CN117361647A - Lithium-rich manganese-based precursor material and preparation method and application thereof - Google Patents
Lithium-rich manganese-based precursor material and preparation method and application thereof Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 83
- 239000011572 manganese Substances 0.000 title claims abstract description 79
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 76
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 74
- 239000000463 material Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 84
- 238000006243 chemical reaction Methods 0.000 claims abstract description 70
- 239000007789 gas Substances 0.000 claims abstract description 67
- 238000000975 co-precipitation Methods 0.000 claims abstract description 61
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000001301 oxygen Substances 0.000 claims abstract description 57
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 57
- 239000002245 particle Substances 0.000 claims abstract description 29
- 239000012266 salt solution Substances 0.000 claims abstract description 24
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000001681 protective effect Effects 0.000 claims abstract description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 239000012716 precipitator Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 44
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 239000002585 base Substances 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 19
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 235000006408 oxalic acid Nutrition 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 9
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 8
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 8
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 8
- 229910001437 manganese ion Inorganic materials 0.000 claims description 8
- 229910001453 nickel ion Inorganic materials 0.000 claims description 8
- 239000007774 positive electrode material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 239000003513 alkali Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000010406 cathode material Substances 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 2
- 229910001416 lithium ion Inorganic materials 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 238000005054 agglomeration Methods 0.000 abstract description 14
- 230000002776 aggregation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 230000003647 oxidation Effects 0.000 abstract description 5
- 230000000052 comparative effect Effects 0.000 description 11
- 239000002002 slurry Substances 0.000 description 8
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical class [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000005119 centrifugation 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
- 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 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- FXOOEXPVBUPUIL-UHFFFAOYSA-J manganese(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Mn+2].[Ni+2] FXOOEXPVBUPUIL-UHFFFAOYSA-J 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction 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
- H01M4/52—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- 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
-
- 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
- C01P2006/40—Electric properties
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a lithium-rich manganese-based precursor material, and a preparation method and application thereof, wherein the preparation method comprises the following steps: and mixing the nickel-cobalt-manganese mixed salt solution, the precipitator solution and the complexing agent solution in a protective gas atmosphere, performing a coprecipitation reaction, starting to introduce oxygen-containing gas when particles enter a growth stage in the coprecipitation reaction, and then continuing the coprecipitation reaction to obtain the lithium-rich manganese-based precursor material. According to the preparation method, the oxidation atmosphere is introduced in the growth stage of the precursor material, so that the problems of compact particle growth, easy agglomeration and poor morphology in the existing preparation process of the lithium-rich manganese precursor material are avoided, and the lithium-rich manganese-based precursor material with high dispersibility and high specific surface area is obtained.
Description
Technical Field
The invention belongs to the technical field of battery materials, and relates to a lithium-rich manganese-based precursor material, and a preparation method and application thereof.
Background
In recent years, lithium ion batteries have achieved great commercial success in the field of portable electronic products, and are also the main energy storage devices of electric automobiles. The lithium-rich manganese-based positive electrode material has high specific capacity>250mAh g -1 ) And low cost, is considered as a positive electrode material with good application prospect. It is well known that the quality of the precursor material is critical to the performance of the lithium-rich manganese-based cathode material.
The current industrialized lithium-rich manganese precursor preparation method mainly adopts a hydroxide coprecipitation method, specifically, a nickel-cobalt-manganese mixed salt solution, a hydroxide precipitant and a complexing agent are mixed, the mixture is put into a reaction kettle with base solution and protective gas for constant-temperature coprecipitation, solid-liquid separation, aging, centrifugation and drying are carried out on overflow materials after reaction, and a quasi-spherical lithium-rich manganese precursor material is obtained, but as the manganese content increases, the agglomeration of small-particle nickel-cobalt-manganese hydroxide becomes serious, the morphology uniformity becomes poor, and the specific surface area and physical and chemical properties of the precursor become poor.
As CN 110323430A discloses a preparation method of a lithium-rich manganese-based material and a lithium-rich manganese-based material, the preparation method comprises the steps of adding Mn to the material 2+ And M 2+ The mixed metal salt solution, the complexing agent, the precipitator and the reducing agent are mixed to prepare a lithium-rich manganese precursor, and the concentration of the reducing agent is controlled to prepare the lithium-rich manganese-based material with better electrochemical performance, but the particle growth is tighter, the agglomeration is serious, the overall morphology of the precursor is difficult to control, the sphericity and the dispersity are poor along with the improvement of the manganese content in the coprecipitation process of the lithium-rich manganese-based precursor, so that the structure of the anode material sintered later is causedUnstable and poor cycle performance.
