CN116768287A - Manganese-rich precursor, preparation method thereof, positive electrode material and lithium ion battery - Google Patents
Manganese-rich precursor, preparation method thereof, positive electrode material and lithium ion battery Download PDFInfo
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- CN116768287A CN116768287A CN202310524746.1A CN202310524746A CN116768287A CN 116768287 A CN116768287 A CN 116768287A CN 202310524746 A CN202310524746 A CN 202310524746A CN 116768287 A CN116768287 A CN 116768287A
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- 239000011572 manganese Substances 0.000 title claims abstract description 118
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 107
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000002243 precursor Substances 0.000 title claims abstract description 93
- 239000007774 positive electrode material Substances 0.000 title claims abstract description 23
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 73
- 239000008139 complexing agent Substances 0.000 claims abstract description 65
- 239000000243 solution Substances 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 36
- 239000012266 salt solution Substances 0.000 claims abstract description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000012716 precipitator Substances 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 18
- 238000000975 co-precipitation Methods 0.000 claims abstract description 15
- 239000002270 dispersing agent Substances 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims description 31
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 238000005303 weighing Methods 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000011164 primary particle Substances 0.000 claims description 11
- 238000005245 sintering Methods 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 5
- 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 4
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 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 4
- 239000001632 sodium acetate Substances 0.000 claims description 4
- 235000017281 sodium acetate Nutrition 0.000 claims description 4
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 3
- DZCAZXAJPZCSCU-UHFFFAOYSA-K sodium nitrilotriacetate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CC([O-])=O DZCAZXAJPZCSCU-UHFFFAOYSA-K 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 229960004249 sodium acetate Drugs 0.000 claims description 2
- 229940083575 sodium dodecyl sulfate Drugs 0.000 claims description 2
- UEUXEKPTXMALOB-UHFFFAOYSA-J tetrasodium;2-[2-[bis(carboxylatomethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]C(=O)CN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O UEUXEKPTXMALOB-UHFFFAOYSA-J 0.000 claims description 2
- 230000002194 synthesizing effect Effects 0.000 claims 1
- 239000000047 product Substances 0.000 abstract description 11
- 239000011163 secondary particle Substances 0.000 abstract description 9
- 239000002244 precipitate Substances 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 28
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 20
- 229910052744 lithium Inorganic materials 0.000 description 20
- 239000008367 deionised water Substances 0.000 description 18
- 229910021641 deionized water Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 17
- 230000001276 controlling effect Effects 0.000 description 9
- 238000001000 micrograph Methods 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 4
- 238000005056 compaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000000635 electron micrograph Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910001428 transition metal ion Inorganic materials 0.000 description 2
- 229910003174 MnOOH Inorganic materials 0.000 description 1
- 208000012868 Overgrowth Diseases 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 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
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
-
- 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
-
- 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
-
- 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
- C01P2006/11—Powder tap density
-
- 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
- C01P2006/32—Thermal properties
-
- 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
Abstract
The invention provides a manganese-rich precursor and a preparation method thereof, a positive electrode material and a lithium ion battery, wherein Mn, ni and Co salts are weighed according to a proportion to prepare a mixed salt solution; preparing a precipitant; preparing a complexing agent; adding pure water, a dispersing agent and a complexing agent into a container filled with inert atmosphere to prepare a base solution, controlling the concentration of the complexing agent in the base solution to be 0.10-0.80 mol/L, and adding a precipitant to adjust the pH value of the base solution to be 9.5-12; adding the mixed salt solution, the precipitator and the complexing agent into a container for coprecipitation reaction, wherein the pH is 9.5-12, the temperature is 50-70 ℃, and the rotating speed of the container is 600-1000 r/min; stopping the reaction when the granularity D50 of the precipitated product is 5-12 um; and centrifuging, washing and drying the precipitate to obtain the manganese-rich precursor with thin and uniform primary flaky particle thickness, good secondary particle sphericity and high tap density.
Description
Technical Field
The invention relates to the field of lithium ion battery materials, in particular to a manganese-rich precursor, a preparation method thereof, a positive electrode material and a lithium ion battery.
