CN113582244A - Method for reducing sodium content in high-sodium nickel cobalt manganese hydroxide - Google Patents
Method for reducing sodium content in high-sodium nickel cobalt manganese hydroxide Download PDFInfo
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- 239000011734 sodium Substances 0.000 title claims abstract description 105
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 102
- 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 title claims abstract description 55
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 26
- 238000001354 calcination Methods 0.000 claims abstract description 36
- -1 sodium nickel cobalt manganese hydroxide Chemical compound 0.000 claims abstract description 23
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 18
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 13
- 239000001099 ammonium carbonate Substances 0.000 claims description 13
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 4
- 229910052744 lithium Inorganic materials 0.000 abstract description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 8
- 230000018044 dehydration Effects 0.000 description 6
- 238000006297 dehydration reaction Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000011164 primary particle Substances 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000007774 positive electrode material Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WGSBLDIOQQANMK-UHFFFAOYSA-N [Mn].[Co].[Ni].[Na] Chemical compound [Mn].[Co].[Ni].[Na] WGSBLDIOQQANMK-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910017709 Ni Co Inorganic materials 0.000 description 1
- 229910003267 Ni-Co Inorganic materials 0.000 description 1
- 229910003262 Ni‐Co Inorganic materials 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- CXULZQWIHKYPTP-UHFFFAOYSA-N cobalt(2+) manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[O--].[Mn++].[Co++].[Ni++] CXULZQWIHKYPTP-UHFFFAOYSA-N 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
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
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
A method for reducing the sodium content in high-sodium nickel cobalt manganese hydroxide comprises the following steps: firstly, dehydrating the nickel-cobalt-manganese hydroxide which is thoroughly washed to obtain a compound with a general formula: ni1‑x‑yCoxMny(OH)2Wherein x is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and x + y>0, high sodium nickel cobalt manganese hydroxide having a Na content of greater than or equal to 200 ppm; secondly, calcining the high-sodium nickel cobalt manganese hydroxide obtained in the step one at a low temperature in calcining equipment; the low-temperature calcination temperature is 250-400 ℃, and the calcination time is 2-15 h; and thirdly, washing and drying the product after low-temperature calcination to obtain the low-sodium nickel-cobalt-manganese precursor with the sodium content of less than or equal to 50ppm and the sodium removal rate of more than 90%. Book (I)The method solves the problem that the structure compact nickel-cobalt-manganese hydroxide has sodium residue limit only by washing, avoids the condition that the nickel-cobalt-manganese hydroxide generates unqualified products due to high sodium content, can reduce the process steps of lithium mixing and calcining, and improves the production efficiency.
Description
Technical Field
The invention relates to the field of lithium ion battery anode materials, in particular to a method for reducing the sodium content in high-sodium nickel cobalt manganese hydroxide.
Background
The positive electrode material is a key component of the lithium ion battery, generally speaking, the positive electrode material occupies the most important position in the components of the lithium ion battery product, and the quality of the positive electrode material directly determines the performance index of the final lithium ion battery product. The performance of the lithium ion battery anode material is limited by various performance indexes of the nickel-cobalt-manganese hydroxide material to a great extent, so that the control of various indexes of the nickel-cobalt-manganese hydroxide is particularly important.
In recent years, ternary cathode materials are rapidly developed, particularly high-nickel ternary cathode materials and lithium-rich manganese-based cathode materials are an important direction for developing products, the market also shows great demand, compared with low-nickel-cobalt-manganese hydroxide, the high-nickel-cobalt-manganese hydroxide has higher requirements on production process and quality management, the control of impurity content is also more accurate, the existence of trace sodium has influence on the appearance and electrochemical performance of the sintered ternary cathode material, the influence generated by different sodium contents is different, and the stability of the product in actual production also needs to be strictly controlled on the sodium content.
In the synthesis process of the nickel-cobalt-manganese hydroxide, the sodium content is higher due to the characteristics of the product and different production processes, and the phenomenon is more obvious in a product with a compact structure. In the process of growing nickel-cobalt-manganese hydroxide, sodium hydroxide is used as a precipitator in the synthesis, a large amount of sodium ions exist in a system, in the process of nucleation and growth, primary particles of nickel-cobalt-manganese hydroxide are accumulated and grow, so that sodium wrapped and clamped in the primary particles of nickel-cobalt-manganese hydroxide and among layers cannot be washed away, sodium impurities cannot be washed away after the sodium impurities are introduced for the second time in the post-treatment process, the content of the sodium introduced for the second time is generally more than 200ppm, the upper limit of the removal of the sodium impurities exists in the washing process, the sodium content cannot be continuously washed away after the sodium content is reduced to a certain range, and the nickel-cobalt-manganese hydroxide product is unqualified due to the high content of the sodium impurities.