And as CN 116216796A discloses a modified nickel-manganese binary precursor, a preparation method and application thereof, wherein a modifier is added into a reaction base solution in advance to control the crystal form of the binary nickel-manganese precursor, the obtained primary crystal form of nickel-manganese hydroxide is compact, and although the problems that in the existing preparation method of the nickel-manganese binary precursor, the primary crystal form is easy to separate out trimanganese tetroxide and the morphology is loose are avoided, the particle growth is more compact and the agglomeration is serious along with the increase of the manganese content in the coprecipitation process of the lithium-rich manganese-based precursor, and the integral morphology of the precursor obtained by the preparation method is difficult to control, the sphericity and the dispersity are poor, so that the sintering of a subsequent positive electrode material is unfavorable.
Based on the above research, it is necessary to provide a preparation method of a lithium-rich manganese-based precursor material, which can solve the problems of particle agglomeration, poor dispersibility and difficult control of morphology due to the increase of manganese content during coprecipitation.
Disclosure of Invention
The invention aims to provide a lithium-rich manganese-based precursor material, a preparation method and application thereof, wherein the preparation method avoids the problems of compact particle growth, easy agglomeration and poor morphology in the existing preparation process of the lithium-rich manganese-based precursor material by introducing an oxidizing atmosphere in the growth stage of the precursor material, and the lithium-rich manganese-based precursor material with high dispersibility and high specific surface is obtained.
In order to achieve the aim of the invention, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a lithium-rich manganese-based precursor material, the method comprising the steps of:
and mixing the nickel-cobalt-manganese mixed salt solution, the precipitator solution and the complexing agent solution in a protective gas atmosphere, performing a coprecipitation reaction, starting to introduce oxygen-containing gas when particles enter a growth stage in the coprecipitation reaction, and then continuing the coprecipitation reaction to obtain the lithium-rich manganese-based precursor material.
In order to avoid the problem of particle agglomeration caused by the increase of manganese content during coprecipitation preparation of the lithium-rich manganese-based precursor, on the basis of coprecipitation in a protective gas atmosphere, oxygen-containing gas is introduced when the particles enter a growth stage after nucleation, so that the system is subjected to micro-oxidation, the particles grow in the protective gas and the oxygen-containing gas (the protective gas is always introduced in the coprecipitation reaction stage), and particle agglomeration is avoided.
Preferably, after the coprecipitation reaction is carried out for 2 to 10 hours, for example, 2 hours, 3 hours, 4 hours, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours or 10 hours, oxygen-containing gas starts to be introduced.
When the coprecipitation reaction is carried out for a specific time, oxygen-containing gas is introduced, if the time of introducing the oxygen-containing gas is too late, the lithium-rich manganese precursor has compact particle growth in the early stage of the growth stage, and is adhered to each other, the agglomeration is serious, and the dispersibility of the lithium-rich manganese precursor is difficult to improve in the later stage; if the time for starting to introduce oxygen-containing gas is too early, the precursor is easily oxidized in the early nucleation stage, and MnO is easily precipitated in the primary crystal form 2 Resulting in non-uniformity of the precursor composition.
Preferably, the oxygen-containing gas comprises air or oxygen, preferably air.
The oxygen-containing gas introduced by the invention is preferably air, and if the oxygen-containing gas is pure oxygen, the oxygen content of the system is too high, and the particle dispersibility and the specific surface area are also affected.
Preferably, the protective gas comprises nitrogen and/or an inert gas.
Preferably, the flow rate of the oxygen-containing gas is 5-15L/h, for example, 5L/h, 7L/h, 9L/h, 11L/h, 13L/h or 15L/h, but the flow rate is not limited to the recited values, and other values not recited in the numerical range are equally applicable.
The flow rate of the oxygen-containing gas can influence the oxidation degree of the system, and if the flow rate of the oxygen-containing gas is too small, the oxidation degree of the introduced system is insufficient, so that the precursor particles still have serious agglomeration and are separatedThe effect of improving the dispersibility is poor, and if the flow rate of the oxygen-containing gas is too large, excessive oxidation occurs, resulting in a small amount of Mn 3 O 4 And MnO 2 The generation of the alien phase is unfavorable for improving the dispersibility of the particles, and the flow of the introduced gas is too large, so that the production cost is additionally increased.