Background
The lithium ion battery has the advantages of high energy density, good environmental compatibility, long cycle life and the like, and is widely applied to the fields of 3C numbers, power tools, electric automobiles, aerospace, power generation base stations and the like. With the rapid development of new energy automobiles and energy storage fields, the energy density of the lithium ion battery needs to be improved, so as to meet the requirement of long endurance mileage. At present, the theoretical specific capacity of traditional commercial anode materials such as lithium iron phosphate, lithium cobalt oxide, lithium manganate, ternary materials and the like is generally low, so that the further improvement of the energy density of the lithium ion battery is limited. In recent years, a lithium-rich manganese-based positive electrode material has been receiving a great deal of attention because of its advantages of high energy density, high voltage plateau, low cobalt content, environmental friendliness, etc., and is considered as one of the key positive electrode materials for realizing the next-generation high specific energy lithium ion battery.
The existing preparation technology of the lithium-rich manganese-based material and the precursor thereof is still immature, and the large-scale and commercialized wide application of the lithium-rich manganese-based material is restricted. The preparation method of the precursor and the difference of ion reaction environments directly influence the size and the morphology of primary particles of the precursor, thereby influencing the agglomeration mode and the spherical structure of secondary spheres of the precursor. Therefore, the exploration of precursor synthesis conditions and morphology control technology are key to preparing the lithium-rich manganese-based cathode material.
At present, a lithium-rich manganese-based material precursor is generally prepared by adopting a carbonate and hydroxide coprecipitation method. When the carbonate technology is adopted, the precursor is easy to form a round secondary sphere, but the decomposition rate of the carbonate is high, so that the internal pores of the secondary sphere of the sintered material are large, the tap density and the specific energy of the battery are influenced, and the secondary sphere is easy to crush under the condition of high compaction density, so that pole piece pulverization failure is caused. When the hydroxide precursor process similar to the ternary material is adopted, as the manganese content in the lithium-rich manganese-based material is higher, mn & lt2+ & gt ions are excessively fast nucleated in the precipitation process, large primary sheet MnOOH is easy to generate, and the large primary sheets are difficult to agglomerate together to form uniform and compact secondary balls, the hydroxide process is not easy to ball, so that the tap density of the precursor is relatively low, the tap density, the compaction density and the processing performance of the material are affected, and the volume energy density of a battery is further affected. The large thick-plate primary particles have low activity during sintering, high sintering temperature is needed, primary particles of the sintering material are large, and the electrochemical activity of the material is not beneficial to being exerted, so that the sintering material of the lithium-rich manganese-based material hydroxide precursor has obviously lower electrochemical performance compared with the carbonate precursor.
There are some reports on increasing the tap density of lithium-rich manganese-based materials, for example, a sintered lithium-rich manganese-based positive electrode material is mixed with a transition metal salt and a lithium salt again to perform secondary sintering to increase the tap density; and carrying out hydrothermal post-treatment on the lithium-rich manganese-based anode material to obtain the material with high tap density. These methods are generally complex and costly, and are not conducive to scale-up. Some high-tap-density lithium-rich manganese-based anode materials are prepared by adopting a conventional complexing agent method, but the sphericity of the materials is not good, and the primary granularity is too large, so that the electrochemical performance is low. Therefore, how to prepare a layered lithium-rich manganese-based positive electrode material precursor of a hydroxide system with good secondary particle sphericity, high tap density, thin primary flaky particle thickness and uniform size, which can meet the requirements of the lithium-rich manganese-based material on the processing performances such as tap density, compaction density and the like, and has very high electrochemical activity is a technical problem to be solved in the field.
Disclosure of Invention
The invention provides a manganese-rich precursor and a preparation method thereof, a positive electrode material and a lithium ion battery, which are used for solving the defects that secondary particles of the manganese-rich precursor material in the prior art are poor in sphericity, low in tap density, thicker in primary flaky particles and uneven in size, and cannot meet the requirements of processing performances such as tap density, compaction density and the like of a lithium-rich manganese-based material, and realizing the effects of preparing the spherical secondary particle precursor with thin and uniform primary flaky particles, good sphericity of the secondary particles and high tap density.
