfate or inaccurate in dosing due to variations in the mass flow meter.
Therefore, the development of a preparation method of the nickel-cobalt-manganese ternary sulfate solution with short time consumption and accurate material preparation is urgently needed.
Disclosure of Invention
The invention provides a preparation method of a battery-grade nickel-cobalt-manganese ternary sulfate solution, which can effectively solve the problems.
The invention is realized by the following steps:
a preparation method of a battery-grade nickel-cobalt-manganese ternary sulfate solution comprises the following steps:
s1, uniformly mixing concentrated sulfuric acid and pure water to obtain a sulfuric acid solution;
s2, adding nickel and cobalt into the sulfuric acid solution, continuously stirring, introducing steam, heating and keeping the temperature at 80-90 ℃ for reacting for 6-8h;
and S3, slowly adding manganese, after the reaction is finished, adjusting the pH value to 5-5.5, filtering, and removing magnetism to obtain the battery-grade nickel-cobalt-manganese ternary sulfate solution.
In some embodiments, in step S1, the sulfuric acid solution has a concentration of 4-6% by volume.
In some embodiments, in step S2, the induced air is also turned on at the same time, and the reaction is performed until the bubbles disappear.
In some embodiments, in step S3, the slow manganese feeding speed is preferably no bubbling.
In some embodiments, in step S3, the adjusting pH is: if the pH value of the solution is more than or equal to 5.5, adding a small amount of hydrogen peroxide, if the pH value of the solution is less than 5, adding 10wt% of sodium hydroxide into the solution at the same time, and adjusting the pH value to 5-5.5.
In some embodiments, in step S3, the filtering is a filter-press followed by a fine filtering.
The beneficial effects of the invention are:
according to the invention, nickel, cobalt and manganese metals are directly used for batching, dissolving and removing impurities, and the battery-grade sulfate solution with qualified metal quantity proportion is prepared at one time, so that inaccurate batching caused by the deviation of the water content of sulfate or inaccurate batching caused by the deviation of a mass flowmeter in the traditional method is avoided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are required to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a flow chart of a preparation process of a battery-grade nickel-cobalt-manganese ternary sulfate solution provided by an embodiment of the invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention. Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention. All other embodiments, which can be obtained by a person skilled in the art without inventive efforts based on the embodiments of the present invention, are within the scope of protection of the present invention.
In the description of the present invention, the terms "first" and "second" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The embodiment of the invention provides a preparation method of a battery-grade nickel-cobalt-manganese ternary sulfate solution, which comprises the following steps:
s1, uniformly mixing concentrated sulfuric acid and pure water to obtain a sulfuric acid solution;
s2, adding nickel and cobalt into the sulfuric acid solution, continuously stirring, introducing steam, heating and keeping the temperature at 80-90 ℃ for reacting for 6-8h;
and S3, slowly adding manganese, after the reaction is finished, adjusting the pH value to 5-5.5, filtering, and removing magnetism to obtain the battery-grade nickel-cobalt-manganese ternary sulfate solution.
In the embodiment of the invention, metal simple substances are directly used, for example, metal nickel is nickel bean or nickel powder (99.8%), metal cobalt is cobalt bean or cobalt powder (99.8%), metal manganese is manganese powder (99.5%), no other auxiliary materials are needed to be added, impurities are controllable, the requirement of preparing the battery-grade ternary precursor on the impurities can be met, the one-time batching qualification rate is high, and the method is not influenced by factors such as raw material purity, moisture, mass flowmeter accuracy and temperature; the metal proportion can be adjusted according to the needs, such as the ternary precursor products of 811/622/523 and the like.
In the embodiment of the invention, the materials are fed in two sections according to the reaction activity of nickel, cobalt and manganese, so that the alkali consumption is reduced, the reaction rate is improved, the prepared solution can be directly used for preparing a ternary precursor for production, the processes of intermediate batching, detection and the like are reduced, and the production efficiency is improved.
In some embodiments, in step S1, the sulfuric acid solution has a concentration of 4 to 6% by volume, which is determined according to the sulfate concentration required for precursor production.
In some embodiments, in step S2, the induced air is also turned on simultaneously, and the reaction is performed until the bubbles disappear.
In some embodiments, in step S3, the slow manganese feeding speed is preferably no bubbling.
In some embodiments, in step S3, the adjusting pH is: if the pH value of the solution is more than or equal to 5.5, adding a small amount of hydrogen peroxide, if the pH value of the solution is less than 5, adding 10wt% of sodium hydroxide simultaneously, adjusting the pH value to 5-5.5, wherein the pH value can hydrolyze iron or aluminum introduced in the raw materials or the production process to obtain iron hydroxide and aluminum hydroxide precipitates, and separating.
In some embodiments, in step S3, the filtering is performed by performing filter pressing and then performing precision filtering, which is an impurity removal process to ensure that the finished product meets the use standard of the precursor.
Example 1
Taking the ternary precursor raw material of nickel, cobalt and manganese 523 as an example, the raw material is fed twice.