Therefore, how to solve the above-mentioned deficiencies of the prior art is a problem to be solved by the present invention.
Disclosure of Invention
The invention aims to provide a method for reducing the sodium content in high-sodium nickel cobalt manganese hydroxide.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for reducing the sodium content in high-sodium nickel cobalt manganese hydroxide comprises the following steps:
step one, dehydrating the nickel-cobalt-manganese hydroxide which is thoroughly washed to obtain a compound with a general formula: ni1-x-yCoxMny(OH)2Wherein x is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and x + y>0, high sodium nickel cobalt manganese hydroxide having a Na content of greater than or equal to 200 ppm;
step two, calcining the high-sodium nickel cobalt manganese hydroxide obtained in the step one at a low temperature in a calcining device; the low-temperature calcination temperature is 250-400 ℃, and the calcination time is 2-15 h;
and step three, washing and drying the product after low-temperature calcination to obtain the low-sodium nickel-cobalt-manganese precursor with the sodium content of less than or equal to 50ppm and the sodium removal rate of more than 90%.
The relevant content in the above technical solution is explained as follows:
1. in the above scheme, in the step one, the thorough water washing means that the sodium content cannot be reduced again by changing the washing temperature, the washing water amount and the washing times.
2. In the scheme, in the second step, ammonium carbonate is added into the high-sodium nickel cobalt manganese hydroxide before low-temperature calcination is carried out, the mass ratio of the ammonium carbonate to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, and the ammonium carbonate and the high-sodium nickel cobalt manganese hydroxide are uniformly mixed; the ammonium carbonate decomposes during the heating stage to produce a gas, the escape of which facilitates the opening of the spacing between the particles of the high sodium nickel cobalt manganese hydroxide and thus facilitates the later sodium removal by scrubbing.
In the third step, the sodium content of the low-sodium nickel cobalt manganese precursor is less than or equal to 30ppm, and the sodium removal rate is more than 95%.
3. In the above scheme, in the third step, the drying temperature of the nickel-cobalt-manganese hydroxide is 120-190 ℃.
4. In the scheme, in the third step, the moisture control range of the dried low-sodium nickel cobalt manganese precursor is 0.1-0.3%.
5. In the above scheme, in the third step, the low-sodium nickel cobalt manganese precursor is a low-sodium nickel cobalt manganese hydroxide or/and a low-sodium nickel cobalt manganese oxide.
6. In the scheme, the average particle size D50 of the high-sodium nickel cobalt manganese hydroxide is 3-20 mu m, and the SPAN SPAN is 0.5-1.2.
7. In the scheme, the specific surface area of the high-sodium nickel cobalt manganese hydroxide is 3-15 m2The specific surface area of the low-sodium nickel-cobalt-manganese precursor is 80-200 m2/g。
The working principle and the advantages of the invention are as follows:
according to the invention, the high-sodium nickel cobalt manganese hydroxide with a compact structure is treated by a low-temperature calcination and washing mode, the primary particle spacing and the interlayer spacing of the nickel cobalt manganese hydroxide are enlarged at high temperature, which means that the specific surface area of the nickel cobalt manganese hydroxide is enlarged, sodium ions entering between primary particles and between layers of the nickel cobalt manganese hydroxide can be easily removed in the nucleation and growth processes of the nickel cobalt manganese hydroxide by washing after calcination, so that the effect of reducing the sodium content is achieved, the nickel cobalt manganese hydroxide can be used only by re-measuring the amount of combination during lithium mixing and sintering, and the generation of the unqualified product caused by the high sodium content is avoided.
Detailed Description
The invention is further described below with reference to the following examples:
example (b): the present disclosure will be described in detail below, and it is to be understood that variations and modifications can be made by the techniques taught in the present disclosure without departing from the spirit and scope of the present disclosure by those skilled in the art after understanding the present disclosure.
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the disclosure.
As used herein, the term (terms), unless otherwise indicated, shall generally have the ordinary meaning as commonly understood by one of ordinary skill in the art, in this written description and in the claims. Certain words used to describe the disclosure are discussed below or elsewhere in this specification to provide additional guidance to those skilled in the art in describing the disclosure.
Example 1:
first, high sodium nickel cobalt manganese hydroxide Ni with a sodium content of the lowest value is washed2+ 0.85Co2+ 0.1Mn2+ 0.15(OH)2And (4) performing centrifugal dehydration.
Then, dehydrating the high sodium nickel cobalt manganese hydroxide Ni2+ 0.85Co2+ 0.1Mn2+ 0.15(OH)2And adding ammonium carbonate, wherein the mass ratio of the added amount to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, mixing, and then putting into a calcining furnace for low-temperature calcination, wherein the temperature is set to be 400 ℃, and the time is set to be 4 hours.