Preferably, the flow rate of the protective gas is 50-200L/h, for example, 50L/h, 75L/h, 100L/h, 125L/h, 150L/h, 175L/h or 200L/h, but not limited to the recited values, and other non-recited values in the range of values are equally applicable.
Similarly, the flow rate of the protective gas provided by the invention also affects the oxygen content in the system.
Preferably, the precipitant solution comprises sodium hydroxide solution and/or potassium hydroxide solution.
Preferably, the mass fraction of the precipitant solution is 30-35wt%, for example, 30wt%, 31wt%, 32wt%, 33wt%, 34wt%, or 35wt%, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the complexing agent solution comprises oxalic acid and/or aqueous ammonia.
Preferably, the complexing agent solution has a mass concentration of 2-10g/L, which may be, for example, 2g/L, 5g/L, 8g/L or 10g/L, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable.
Preferably, the nickel-cobalt-manganese mixed salt solution, the precipitator solution and the complexing agent solution are circulated into the base solution to carry out coprecipitation reaction.
Preferably, the pH of the base liquid is 11.5-12, which may be 11.5, 11.75 or 12, for example, and the base liquid comprises water, a precipitant solution and a complexing agent solution.
Preferably, the nickel cobalt manganese mixed salt solution comprises any one or a combination of at least two of sulfate, nitrate or chloride.
Preferably, in the nickel cobalt manganese mixed salt solution, the molar ratio of nickel ions, cobalt ions and manganese ions is x:y:z, wherein x+y+z=1, z is larger than or equal to 0.6, and can be, for example, 0.6, 0.7, 0.8 or 0.9,0 < x < 0.4, and can be, for example, 0.1, 0.2 or 0.3,0 < y < 0.4, and can be, for example, 0.1, 0.2 or 0.3, but not limited to the listed values, and other non-listed values in the numerical range are equally applicable.
Preferably, the mass concentration of the nickel-cobalt-manganese mixed salt solution is 80-120g/L, for example, 80g/L, 90g/L, 100g/L, 110g/L or 120g/L, but the nickel-cobalt-manganese mixed salt solution is not limited to the listed values, and other non-listed values in the numerical range are applicable.
Preferably, the temperature of the coprecipitation reaction is 50-60 ℃, such as 50 ℃, 55 ℃ or 60 ℃, the pH is 9.5-11.5, such as 9.5, 10, 11 or 11.5, the stirring speed is 400-700rpm, such as 400rpm, 500rpm, 600rpm or 700rpm, but not limited to the recited values, and other non-recited values within the numerical range are equally applicable.
Preferably, after the coprecipitation reaction is finished, suction filtration, washing and drying are also carried out.
Preferably, the temperature of the drying is 100-150 ℃, for example, 100 ℃, 120 ℃, 140 ℃ or 150 ℃, but is not limited to the recited values, and other non-recited values within the range of values are equally applicable.
Preferably, the washing comprises washing with lye and then with each other 2-5 times, for example 2, 3, 4 or 5 times.
The water used for washing is hot water.
As a preferable technical scheme of the preparation method, the preparation method comprises the following steps:
under the protective gas atmosphere, the nickel-cobalt-manganese mixed salt solution, the precipitator solution and the complexing agent solution are circulated and introduced into the base solution, the coprecipitation reaction is carried out, oxygen-containing gas is introduced after the coprecipitation reaction is carried out for 2-10 hours, then the coprecipitation reaction is continued, and after the coprecipitation reaction is finished, suction filtration, washing and drying treatment at the temperature of 100-150 ℃ are carried out, so that the lithium-rich manganese-based precursor material is obtained;
the oxygen-containing gas comprises air or oxygen, and the flow rate of the oxygen-containing gas is 5-15L/h; the protective gas comprises nitrogen and/or inert gas, and the inlet flow rate of the protective gas is 50-200L/h; the temperature of the coprecipitation reaction is 50-60 ℃, the pH is 9.5-11.5, and the stirring speed is 400-700rpm;
the pH value of the base solution is 11.5-12, the base solution comprises water, a precipitator solution and a complexing agent solution, and the molar ratio of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese mixed salt solution is x:y:z, wherein x+y+z=1, z is more than or equal to 0.6,0 and less than x and less than 0.4, and y is more than or equal to 0 and less than 0.4.