The invention provides a preparation method of a manganese-rich precursor, which comprises the following steps:
s1, weighing Mn salt, ni salt and Co salt according to a proportion, and dissolving the Mn salt, the Ni salt and the Co salt in water to prepare a mixed salt solution; preparing a precipitant; preparing a complexing agent;
s2, adding pure water, a dispersing agent and the complexing agent into a container filled with inert atmosphere to prepare a base solution, controlling the concentration of the complexing agent in the base solution to be 0.10-0.80 mol/L, and adding the precipitating agent to adjust the pH value of the base solution to be 9.5-12;
s3, adding the mixed salt solution, the precipitator and the complexing agent into the container at the same time to carry out coprecipitation reaction, wherein the pH value in the reaction is maintained at 9.5-12, the temperature in the reaction is maintained at 50-70 ℃, and the rotating speed of the container is 600-1000 r/min; stopping the reaction when the particle size D50 of the precipitated product in the container is 5-12 um;
s4, centrifuging, washing and drying the precipitation product to obtain a manganese-rich precursor.
According to the preparation method of the manganese-rich precursor, the dispersing agent is one or the combination of two of sodium oleate, sodium acetate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate in any proportion; the concentration of the dispersing agent in the base solution is 0.1-10g/L.
According to the preparation method of the manganese-rich precursor, in the mixed salt solution in the step S1, the ratio of Mn salt to Ni salt to Co salt is 0.50-0.80:0.10-0.40:0.05-0.30, and the concentration of the mixed salt solution is 1-4 mol/L.
According to the preparation method of the manganese-rich precursor, the concentration of the precipitant solution in the step S1 is 2-8 mol/L, and the precipitant comprises at least one of sodium hydroxide and potassium hydroxide.
According to the preparation method of the manganese-rich precursor, the concentration of the complexing agent in the step S1 is 0.5-2 mol/L, and the complexing agent comprises one or a combination of two of ammonia water, sodium nitrilotriacetate, ethylenediamine tetraacetic acid and ethylenediamine tetraacetic acid in any proportion.
According to the preparation method of the manganese-rich precursor provided by the invention, in the step S3, the molar ratio of the complexing agent to the mixed salt solution added into the container in unit time is 0.10-0.80: 1.
the invention also provides a manganese-rich precursor, which is prepared by any one of the preparation methods of the manganese-rich precursor.
According to the manganese-rich precursor provided by the invention, the primary particle thickness of the manganese-rich precursor is 10-50 nm, dmin is more than or equal to 3 mu m, D50 is 5-12 mu m, dmax is less than or equal to 30 mu m, and tap density is more than or equal to 1.5g/cm 3 。
The invention also provides a positive electrode material which is prepared by sintering the manganese-rich precursor.
The invention also provides a lithium ion battery, which comprises the positive electrode material.
The invention provides a manganese-rich precursor and a preparation method thereof, a positive electrode material and a lithium ion battery, wherein Mn salt, ni salt and Co salt are weighed according to a proportion and dissolved in water to prepare a mixed salt solution; preparing a precipitant; preparing a complexing agent; adding a precipitator, a complexing agent, pure water and a dispersing agent into a container filled with inert atmosphere to prepare a base solution, controlling the concentration of the complexing agent in the base solution to be 0.10-0.80 mol/L, adding the precipitator to adjust the pH value of the base solution to be 9.5-12, wherein the complexing agent adjusts the supersaturation degree and the precipitation speed of transition metal ions in a reaction system, and inhibiting the overgrowth of primary crystal nuclei; the dispersing agent inhibits the aggregation of the secondary balls and controls the granularity and the distribution of the secondary balls. The synergistic effect of the two can well solve the problems of large primary particle size, poor secondary particle sphericity, low tap density and the like of the manganese-rich precursor prepared by a hydroxide coprecipitation method. Adding the mixed salt solution, the precipitator and the complexing agent into a container simultaneously for coprecipitation reaction, wherein the pH value in the reaction is maintained at 9.5-12, the temperature in the reaction is maintained at 50-70 ℃, and the rotating speed of the container is 600-1000 r/min; stopping the reaction when the particle size D50 of the precipitated product in the container is 5-12 um; and centrifuging, washing and drying the precipitate to obtain the manganese-rich precursor. The manganese-rich precursor primary flaky particles prepared by the method are thin and uniform in thickness, the secondary particles are good in sphericity and high in tap density, a good foundation is laid for the preparation of the subsequent lithium-rich manganese-based positive electrode material, the method is simple, the applicability is strong, the required equipment is relatively simple, the operation is convenient, the control difficulty is small, the industrial manufacturing efficiency is high, the cost is low, the amplification popularization and the application are convenient, and the lithium-rich manganese-based positive electrode material obtained by the manganese-rich precursor provided by the invention has high tap density, can be remarkably improved in volume energy density of a battery when being applied to the battery, and has a wide market prospect.