And finally, washing the product calcined at the low temperature for 2 times, and continuously drying at 150 ℃ until the moisture is 0.1% to obtain the low-sodium nickel cobalt manganese precursor.
Example 2:
first, high sodium nickel cobalt manganese hydroxide Ni with a sodium content of the lowest value is washed2+ 0.92Co2+ 0.05Mn2+ 0.03(OH)2And (4) performing centrifugal dehydration.
Then, dehydrating the high sodium nickel cobalt manganese hydroxide Ni2+ 0.92Co2+ 0.05Mn2+ 0.03(OH)2And adding ammonium carbonate, wherein the mass ratio of the added amount to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, mixing, and then putting into a calcining furnace for low-temperature calcination, wherein the temperature is set to 300 ℃, and the time is set to 6 hours.
And finally, washing the product calcined at the low temperature for 2 times, and continuously drying at 120 ℃ until the moisture is 0.3% to obtain the low-sodium nickel cobalt manganese precursor.
Example 3:
first, high sodium nickel cobalt manganese hydroxide Ni with a sodium content of the lowest value is washed2+ 0.92Co2+ 0.05Mn2+ 0.03(OH)2And (4) performing filter pressing dehydration.
Then, dehydrating the high sodium nickel cobalt manganese hydroxide Ni2+ 0.92Co2+ 0.05Mn2+ 0.03(OH)2And adding ammonium carbonate, wherein the mass ratio of the added amount to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, mixing, and then putting into a calcining furnace for low-temperature calcination at the temperature of 400 ℃ for 2 hours.
And finally, washing the product calcined at the low temperature for 2 times, and continuously drying at 120 ℃ until the moisture is 0.3% to obtain the low-sodium nickel cobalt manganese precursor.
Example 4:
first, high sodium nickel cobalt hydroxide Ni with a sodium content of the lowest value is washed2+ 0.85Co2+ 0.15(OH)2And (4) performing filter pressing dehydration.
Then, dehydrating the Ni-Co hydroxide with high sodium content2+ 0.85Co2+ 0.15(OH)2And adding ammonium carbonate, wherein the mass ratio of the added amount to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, mixing, and then putting into a calcining furnace for low-temperature calcination, wherein the temperature is set to 350 ℃, and the time is set to 4 hours.
And finally, washing the product calcined at the low temperature for 2 times, and continuously drying at 170 ℃ until the moisture is 0.3% to obtain the low-sodium nickel cobalt precursor.
Example 5:
first, high sodium nickel manganese hydroxide Ni with a sodium content of the lowest value is washed2+ 0.80Mn2+ 0.20(OH)2And (4) performing filter pressing dehydration.
Then, dehydrating the high sodium nickel manganese hydroxide Ni2+ 0.80Mn2+ 0.20(OH)2And adding ammonium carbonate, wherein the mass ratio of the added amount to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, mixing, and then putting into a calcining furnace for low-temperature calcination, wherein the temperature is set to be 250 ℃, and the time is set to be 6 hours.
And finally, washing the product calcined at the low temperature for 2 times, and continuously drying at 190 ℃ until the moisture is 0.3% to obtain the low-sodium nickel manganese precursor.
Example 6:
first, high sodium nickel manganese hydroxide Ni with a sodium content of the lowest value is washed2+ 0.20Mn2+ 0.80(OH)2And (4) performing filter pressing dehydration.
Then, dehydrating the high sodium nickel manganese hydroxide Ni2+ 0.20Mn2+ 0.80(OH)2And adding ammonium carbonate, wherein the mass ratio of the added amount to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, mixing, and then putting into a calcining furnace for low-temperature calcination, wherein the temperature is set to be 250 ℃, and the time is set to be 15 hours.
And finally, washing the product calcined at the low temperature for 2 times, and continuously drying at 190 ℃ until the moisture is 0.2% to obtain the low-sodium nickel manganese precursor.
Comparative example 1:
high sodium nickel cobalt manganese hydroxide Ni with minimal sodium content2+ 0.85Co2+ 0.1Mn2+ 0.15(OH)2Drying in a calcining furnace at 150 ℃ until the moisture is 0.1 percent, and stopping drying to obtain the dehydrated high-sodium nickel cobalt manganese hydroxide.
Comparative example 2:
high sodium nickel cobalt manganese hydroxide Ni with minimal sodium content2+ 0.92Co2+ 0.05Mn2+ 0.03(OH)2And drying in a calcining furnace at 120 ℃ until the moisture is 0.3 percent, namely stopping drying to obtain the dehydrated high-sodium nickel cobalt manganese hydroxide.