Production raw materials: raw materials in mole fraction ratio: 1000kg of nickel beans, 400kg of cobalt beans, 560kg of manganese powder, 2400L of concentrated sulfuric acid, pure water, 28v/v% of hydrogen peroxide and 10wt% of sodium hydroxide.
(1) Preparing liquid: 50000L of pure water was added to the reaction kettle, 2400L of 98% concentrated sulfuric acid was slowly added to the pure water, and stirring was started during the process (it took 0.5 h).
(2) Feeding 1: putting 1000kg of nickel beans and 400kg of cobalt beans into a reaction kettle for reaction, continuously stirring in the process, introducing steam, heating to keep the temperature at 80-90 ℃, simultaneously starting induced air, reacting until the acidity of the solution is about 1mol/L, and eliminating bubbles in the reaction kettle (the reaction time is 6-8 h).
(3) Feeding 2: 560kg of manganese powder is slowly put into the reaction kettle in the last step at a speed which is suitable for avoiding overflowing the tank, and after the material is put, the reaction is carried out until no bubbles are generated (a small amount of acid can be supplemented when the reaction is too slow, and the reaction time is about 4-8 h).
(4) Detecting the pH value of the solution, and adding a small amount of hydrogen peroxide to perform the next step if the pH value of the solution is more than or equal to 5; if the pH value of the solution is less than 5, adding hydrogen peroxide and 10wt% of liquid alkali at the same time to adjust the pH value until the pH value is more than or equal to 5 (reacting for 0-1 h).
(5) And (3) carrying out filter pressing on the solution, carrying out precise filtration, transferring the solution into a finished product storage tank after a pipeline demagnetizer, and sampling, inspecting and analyzing (the time is 1.5 h).
The inspection method of this embodiment is an inspection using ICP or atomic absorption spectroscopy.
The total time consumed in this example was 12-19h.
The test data are shown in Table 1.
TABLE 1 ternary Ni-Co-Mn feed liquid detection data
As can be seen from the data in Table 1, the method of the present embodiment can control the proportion of nickel, cobalt and manganese and the finished product can reach the use standard of the precursor (GB/T26300-2020), and can directly perform precursor production.
Comparative example 1
Taking the ternary precursor raw material of nickel, cobalt and manganese 523 as an example, the raw material is fed for three times.
Production raw materials: raw materials in mole fraction ratio: 1000kg of nickel beans, 400kg of cobalt beans, 560kg of manganese powder, 2400kg of concentrated sulfuric acid, pure water, 28v/v% of hydrogen peroxide and 10wt% of sodium hydroxide.
(1) Preparing a liquid: 50000L of pure water was added to the reaction kettle, 3000L of 98% concentrated sulfuric acid was slowly added to the pure water, and stirring was started during the process (time consumed 0.5 h).
(2) Feeding: putting 2500kg of nickel beans into a reaction kettle, continuously stirring in the process, introducing steam, heating to keep the temperature at 80-90 ℃, simultaneously starting induced air, reacting until the acidity of the solution is about 1mol/L, and eliminating bubbles in the reaction kettle (the reaction time is 6-8 h).
(3) Detecting the pH value of the solution, and adding a small amount of hydrogen peroxide to perform the next step if the pH value of the solution is more than or equal to 5.5; if the pH value of the solution is less than 5, adding hydrogen peroxide and 10wt% of liquid alkali at the same time to adjust the pH value until the pH value is more than or equal to 5 (reacting for 1-2 h).
(4) And (3) carrying out filter pressing on the nickel sulfate solution, carrying out precision filtration, transferring the nickel sulfate solution into a nickel sulfate finished product storage tank after a pipeline demagnetizer is removed, and sampling, inspecting and analyzing (the time is 1.5 h).
(5) And (3) repeating the steps 1-4, putting 2500kg of cobalt beans into the reaction kettle, preparing a cobalt sulfate solution, transferring the cobalt sulfate solution into a cobalt sulfate finished product storage tank, and sampling for analysis (the time is 9-12 hours).
(6) And (5) repeating the steps 1-4, putting 2500kg of manganese powder into the reaction kettle to prepare a manganese sulfate solution, transferring the manganese sulfate solution into a finished manganese sulfate storage tank, and sampling and sending for analysis (the time is 7-10 hours).
(7) Preparing materials: taking 1000kg of nickel sulfate, 400kg of cobalt sulfate and 560kg of manganese sulfate according to the concentration calculation of the nickel-cobalt-manganese sulfate solution, and mixing in a reaction kettle for dosing (the time is 0.5 h).
(8) Taking the mixed feed liquid, inspecting, and transferring to a product storage tank (consuming 1.5 h).
The comparative example was examined in the same manner as in example 1.
The total time of this comparative example was 29 to 36 hours.
Comparative example 2
Taking the ternary precursor raw material of nickel, cobalt and manganese 523 as an example, the raw material is fed once.