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic flow chart of a manganese-rich precursor and a preparation method thereof;
FIG. 2 is a 2000 x electron microscope image of the manganese rich precursor prepared in example 1 of the present invention;
FIG. 3 is a 20000 x electron microscope image of the manganese rich precursor prepared in example 1 of the present invention;
FIG. 4 is a 2000 x electron microscope image of the manganese rich precursor prepared in comparative example 1 of the present invention;
FIG. 5 is a 20000 x electron microscope image of the manganese-rich precursor prepared in comparative example 1 of the present invention;
FIG. 6 is an electron micrograph of a manganese rich precursor frit prepared in example 1 of the present invention;
FIG. 7 is an electron microscopic view of the manganese rich precursor sintered compact prepared in comparative example 1 of the present invention;
FIG. 8 is a graph of charge and discharge curves for two positive electrode materials prepared using the manganese rich precursors prepared in example 1 and comparative example 1 of the present invention;
fig. 9 is a graph of cycling of two positive electrode materials prepared using the manganese rich precursors prepared in example 1 and comparative example 1 of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The following describes a method for preparing a manganese-rich precursor according to the present invention with reference to fig. 1.
As shown in fig. 1, the preparation method of the manganese-rich precursor provided by the invention comprises the following steps:
s1, weighing Mn salt, ni salt and Co salt according to a proportion, and dissolving the Mn salt, the Ni salt and the Co salt in water to prepare a mixed salt solution; preparing a precipitant; preparing complexing agent.
S2, adding pure water, a dispersing agent and a complexing agent into a container filled with inert atmosphere to prepare a base solution, controlling the concentration of the complexing agent in the base solution to be 0.10-0.80 mol/L, and adding a precipitant to enable the pH value of the base solution to be 9.5-12. In an alternative embodiment of the invention, a reaction kettle can be used as the container, and after inert atmosphere is introduced into the reaction kettle, the inert atmosphere can be used as a protective gas to isolate air, so that oxidation of Mn < 2+ > ions by oxygen in the air is avoided, and the reaction result is influenced. The complexing agent can adjust the supersaturation degree and the precipitation speed of transition metal ions in a reaction system, and inhibit the overquick growth of primary crystal nuclei; the dispersing agent can inhibit the aggregation of the secondary balls and control the granularity and the distribution of the secondary balls. The synergistic effect of the two can well solve the problems of large primary particle size, poor secondary particle sphericity, low tap density and the like of the manganese-rich precursor prepared by a hydroxide coprecipitation method.
S3, adding the mixed salt solution, the precipitator solution and the complexing agent solution into a container at the same time to carry out coprecipitation reaction, wherein the pH value in the reaction is maintained at 9.5-12, the temperature in the reaction is maintained at 50-70 ℃, and the rotating speed of the container is 600-1000 r/min; the reaction is stopped when the particle size D50 of the precipitated product in the vessel is 5 to 12. Mu.m.
S4, centrifuging, washing and drying the precipitate to obtain the manganese-rich precursor.
The manganese-rich precursor prepared by the preparation method of the manganese-rich precursor has the advantages of thin thickness of the primary flaky particles, uniform thickness, good sphericity of the secondary particles and high tap density, can obviously improve the volume energy density of the battery when applied to the battery, has wide market prospect, and lays a good foundation for the preparation of the subsequent lithium-rich manganese-based positive electrode material; the preparation method is simple, high in applicability, relatively simple in required equipment, convenient to operate, low in control difficulty, high in industrial manufacturing efficiency, low in cost and convenient to amplify, popularize and apply.
