CN114105222A - Nickel-cobalt-manganese hydroxide with porous structure and preparation method thereof - Google Patents
Nickel-cobalt-manganese hydroxide with porous structure and preparation method thereof Download PDFInfo
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- CN114105222A CN114105222A CN202111437208.6A CN202111437208A CN114105222A CN 114105222 A CN114105222 A CN 114105222A CN 202111437208 A CN202111437208 A CN 202111437208A CN 114105222 A CN114105222 A CN 114105222A
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- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 18
- 239000011148 porous material Substances 0.000 claims abstract description 18
- 238000000034 method Methods 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 19
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 19
- 238000005406 washing Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- 239000003513 alkali Substances 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 14
- 229910052751 metal Inorganic materials 0.000 claims description 14
- 239000002184 metal Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 6
- 239000002585 base Substances 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000007873 sieving Methods 0.000 claims description 5
- 239000010941 cobalt Chemical class 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 239000011163 secondary particle Substances 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- 229910003678 NixCoyMnz(OH)2 Inorganic materials 0.000 claims description 2
- 229910052748 manganese Chemical class 0.000 claims description 2
- 239000011572 manganese Chemical class 0.000 claims description 2
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 239000007774 positive electrode material Substances 0.000 abstract description 6
- 230000000087 stabilizing effect Effects 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000002243 precursor Substances 0.000 description 11
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910017071 Ni0.6Co0.2Mn0.2(OH)2 Inorganic materials 0.000 description 4
- 239000010405 anode material Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 239000010406 cathode material Substances 0.000 description 3
- 229940044175 cobalt sulfate Drugs 0.000 description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 239000011702 manganese sulphate Substances 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229940053662 nickel sulfate Drugs 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000008595 infiltration Effects 0.000 description 2
- 238000001764 infiltration Methods 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process 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
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 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
- IPJKJLXEVHOKSE-UHFFFAOYSA-L manganese dihydroxide Chemical compound [OH-].[OH-].[Mn+2] IPJKJLXEVHOKSE-UHFFFAOYSA-L 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
-
- 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
- C01P2006/12—Surface area
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery materials, and discloses a nickel-cobalt-manganese hydroxide with a porous structure and a preparation method thereof. In addition, due to the existence of the pores, the volume change of the positive electrode material in the charge/discharge process can be buffered, and the effect of stabilizing the structure is achieved, so that the aims of improving the specific capacity and the cycle performance are fulfilled.
Description
Technical Field
The invention relates to the technical field of lithium ion battery materials, in particular to a nickel-cobalt-manganese hydroxide with a porous structure and a preparation method thereof.
Background
With the rapid development of science and technology and the increasing demand for new energy, the demand for clean energy by human beings is increasingly urgent. The lithium ion battery has the characteristics of high energy density, small self-discharge, no memory effect and the like, and is widely applied to various fields of new energy automobiles, 3C intelligent products, energy storage and the like. The excellent performance of the lithium ion battery depends on the performance of the anode material of the lithium ion battery to a great extent, and the anode material is a key part of the research of the lithium ion battery and is also the research focus of the current lithium ion battery.
At present, the anode material of the lithium ion battery mainly comprises ternary materials of lithium cobaltate, lithium manganate, lithium iron phosphate and nickel cobalt manganese. The ternary material has higher specific capacity, good cycle performance and stable structure under the synergistic action of three elements of nickel-cobalt-manganese, and is gradually accepted by the market as the anode material of the vehicle-mounted power battery in recent years. Meanwhile, with the implementation of a series of policies of our country on new energy automobiles, the ternary cathode material has a good development prospect in the field of power batteries.
The ternary precursor is a key material for preparing the ternary cathode material, and the core physical and chemical properties of the ternary cathode material are directly determined by the performance of the ternary precursor. At present, the main method for preparing the nickel-cobalt-manganese ternary precursor is a coprecipitation method, namely under the protection of nitrogen, a nickel-cobalt-manganese metal salt solution is complexed with a complexing agent, and then a precipitator sodium hydroxide is subjected to saline-alkali neutralization reaction to prepare spheroidal secondary particles. And finally obtaining the nickel-cobalt-manganese hydroxide precursor after aging, alkaline treatment, solid-liquid separation, washing and drying.