Production raw materials: raw materials in mole fraction ratio: 1000kg of nickel beans, 400kg of cobalt beans, 560kg of manganese powder, 2400kg of concentrated sulfuric acid, pure water, 28v/v% of hydrogen peroxide and 10wt% of sodium hydroxide.
(1) Preparing a liquid: 50000L of pure water was added to the reaction kettle, 2400L of 98% concentrated sulfuric acid was slowly added to the pure water, and stirring was started during the process (it took 0.5 h).
(2) Feeding 1: putting 1000kg of nickel beans, 400kg of cobalt beans and 560kg of manganese powder into a reaction kettle for reaction, continuously stirring in the process, introducing steam, heating to keep the temperature at 80-90 ℃, simultaneously starting induced air, reacting until the solution has no obvious solid, and eliminating bubbles in the reaction kettle (the reaction can supplement a small amount of acid when the reaction is too slow, and the reaction time is 16-24 h).
(3) Detecting the pH value of the solution, and adding a small amount of hydrogen peroxide to perform the next step if the pH value of the solution is more than or equal to 5.5; if the pH value of the solution is less than 5, adding hydrogen peroxide and 10% liquid alkali at the same time to adjust the pH value until the pH value is more than or equal to 5 (reacting for 0-1 h).
(4) Carrying out filter pressing on the solution, carrying out precise filtration, and transferring the solution into a finished product storage tank after a pipeline demagnetizer; the sample was taken for analysis (time-consuming 1.5 h).
The comparative example was examined in the same manner as in example 1.
The total time consumption of the comparative example is 20-27h.
A combined analysis of example 1 and comparative examples 1 and 2 revealed that the total time consumption of example 1 was significantly lower than that of comparative examples 1 and 2. The analysis reason is considered as follows: in example 1, since the reaction rate was high in the case of the manganese powder having a high metal activity and a low acid concentration, the solution of charge 2 had a pH adjusting effect at the same time, and the free acid in the solution was small at the end of the reaction, and the pH adjusting time was shortened. In comparative example 1, it took about 12 hours to prepare a single sulfate solution, and more three sulfate solutions were tested, which took 4.5 hours more to test, and in order to ensure that each time of the reaction rate was excessive, the excessive acid in the solution was still excessive after the metal dissolution reaction was completed, and the pH adjustment consumed a large amount of alkali, and consumed a long time. In comparative example 2, since manganese powder has strong metal activity, it reacts preferentially and reacts violently when being charged together, and in order to ensure safety, the charging time is longer, and if acid is not supplemented during the reaction, the concentration of acid in the liquid after the reaction of manganese powder is reduced, the reaction rate of nickel beans and cobalt beans is slowed down, and the reaction time is prolonged.
In addition, in example 1, the time for adjusting the pH was short, and the amount of alkali consumption was also smaller than in comparative example 1 and comparative example 2. In the practical production in the comparative example 1, in order to improve the rate and the acid utilization rate, the multi-stage gradient reaction is adopted to prepare the sulfate solution, the required equipment is more, the occupied area is wide, and the problem does not exist in the embodiment 1.
In conclusion, in example 1, the feeding is performed twice, the time consumption is shorter than that of three times of feeding and one time of feeding, the alkali consumption is low, and the unexpected technical effect and the remarkable technical progress are achieved.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. A preparation method of a battery-grade nickel-cobalt-manganese ternary sulfate solution is characterized by comprising the following steps:
s1, uniformly mixing concentrated sulfuric acid and pure water to obtain a sulfuric acid solution;
s2, adding nickel and cobalt into the sulfuric acid solution, continuously stirring, introducing steam, heating and keeping the temperature at 80-90 ℃ for reacting for 6-8h;
and S3, slowly adding manganese, adjusting the pH to 5-5.5 after the reaction is finished, filtering, and demagnetizing to obtain the battery-grade nickel-cobalt-manganese ternary sulfate solution.
2. The method for preparing a battery grade nickel cobalt manganese ternary sulfate solution according to claim 1, wherein in step S1, the volume concentration of the sulfuric acid solution is 4-6%.
3. The method for preparing the battery-grade nickel-cobalt-manganese ternary sulfate solution according to claim 1, wherein in step S2, the induced air is also turned on simultaneously, and the reaction is carried out until bubbles disappear.
4. The method for preparing a battery grade nickel cobalt manganese ternary sulfate solution according to claim 1, wherein in step S3, the slow manganese feeding speed is preferably no bubbling.
5. The method of claim 1, wherein in step S3, the pH is adjusted to be: if the pH value of the solution is more than or equal to 5.5, adding a small amount of hydrogen peroxide, if the pH value of the solution is less than 5, adding 10wt% of sodium hydroxide into the solution at the same time, and adjusting the pH value to 5-5.5.
6. The method for preparing the battery-grade nickel-cobalt-manganese ternary sulfate solution according to claim 1, wherein in step S3, the filtering is performed by performing filter pressing first and then performing precision filtering.
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