The method for preparing the manganese-rich precursor provided by the invention is specifically described in several examples.
Example 1:
a method for preparing a manganese-rich precursor, comprising the steps of:
(1) The molar ratio is 0.60:0.25:0.15, weighing Mn, ni and Co salts, dissolving in deionized water, and preparing to obtain a mixed salt solution with the total concentration of 2 mol/L;
NaOH is weighed and dissolved in deionized water to prepare a solution with the concentration of 4mol/L as a precipitator;
weighing ammonia water, dissolving in deionized water, and preparing a solution with the total concentration of 1mol/L as a complexing agent;
(2) Adding pure water into a reaction kettle filled with inert atmosphere, adding sodium acetate according to the proportion of 1g/L, stirring and dissolving, adding a complexing agent to control the concentration of the complexing agent in the base solution to be 0.20mol/L, adding a precipitator, and adjusting the pH value of the base solution to be 11;
(3) The mixed salt solution, the precipitator and the complexing agent are simultaneously added into a reaction kettle in a dropwise manner for coprecipitation reaction, the pH value is maintained at 11 in the reaction process, the reaction temperature is maintained at 60 ℃, the rotating speed of the reaction kettle is 900r/min, and the adding speed of the complexing agent is controlled to be 0.20 in the molar ratio of the complexing agent to the mixed salt solution in unit time: 1, a step of;
until the granularity D50 of the materials in the reaction kettle grows to 5-12 um, stopping the reaction;
(4) And centrifuging, washing and drying the product to obtain the high-tap-density spheroidal manganese-rich precursor.
For the manganese-rich precursor prepared by the method of the above example 1, the 2000-time electron microscope image is shown in fig. 1, the 20000-time electron microscope image is shown in fig. 2, and as can be seen from fig. 1 and 2, the manganese-rich precursor has the advantages of thin primary flaky particle thickness, smooth secondary sphere surface, good sphericity and high tap density.
Example 2
A method for preparing a manganese-rich precursor, comprising the steps of:
(1) The molar ratio is 0.75:0.20:0.05 weighing Mn, ni and Co salts, and dissolving the Mn, ni and Co salts in deionized water to prepare a metal salt solution with the total concentration of 1 mol/L;
NaOH is weighed and dissolved in deionized water to prepare a solution with the concentration of 2mol/L as a precipitator;
the molar ratio is 1:1, weighing ammonia water and ethylenediamine tetraacetic acid, dissolving in deionized water, and preparing 0.5mol/L solution serving as a complexing agent;
(2) Adding pure water into a reaction kettle filled with inert atmosphere, adding sodium oleate according to the proportion of 10g/L, stirring and dissolving, adding a complexing agent, controlling the ammonia concentration in the base solution to be 0.10mol/L, and adding a precipitant to adjust the pH value of the base solution to be 10;
(3) The mixed salt solution, the precipitator and the complexing agent are simultaneously added into a reaction kettle in a dropwise manner for coprecipitation reaction, the pH value is maintained at 10 in the reaction process, the reaction temperature is maintained at 50 ℃, the rotating speed of the reaction kettle is 1000r/min, and the adding speed of the complexing agent is controlled at 0.10 of the mole ratio of the complexing agent to the mixed salt solution in unit time: 1, a step of;
until the granularity D50 of the materials in the reaction kettle grows to 5-12 um, stopping the reaction;
(4) And centrifuging, washing and drying the product to obtain the high-tap-density spheroidal manganese-rich precursor.