The invention discloses a nickel-cobalt-manganese hydroxide precursor and a preparation method thereof, wherein a metal mixed salt solution containing saturated dissolved oxygen is used, oxygen is enriched in a reaction bottom solution in the early stage of coprecipitation reaction to obtain a trace amount of oxidized nickel-cobalt-manganese hydroxide, and inert gas is blown in the later stage to ensure that a reaction kettle is oxygen-deficient. Because oxygen is enriched in the early stage of the reaction and is deficient in the later stage of the reaction, a precursor with a loose inner part and a compact outer part structure is obtained by the reaction, and the structure is favorable for overcoming the defects that the material is easy to crack in the sintering process and the battery reaction process, thereby improving the battery capacity and the cycling stability. But the structure has compact surface, is not beneficial to lithium ion transmission and the infiltration of electrolyte, and reduces the rate capability, the cycle performance and other electrochemical performances of the lithium ion battery.
Disclosure of Invention
The invention aims to provide a nickel-cobalt-manganese hydroxide with a porous structure and a preparation method thereof, and the prepared precursor has abundant and uniform pores and relatively high specific surface area. After being sintered with a lithium source, the pores provide abundant and various transmission channels for lithium ions, so that the electrolyte can permeate in the material, the transmission channels can be shortened, and the transmission efficiency can be effectively improved. In addition, due to the existence of the pores, the volume change of the positive electrode material in the charge/discharge process can be buffered, and the effect of stabilizing the structure is achieved, so that the aims of improving the specific capacity and the cycle performance are fulfilled.
The technical purpose of the invention is realized by the following technical scheme: the nickel-cobalt-manganese hydroxide with a porous structure has a chemical formula of Nix Coy Mnz(OH)2Wherein x + y + z is 1, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 0.5, and z is more than 0 and less than 0.5; the particle size D10 of the nickel-cobalt-manganese hydroxide secondary particles with porous structures is more than 2.0 μm; d50 is 4-18 μm; d90 is less than 30 mu m; tap density is more than or equal to 1.50g/cm3The specific surface area is 4-20m2/g。
The invention is further provided with: the nickel-cobalt-manganese hydroxide particles have abundant and uniform pores inside.
A preparation method of nickel-cobalt-manganese hydroxide with a porous structure is characterized by comprising the following steps:
s1: soluble salts of nickel, cobalt and manganese are mixed according to a molar ratio x: y: z is dissolved in pure water to prepare a metal mixed salt solution with a certain concentration, wherein in the molar ratio of the nickel, the cobalt and the manganese, the ranges of x, y and z are respectively that x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 0.5, z is more than 0 and less than 0.5, and x + y + z is equal to 1; preparing a sodium hydroxide solution and ammonia water with certain molar concentration;
s2: adding pure water into the reaction kettle to submerge the bottom layer stirring slurry, and then sequentially adding the ammonia water and the sodium hydroxide solution prepared in the step S1 to serve as a reaction starting bottom solution;
s3: introducing nitrogen and air or mixed gas of nitrogen and oxygen into the reaction kettle, controlling the concentration of oxygen and starting heating;
s4: adding the metal mixed salt solution prepared in the step S1, a sodium hydroxide solution and ammonia water into a reaction kettle by using a metering pump, starting stirring, and controlling the pH value and the reaction temperature in the reaction process;
s5: continuing feeding according to the step S4, gradually adjusting the entering amount of the mixed gas along with the growth of the particle size, and increasing the oxygen concentration; when the granularity of the materials in the reaction kettle reaches the required range, starting to collect the qualified materials through overflow, and aging the collected qualified materials in an aging kettle;
s6: performing solid-liquid separation on the aged material through a filter press, adding dilute alkali for alkali washing, controlling the alkali washing temperature, and adding hot pure water for washing after alkali washing;
s7: and (5) drying the material washed by the water in the step S6, and sequentially sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the porous structure.
The invention is further provided with: in the step S1, the molar concentration of the metal mixed salt solution is 1.0-2.8 mol/L, the molar concentration of the sodium hydroxide solution is 1.0-12.0 mol/L, and the molar concentration of the ammonia water is 1.0-12.0 mol/L.