In a second aspect, the present invention provides a lithium-rich manganese-based precursor material according to the first aspect, which is prepared by the preparation method according to the first aspect.
In a third aspect, the present invention provides a lithium-rich manganese-based cathode material obtained by mixing and sintering a lithium-rich manganese-based precursor material as described in the second aspect with a lithium source.
In a fourth aspect, the present invention provides a battery comprising a lithium-rich manganese-based positive electrode material according to the third aspect.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, micro-oxidation is introduced in the growth stage of the precursor, only one three-way joint is added at the air inlet, and the oxygen-containing atmosphere is introduced, so that the modification and the addition of an air inlet pipeline of the existing kettle body are not required, the preparation process is simple, and the production cost can be reduced;
(2) The method carries out micro-oxidation on the particles in the growth stage of the precursor, effectively avoids the defects of particle agglomeration and poor dispersibility of the prior lithium-rich manganese precursor in the reaction stage, obtains the high-dispersibility lithium-rich manganese-based precursor with uniformly distributed particles, and maintains the specific surface area at 25-30m 2 And about/g, the precursor with uniform particle distribution and high proportion is favorable for the structural stability and the improvement of the cycle performance of the subsequent positive electrode material.
Drawings
FIG. 1 is an SEM image at 3000 times magnification of a lithium-rich manganese-based precursor material obtained according to example 1 of the present invention;
FIG. 2 is an SEM image at 5000 times magnification of a lithium-rich manganese-based precursor material obtained in example 1 of the present invention;
FIG. 3 is an SEM image at 3000 times magnification of a lithium-rich manganese-based precursor material obtained according to comparative example 1 of the present invention;
fig. 4 is an SEM image of the lithium-rich manganese-based precursor material obtained in comparative example 1 of the present invention at 5000 x magnification.
Detailed Description
The technical scheme of the invention is further described by the following specific embodiments. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Example 1
The embodiment provides a preparation method of a lithium-rich manganese-based precursor material, which comprises the following steps:
(1) Adding 33.5kg of pure water into a reaction kettle, adding 150g of sodium hydroxide solution and 200g of oxalic acid solution as reaction base solution, introducing nitrogen for 3 hours, controlling the flow rate of the nitrogen to be 200L/h, and controlling the initial pH value of the base solution to be 11.6-11.8;
(2) Under the nitrogen atmosphere, a nickel-cobalt-manganese mixed salt solution is introduced into the base solution in the step (1) at a flow rate of 1.5kg/h, a sodium hydroxide solution is introduced into the base solution at a flow rate of 0.69kg/h and an oxalic acid solution is introduced into the base solution at a flow rate of 0.18kg/h, a coprecipitation reaction is carried out, oxygen-containing gas is introduced after the coprecipitation reaction is carried out for 6h, then the coprecipitation reaction is continued, after the coprecipitation reaction is finished, the slurry after the reaction is transferred into a suction filtration bottle, alkali liquor and hot water are selected for three times, and then the slurry is dried at a temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor material;
the oxygen-containing gas is air, and the flow rate of the oxygen-containing gas is 8L/h; the flow rate of the nitrogen is 200L/h; the temperature of the coprecipitation reaction is 58 ℃, the pH is controlled between 10.4 and 10.6, and the stirring speed is 600rpm;
in the nickel-cobalt-manganese mixed salt solution, the mass concentration is 100g/L, and the molar ratio of nickel ions to cobalt ions to manganese ions is 0.167:0.167:0.666; the mass fraction of the sodium hydroxide solution is 32%, and the concentration of oxalic acid is 5g/L;
SEM images of the lithium-rich manganese-based precursor material obtained in this example at 3000 times magnification are shown in fig. 1 and at 5000 times magnification are shown in fig. 2.