Example 3
A method for preparing a manganese-rich precursor, comprising the steps of:
(1) The molar ratio is 0.5:0.4:0.1 weighing Mn, ni and Co salts, dissolving in deionized water, and preparing to obtain a metal salt solution with the total concentration of 3 mol/L;
weighing KOH and dissolving in deionized water to prepare a solution with the concentration of 6mol/L as a precipitator;
weighing sodium nitrilotriacetate, and dissolving in deionized water to prepare a solution with the concentration of 2mol/L serving as a complexing agent;
(2) Adding pure water into a reaction kettle filled with inert atmosphere, adding sodium dodecyl sulfate according to the proportion of 0.1g/L, stirring for dissolution, adding a complexing agent, controlling the concentration of the complexing agent in the base solution to be 0.40mol/L, adding a precipitator, and controlling the pH value of the base solution to be 12;
(3) The mixed salt solution, the precipitator and the complexing agent are simultaneously added into a reaction kettle in a dropwise manner for coprecipitation reaction, the pH value is maintained at 12 in the reaction process, the reaction temperature is maintained at 65 ℃, the rotating speed of the reaction kettle is 800r/min, and the adding speed of the complexing agent is controlled to be 0.40 in the molar ratio of the complexing agent to the mixed salt solution in unit time: 1, a step of;
until the granularity D50 of the materials in the reaction kettle grows to 5-12 um, stopping the reaction;
(4) And centrifuging, washing and drying the product to obtain the high-tap-density spheroidal manganese-rich precursor.
Example 4
A method for preparing a manganese-rich precursor, comprising the steps of:
(1) The molar ratio is 0.6:0.2:0.2 weighing Mn, ni and Co salts, dissolving in deionized water, and preparing to obtain a metal salt solution with total concentration of 4 mol/L;
weighing KOH and dissolving in deionized water to prepare 8mol/L solution serving as a precipitator;
weighing sodium ethylenediamine tetraacetate, dissolving in deionized water to prepare a 1mol/L solution serving as a complexing agent;
(2) Adding pure water into a reaction kettle filled with inert atmosphere, adding sodium dodecyl benzene sulfonate according to the proportion of 5g/L, stirring and dissolving, adding a complexing agent, controlling the concentration of the complexing agent in the base solution to be 0.30mol/L, adding a precipitator, and adjusting the pH value of the base solution to be 11;
(3) The mixed salt solution, the precipitator and the complexing agent are simultaneously added into a reaction kettle in a dropwise manner for coprecipitation reaction, the pH value is maintained at 11 in the reaction process, the reaction temperature is maintained at 70 ℃, the rotating speed of the reaction kettle is 900r/min, and the adding speed of the complexing agent is controlled to be 0.30 in the molar ratio of the complexing agent to the mixed salt solution in unit time: 1, a step of;
until the granularity D50 of the materials in the reaction kettle grows to 5-12 um, stopping the reaction;
(4) And centrifuging, washing and drying the product to obtain the high-tap-density spheroidal manganese-rich precursor.
Example 5
A method for preparing a manganese-rich precursor, comprising the steps of:
(1) The molar ratio is 0.8:0.1:0.1 weighing Mn, ni and Co salts, dissolving in deionized water, and preparing to obtain a metal salt solution with the total concentration of 2 mol/L;
NaOH is weighed and dissolved in deionized water to prepare a solution with the concentration of 4mol/L as a precipitator;
weighing ammonia water, dissolving in deionized water, and preparing a 1mol/L solution serving as a complexing agent;
(2) Adding pure water into a reaction kettle filled with inert atmosphere, then adding sodium acetate and sodium dodecyl benzene sulfonate according to the proportion of 2g/L and 3g/L respectively, stirring and dissolving, adding a complexing agent, controlling the concentration of the complexing agent in the base solution to be 0.80mol/L, adding a precipitant, and regulating the pH value of the base solution to be 9.5;
(3) The mixed salt solution, the precipitator and the complexing agent are simultaneously added into a reaction kettle in a dropwise manner for coprecipitation reaction, the pH value is maintained at 9.5 in the reaction process, the reaction temperature is maintained at 55 ℃, the rotating speed of the reaction kettle is 600r/min, and the adding speed of the complexing agent is controlled to be 0.80 in the molar ratio of the complexing agent to the mixed salt solution in unit time: 1, a step of;
until the granularity D50 of the materials in the reaction kettle grows to 5-12 um, stopping the reaction;
(4) And centrifuging, washing and drying the product to obtain the high-tap-density spheroidal manganese-rich precursor.