Comparative example 3:
high sodium nickel cobalt hydroxide Ni with minimal sodium content2+ 0.85Co2+ 0.15(OH)2Drying at 170 deg.C to water content of 0.3%, stopping drying to obtain dehydrated high sodium nickel cobalt hydroxide.
Comparative example 4:
high sodium nickel manganese hydroxide Ni washed to minimum sodium content2+ 0.80Mn2+ 0.20(OH)2And drying at 190 ℃ until the moisture is 0.3%, namely stopping drying to obtain the dehydrated high-sodium nickel manganese hydroxide.
Comparative example 5:
high sodium nickel manganese hydroxide Ni washed to minimum sodium content2+ 0.20Mn2+ 0.80(OH)2And drying at 190 ℃ until the moisture is 0.2%, namely stopping drying to obtain the dehydrated high-sodium nickel manganese hydroxide.
The nickel cobalt manganese hydroxide materials obtained in the examples and comparative examples were tested under the same conditions, and the test data are shown in tables 1 and 2 below:
table 1 high sodium nickel cobalt manganese hydroxide test data:
TABLE 1
The examples in table 1 all use the high nickel cobalt manganese hydroxide of the comparative example, and from the test data it can be seen that: the limit value for reducing the sodium content exists only by removing sodium by a washing method, and the sodium content can not be further reduced after the limit value is reduced to a certain degree.
Table 2 low sodium nickel cobalt manganese precursor test data:
TABLE 2
As can be seen from table 2, the high sodium nickel cobalt manganese hydroxide in the comparative example is calcined and washed by the treatment method of the present invention to obtain a low sodium nickel cobalt manganese precursor, and test data shows that the sodium content is significantly reduced, the sodium removal rate is above 95%, and the reduction range is much larger than that of the conventional washing treatment method; and the specific surface area of the treated product is obviously increased, and the rate capability of the anode material can be further improved.
According to the invention, the nickel-cobalt-manganese hydroxide synthesized by a coprecipitation method and thoroughly washed is taken as a research object, sodium ions remained in primary particles and between layers of the nickel-cobalt-manganese hydroxide are removed by low-temperature calcination and secondary washing, so that the problem of secondary sodium introduction in post-treatment is solved, the problem that the nickel-cobalt-manganese hydroxide with a compact structure has sodium residue limit only by washing is also solved, the condition that the nickel-cobalt-manganese hydroxide generates unqualified products due to higher sodium content is avoided, the process steps of lithium mixing and calcination can be reduced, and the production efficiency is improved.
The above embodiments are merely illustrative of the technical ideas and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (6)
1. A method for reducing the sodium content in high-sodium nickel cobalt manganese hydroxide is characterized by comprising the following steps: the method comprises the following steps:
step one, dehydrating the nickel-cobalt-manganese hydroxide which is thoroughly washed to obtain a compound with a general formula: ni1-x-yCoxMny(OH)2Wherein x is more than or equal to 0 and less than 1, y is more than or equal to 0 and less than 1, and x + y>0, high sodium nickel cobalt manganese hydroxide having a Na content of greater than or equal to 200 ppm;
step two, calcining the high-sodium nickel cobalt manganese hydroxide obtained in the step one at a low temperature in a calcining device, wherein the low-temperature calcining temperature is 250-400 ℃, and the calcining time is 2-15 hours;
and step three, washing and drying the product after low-temperature calcination to obtain the low-sodium nickel-cobalt-manganese precursor with the sodium content of less than or equal to 50ppm and the sodium removal rate of more than 90%.
2. The method of claim 1, wherein: adding ammonium carbonate into the high-sodium nickel cobalt manganese hydroxide before low-temperature calcination, wherein the mass ratio of the ammonium carbonate to the high-sodium nickel cobalt manganese hydroxide is 0.2-1, and uniformly mixing the ammonium carbonate and the high-sodium nickel cobalt manganese hydroxide;
in the third step, the sodium content of the low-sodium nickel cobalt manganese precursor is less than or equal to 30ppm, and the sodium removal rate is more than 95%.
3. The method of claim 1, wherein: in the third step, the drying temperature is 120-190 ℃.
4. The method of claim 1, wherein: in the third step, the moisture control range of the dried low-sodium nickel cobalt manganese precursor is 0.1-0.3%.
5. The method of claim 1, wherein: the average particle size D50 of the high-sodium nickel cobalt manganese hydroxide is 3-20 mu m, and the SPAN SPAN is 0.5-1.2.
6. The method of claim 1, wherein: the specific surface area of the high-sodium nickel cobalt manganese hydroxide is 3-15 m2The specific surface area of the low-sodium nickel-cobalt-manganese precursor is 80-200 m2/g。
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