Example 2
The embodiment provides a preparation method of a lithium-rich manganese-based precursor material, which comprises the following steps:
(1) Adding 33.5kg of pure water into a reaction kettle, adding 200g of sodium hydroxide solution and 250g of oxalic acid solution as reaction base solution, introducing nitrogen for 3 hours, controlling the flow rate of the nitrogen to be 200L/h, and controlling the initial pH value of the base solution to be 12;
(2) Under the nitrogen atmosphere, a nickel-cobalt-manganese mixed salt solution is introduced into the base solution in the step (1) at a flow rate of 1.5kg/h, a sodium hydroxide solution is introduced into the base solution at a flow rate of 0.69kg/h and an oxalic acid solution is introduced into the base solution at a flow rate of 0.18kg/h, a coprecipitation reaction is carried out, oxygen-containing gas is introduced after the coprecipitation reaction is carried out for 2h, then the coprecipitation reaction is continued, after the coprecipitation reaction is finished, the slurry after the reaction is transferred into a suction filtration bottle, alkali liquor and hot water are selected for three times, and then the slurry is dried at a temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor material;
the oxygen-containing gas is air, and the flow rate of the oxygen-containing gas is 15L/h; the flow rate of the nitrogen is 200L/h; the temperature of the coprecipitation reaction is 50 ℃, the pH is controlled between 10.0 and 10.4, and the stirring speed is 400rpm;
in the nickel-cobalt-manganese mixed salt solution, the mass concentration is 80g/L, and the molar ratio of nickel ions to cobalt ions to manganese ions is 0.167:0.167:0.666; the mass fraction of the sodium hydroxide solution is 30%, and the concentration of oxalic acid is 2g/L.
Example 3
The embodiment provides a preparation method of a lithium-rich manganese-based precursor material, which comprises the following steps:
(1) Adding 33.5kg of pure water into a reaction kettle, adding 100g of sodium hydroxide solution and 200g of oxalic acid solution as reaction base solution, introducing nitrogen for 3 hours, controlling the flow rate of the nitrogen to be 50L/h, and controlling the initial pH value of the base solution to be 11.5;
(2) Under the nitrogen atmosphere, a nickel-cobalt-manganese mixed salt solution is introduced into the base solution in the step (1) at a flow rate of 1.5kg/h, a sodium hydroxide solution is introduced into the base solution at a flow rate of 0.69kg/h and an oxalic acid solution is introduced into the base solution at a flow rate of 0.18kg/h, a coprecipitation reaction is carried out, oxygen-containing gas is introduced after the coprecipitation reaction is carried out for 10h, then the coprecipitation reaction is continued, after the coprecipitation reaction is finished, the slurry after the reaction is transferred into a suction filtration bottle, alkali liquor and hot water are selected for three times, and then the slurry is dried at a temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor material;
the oxygen-containing gas is air, and the flow rate of the oxygen-containing gas is 5L/h; the flow rate of the nitrogen is 50L/h; the temperature of the coprecipitation reaction is 60 ℃, the pH is controlled between 10.6 and 11.0, and the stirring speed is 400rpm;
in the nickel-cobalt-manganese mixed salt solution, the mass concentration is 120g/L, and the molar ratio of nickel ions to cobalt ions to manganese ions is 0.30:0.05:0.65; the mass fraction of the sodium hydroxide solution is 35%, and the concentration of oxalic acid is 10g/L.
Example 4
The embodiment provides a preparation method of a lithium-rich manganese-based precursor material, which comprises the following steps:
(1) Adding 33.5kg of pure water into a reaction kettle, adding 200g of sodium hydroxide solution and 250g of oxalic acid solution as reaction base solution, introducing nitrogen for 3 hours, controlling the flow rate of the nitrogen to be 120L/h, and controlling the initial pH value of the base solution to be 12;
(2) Under the nitrogen atmosphere, a nickel-cobalt-manganese mixed salt solution is introduced into the base solution in the step (1) at a flow rate of 1.5kg/h, a sodium hydroxide solution is introduced into the base solution at a flow rate of 0.69kg/h and an oxalic acid solution is introduced into the base solution at a flow rate of 0.18kg/h, a coprecipitation reaction is carried out, oxygen-containing gas is introduced after the coprecipitation reaction is carried out for 6h, then the coprecipitation reaction is continued, after the coprecipitation reaction is finished, the slurry after the reaction is transferred into a suction filtration bottle, alkali liquor and hot water are selected for three times, and then the slurry is dried at a temperature of 120 ℃ to obtain the lithium-rich manganese-based precursor material;
the oxygen-containing gas is oxygen, and the flow rate of the oxygen-containing gas is 6L/h; the flow rate of the nitrogen is 120L/h; the temperature of the coprecipitation reaction is 58 ℃, the pH is controlled between 10.4 and 10.6, and the stirring speed is 600rpm;
in the nickel-cobalt-manganese mixed salt solution, the mass concentration is 100g/L, and the molar ratio of nickel ions to cobalt ions to manganese ions is 0.30:0.05:0.65; the mass fraction of the sodium hydroxide solution is 32%, and the concentration of oxalic acid is 8g/L.