As a comparison with the above-described example 1, the present invention provides a comparative example 1 corresponding to the above-described example 1, and the following specifically describes the comparative example 1:
comparative example 1
A method for preparing a manganese-rich precursor, comprising the steps of:
(1) The molar ratio is 0.60:0.25:0.15, weighing Mn, ni and Co salts, dissolving in deionized water, and preparing to obtain a mixed salt solution with the total concentration of 2 mol/L;
NaOH is weighed and dissolved in deionized water to prepare a solution with the concentration of 4mol/L as a precipitator;
weighing ammonia water, dissolving in deionized water, and preparing a solution with the total concentration of 1mol/L as a complexing agent;
(2) Adding pure water into a reaction kettle filled with inert atmosphere, adding a complexing agent, controlling the concentration of the complexing agent in the base solution to be 0.20mol/L, adding a precipitator, and adjusting the pH value of the base solution to be 11;
(3) The mixed salt solution, the precipitator and the complexing agent are simultaneously added into a reaction kettle in a dropwise manner for coprecipitation reaction, the pH value is maintained at 11 in the reaction process, the reaction temperature is maintained at 60 ℃, the rotating speed of the reaction kettle is 900r/min, and the adding speed of the complexing agent is controlled to be 0.20 in the molar ratio of adding the complexing agent to the metal salt in unit time: 1, a step of;
until the granularity D50 of the materials in the reaction kettle grows to 5-12 um, stopping the reaction;
(4) And centrifuging, washing and drying the product to obtain the manganese-rich precursor.
As for the manganese-rich precursor prepared by the above-described method of comparative example 1, 2000 x electron microscope images thereof are shown in fig. 3 and 20000 x electron microscope images thereof are shown in fig. 4, and by comparing fig. 3 and fig. 4 with fig. 1 and fig. 2 of the manganese-rich precursor in example 1, and by the data in table 1, it is known that the manganese-rich precursor prepared by the method of comparative example 1 has a thicker primary platelet particle thickness, a coarser secondary sphere surface, a poorer sphericity, and a lower tap density than the manganese-rich precursor prepared by the method of example 1.
Similarly, as can be seen from table 1, the manganese-rich precursor prepared in examples 2 to 5, in which the dispersant and the complexing agent were added during the coprecipitation reaction to synthesize the precursor, had a smaller thickness of the primary flaky particles and a higher tap density than the manganese-rich precursor prepared in the method of comparative example 1. The manganese-rich precursor prepared in examples 2-5 has smooth surface and good sphericity of the secondary sphere. The corresponding sintered material has small primary granularity, uniform granularity, high density and tap density of the secondary balls and good sphericity.
TABLE 1 physical Properties of the Mn-rich precursor prepared in examples 1-5 and comparative example 1 and tap Density test data of sintered compact
The invention provides a manganese-rich precursor, which is prepared by any one of the preparation methods of the manganese-rich precursor. The thickness of primary particles of the manganese-rich precursor is 10-50 nm, D min (minimum particle size) is more than or equal to 3 mu m, D50 (particle size corresponding to the cumulative particle size distribution percentage of the sample reaching 50%) is 5-12 mu m, D max (maximum particle size) is less than or equal to 30 mu m, and tap density is more than or equal to 1.5g/cm 3 。
The invention provides a positive electrode material which is prepared by sintering the manganese-rich precursor.
And (3) uniformly mixing the manganese-rich precursor prepared in the step (4) in the embodiment 1 and the comparative example 1 with lithium carbonate according to the molar ratio of TM:Li=1:1.4, placing the mixture in a muffle furnace, heating to 500 ℃ at the heating rate of 5 ℃/min in an air atmosphere, preserving heat for 5 hours, heating to 900 ℃ and preserving heat for 12 hours, and finally naturally cooling to room temperature to prepare the two lithium-rich manganese-based positive electrode materials. FIGS. 6 and 7 are electron micrographs of the frits of example 1 and comparative example 1, respectively, from which it can be seen that the primary particles of the frits of example 1 are relatively uniform and have a particle size of about 0.2 to 0.5. Mu.m, the primary particles are tightly aggregated into a secondary sphere, and the primary particles of the frits of comparative example 1 are in the form of long plates having an uneven size, a thickness of 0.2 to 0.4. Mu.m, a length of 0.2 to 1.8. Mu.m, and the surface of the secondary sphere is very rough and dense.