Example 5
The present example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as that of example 1, except that the co-precipitation reaction in step (2) is started to be performed for 1h, and then an oxygen-containing gas is introduced.
Example 6
The present example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as that of example 1, except that the co-precipitation reaction in step (2) is started to be performed for 12 hours, and then an oxygen-containing gas is introduced.
Example 7
The present example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as that of example 1 except that the flow rate of the oxygen-containing gas in step (2) is 3L/h.
Example 8
The present example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as that of example 1 except that the flow rate of the oxygen-containing gas in step (2) is 20L/h.
Example 9
This example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as example 1 except that the oxygen-containing gas in step (2) is oxygen.
Comparative example 1
This comparative example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as example 1 except that the oxygen-containing gas is not introduced in step (2) but the coprecipitation reaction is always performed in a nitrogen atmosphere;
SEM images of the lithium-rich manganese-based precursor material obtained in this comparative example at 3000 times magnification are shown in fig. 3 and at 5000 times magnification are shown in fig. 4.
Comparative example 2
This comparative example provides a method for preparing a lithium-rich manganese-based precursor material, which is the same as example 1 except that nitrogen is not introduced in both step (1) and step (2), but the coprecipitation reaction is always performed in the oxygen-containing gas atmosphere.
The lithium-rich manganese-based precursor materials obtained in the above examples and comparative examples were subjected to particle size distribution and BET test, and the test results are shown in table 1:
TABLE 1
From table 1, the following points can be seen:
(1) The (D90-D10)/D50 of the lithium-rich manganese precursor material obtained by the invention is below 0.71, and the BET is between 25 and 30m 2 About/g; as can be seen from the combination of examples 1-4 and comparative example 1, the high-dispersibility and high-proportion-surface lithium-rich manganese-based precursor particles obtained by the method have relatively uniform particle size distribution, and the purpose of improving the dispersibility of the lithium-rich manganese-based precursor is achieved. The introduction of micro-oxidation effectively inhibits the collision agglomeration of precursor particles in the growth stage, the BET of the precursor is obviously improved and maintained at 25-30m 2 Between/g; the increase of BET is beneficial to the full contact between the precursor and the lithium source in the subsequent positive electrode sintering process, and is important for the development of the lithium-rich manganese-based positive electrode material with stable structure and good cycle performance; as can be seen from example 1 and comparative example 2, if the coprecipitation reaction is always performed in an oxygen-containing gas, and no nitrogen is introduced, the lithium-rich manganese precursor is directly oxidized into nickel cobalt manganese oxide, and a large amount of Mn is present 3 O 4 And MnO 2 The mixed phases are equal, the particles are mutually agglomerated and adhered, the overall morphology and the dispersibility are poor, and the electrochemical performance of the subsequent positive electrode material is seriously influenced; as is clear from examples 1 and 5 to 9, the time for starting the introduction of the oxygen-containing gas, the type of the oxygen-containing gas after the introduction flow rate of the oxygen-containing gas, influences the oxidation degree of the system, and thus influences the dispersibility and specific surface area of the product.
(2) As can be seen from the SEM images of fig. 1 to 4, the precursor secondary particles in comparative example 1 are mutually adhered and agglomerated in the growth stage, so that the dispersibility and the overall morphology of the precursor particles are poor; in the embodiment, the introduction of micro-oxidation effectively inhibits the collision agglomeration of particles in the growth stage, the obtained precursor secondary particles are uniformly distributed, the dispersibility is obviously improved, and the sphericity of the whole appearance is also improved.
In summary, the invention provides a lithium-rich manganese-based precursor material, and a preparation method and application thereof, wherein the preparation method introduces an oxidizing atmosphere in the growth stage of the precursor material, so that the problems of compact particle growth, easy agglomeration and poor morphology in the existing preparation process of the lithium-rich manganese-based precursor material are avoided, and the lithium-rich manganese-based precursor material with high dispersibility and high specific surface is obtained.
The foregoing is merely illustrative of the present invention, and the present invention is not limited thereto, and it should be apparent to those skilled in the art that any changes or substitutions that fall within the technical scope of the present invention disclosed herein are within the scope of the present invention.
Claims (10)
1. The preparation method of the lithium-rich manganese-based precursor material is characterized by comprising the following steps of:
and mixing the nickel-cobalt-manganese mixed salt solution, the precipitator solution and the complexing agent solution in a protective gas atmosphere, performing a coprecipitation reaction, starting to introduce oxygen-containing gas when particles enter a growth stage in the coprecipitation reaction, and then continuing the coprecipitation reaction to obtain the lithium-rich manganese-based precursor material.
2. The method according to claim 1, wherein the co-precipitation reaction is started to be carried out for 2 to 10 hours, and then the oxygen-containing gas is introduced;
preferably, the oxygen-containing gas comprises air or oxygen, preferably air;
preferably, the protective gas comprises nitrogen and/or an inert gas.
3. The production method according to claim 1 or 2, wherein the flow rate of the oxygen-containing gas is 5 to 15L/h;
preferably, the flow rate of the protective gas is 50-200L/h.
4. A method of preparation according to any one of claims 1-3, characterized in that the precipitant solution comprises sodium hydroxide solution and/or potassium hydroxide solution;
preferably, the mass fraction of the precipitant solution is 30-35wt%;
preferably, the complexing agent solution comprises oxalic acid and/or ammonia;
preferably, the mass concentration of the complexing agent solution is 2-10g/L.
5. The method according to any one of claims 1 to 4, wherein the nickel cobalt manganese mixed salt solution, the precipitant solution and the complexing agent solution are circulated into the base solution to perform a coprecipitation reaction;
preferably, the pH of the base solution is 11.5-12, and the base solution comprises water, a precipitant solution and a complexing agent solution;
preferably, in the nickel-cobalt-manganese mixed salt solution, the molar ratio of nickel ions to cobalt ions to manganese ions is x, y and z, wherein x+y+z=1, z is larger than or equal to 0.6,0 and is smaller than x and smaller than 0.4, and 0 is smaller than y and smaller than 0.4.
6. The process according to any one of claims 1 to 5, wherein the coprecipitation reaction is carried out at a temperature of 50 to 60 ℃, a pH of 9.5 to 11.5 and a stirring speed of 400 to 700rpm;
preferably, after the coprecipitation reaction is finished, suction filtration, washing and drying are also carried out;
preferably, the temperature of the drying is 100-150 ℃;
preferably, the washing comprises washing with alkali liquor and water 2-5 times respectively.
7. The preparation method according to any one of claims 1 to 6, characterized in that the preparation method comprises the steps of:
under the protective gas atmosphere, the nickel-cobalt-manganese mixed salt solution, the precipitator solution and the complexing agent solution are circulated and introduced into the base solution, the coprecipitation reaction is carried out, oxygen-containing gas is introduced after the coprecipitation reaction is carried out for 2-10 hours, then the coprecipitation reaction is continued, and after the coprecipitation reaction is finished, suction filtration, washing and drying treatment at the temperature of 100-150 ℃ are carried out, so that the lithium-rich manganese-based precursor material is obtained;
the oxygen-containing gas comprises air or oxygen, and the flow rate of the oxygen-containing gas is 5-15L/h; the protective gas comprises nitrogen and/or inert gas, and the inlet flow rate of the protective gas is 50-200L/h; the temperature of the coprecipitation reaction is 50-60 ℃, the pH is 9.5-11.5, and the stirring speed is 400-700rpm;
the pH value of the base solution is 11.5-12, the base solution comprises water, a precipitator solution and a complexing agent solution, and the molar ratio of nickel ions, cobalt ions and manganese ions in the nickel-cobalt-manganese mixed salt solution is x:y:z, wherein x+y+z=1, z is more than or equal to 0.6,0 and less than x and less than 0.4, and y is more than or equal to 0 and less than 0.4.
8. A lithium-rich manganese-based precursor material, characterized in that the lithium-rich manganese-based precursor material is prepared by the preparation method according to any one of claims 1-7.
9. A lithium-rich manganese-based cathode material, characterized in that it is obtained by mixing and sintering the lithium-rich manganese-based precursor material according to claim 8 with a lithium source.
10. A lithium ion battery comprising the lithium-rich manganese-based positive electrode material of claim 9.
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