The initial charge-discharge curve (2-4.8V) and the 1C cycle curve (2-4.6V) of the lithium-rich manganese-based positive electrode material button cell 0.1C prepared in example 1 and comparative example 1 are shown in fig. 8 and 9, respectively. Through electrical property tests, the specific capacity of the lithium-rich manganese-based material prepared in the example 1 for buckling electricity at 0.1C is 264.2mAh/g, and the retention rate of the 1C200 cycle capacity can reach 87.0%, which are far higher than 240.7mAh/g and 75.1% of the material of the comparative example 1.
The invention also provides a lithium ion battery, which comprises the positive electrode material.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for synthesizing a manganese-rich precursor is characterized by comprising the following steps: the method comprises the following steps:
s1, weighing Mn salt, ni salt and Co salt according to a proportion, and dissolving the Mn salt, the Ni salt and the Co salt in water to prepare a mixed salt solution; preparing a precipitant; preparing a complexing agent;
s2, adding pure water, a dispersing agent and the complexing agent into a container filled with inert atmosphere to prepare a base solution, controlling the concentration of the complexing agent in the base solution to be 0.10-0.80 mol/L, and adding the precipitating agent to adjust the pH value of the base solution to be 9.5-12;
s3, adding the mixed salt solution, the precipitator and the complexing agent into the container at the same time to carry out coprecipitation reaction, wherein the pH value in the reaction is maintained at 9.5-12, the temperature in the reaction is maintained at 50-70 ℃, and the rotating speed of the container is 600-1000 r/min; stopping the reaction when the particle size D50 of the precipitated product in the container is 5-12 um;
s4, centrifuging, washing and drying the precipitation product to obtain a manganese-rich precursor.
2. The method of preparing a manganese-rich precursor according to claim 1, wherein the dispersant comprises one or a combination of two of sodium oleate, sodium acetate, sodium dodecyl sulfate and sodium dodecyl benzene sulfonate in any proportion; the concentration of the dispersing agent in the base solution is 0.1-10g/L.
3. The method for preparing a manganese-rich precursor according to claim 1, wherein the ratio of Mn salt, ni salt and Co salt in the mixed salt solution in step S1 is 0.50-0.80:0.10-0.40:0.05-0.30, and the concentration of the mixed salt solution is 1-4 mol/L.
4. The method of preparing a manganese rich precursor according to claim 1, wherein the concentration of the precipitant solution in step S1 is 2 to 8mol/L, and the precipitant includes at least one of sodium hydroxide and potassium hydroxide.
5. The method for preparing a manganese-rich precursor according to claim 1, wherein the concentration of the complexing agent in the step S1 is 0.5-2 mol/L, and the complexing agent comprises one or a combination of two of ammonia water, sodium nitrilotriacetate, ethylenediamine tetraacetic acid and sodium ethylenediamine tetraacetate in any proportion.
6. The method for preparing a manganese-rich precursor according to claim 1, wherein in the step S3, a molar ratio of the complexing agent to the mixed salt solution added to the container per unit time is 0.10 to 0.80:1.
7. a manganese rich precursor prepared by the method of preparing a manganese rich precursor according to any one of claims 1 to 6.
8. The manganese rich precursor according to claim 7, wherein the primary particles of the manganese rich precursor have a thickness of 10-50 nm, a Dmin 3 μm or more, a D50 of 5-12 μm, a Dmax 30 μm or less, and a tap density 1.5g/cm or more 3 。
9. A positive electrode material, characterized in that it is prepared by sintering the manganese-rich precursor according to claim 7 or 8.
10. A lithium ion battery comprising the positive electrode material of claim 9.
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| CN117230312B (en) * | 2023-11-13 | 2024-03-19 | 帕瓦(长沙)新能源科技有限公司 | Alkaline leaching process of waste lithium ion battery anode material |
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