The invention is further provided with: in the step S2, the pH value of the starting-up base solution is 11.0-12.0, and the ammonia concentration is 1.0-14.0 g/L.
The invention is further provided with: in the step S3, the volume concentration of the oxygen is less than or equal to 2 percent.
The invention is further provided with: in the step S4, the stirring speed is 50-600 rpm, the pH value is 10.0-12.0, the reaction temperature is 50.0-70.0 ℃, and the ammonia water concentration is 1.0-14.0 g/L.
The invention is further provided with: in the step S6, the washing step is washing with prepared dilute alkali liquor and then washing with pure water; the concentration of the dilute alkali liquor is 0.1mol/L, and the temperature is 50-70 ℃; the temperature of the pure water is 50-70 ℃.
The invention is further provided with: in the step S7, the drying temperature is 100-130 ℃.
The invention has the beneficial effects that:
1. the nickel-cobalt-manganese hydroxide particles prepared by the method have a loose and porous structure inside, and can have more contact area with a lithium source when being sintered to prepare a positive electrode material.
2. The positive electrode material obtained by adopting the nickel-cobalt-manganese hydroxide particles prepared by the method can contain more pores, so that the number of lithium ion transmission channels is increased, the infiltration of electrolyte is facilitated, the diffusion path of lithium ions is shortened, and the electrochemical properties such as the rate capability, the cycle performance and the like of the lithium ion battery are effectively improved.
3. Due to the existence of the pores, the volume change of the positive electrode material in the charge/discharge process can be buffered, so that the aim of stabilizing the structure is fulfilled.
4. The nickel-cobalt-manganese hydroxide with the porous structure has simple preparation process and is suitable for industrial production.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 is a schematic diagram of the process of the present invention.
Fig. 2 is a cross-sectional view of a precursor pellet prepared in example 1.
Fig. 3 is a cross-sectional view of a precursor particle prepared in comparative example 1.
Fig. 4 is a cross-sectional view of a precursor particle prepared in comparative example 2.
Detailed Description
The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present invention without any inventive step, are within the scope of the present invention.
Example 1
S1, mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 6: 2: 2 preparing 2mol/L nickel-cobalt-manganese metal salt solution, preparing 10.5mol/L sodium hydroxide solution and preparing 12mol/L ammonia water;
s2, sequentially adding pure water, the ammonia water and the sodium hydroxide into the reaction kettle to form a starting-up base solution with the pH value of 11.30 and the ammonia concentration of 4.5 g/L;
s3, introducing mixed gas of nitrogen and air into the reaction kettle, and controlling the volume concentration of oxygen in the mixed gas to be less than or equal to 2%; starting stirring at the rotating speed of 350rmp, and heating to 58 ℃;
s4, adding the nickel-cobalt-manganese metal mixed salt solution prepared in the step S1, ammonia water and sodium hydroxide into a reaction kettle in sequence by using a metering pump, and starting to react in the atmosphere of mixed gas; controlling the temperature to be 58 ℃, the pH value to be 10.60-11.20 and the ammonia concentration to be 9-10g/L during the reaction period;
s5, continuing feeding according to the step S4, increasing the volume concentration of oxygen to 5% when D50 reaches 3.0 μm, increasing the volume concentration of oxygen to 8% when D50 reaches 6.0 μm, stopping feeding when D50 reaches 9.5 μm, continuing stirring in the reaction kettle for 0.5h, transferring to an aging kettle, and aging for 4 h;
s6, after solid-liquid separation of the aging kettle slurry, washing the slurry with 0.1mol/L alkali liquor at the temperature of 60 ℃ and pure water at the temperature of 60 ℃ in sequence to obtain a washed filter cake;
s7, drying the filter cake washed in the step S6 in a dryer with the set temperature of 120 ℃, and then sequentially sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the internal pore structure.
Prepared to obtain a chemical formula of Ni0.6Co0.2Mn0.2(OH)2Nickel cobalt ofThe microstructure of the manganese hydroxide is of a sphere-like shape, and the specific surface area is 14.77m2(g), tap density measured by tap density instrument is 1.98g/cm3D50 shows radial growth inside the 9.61 μm particle, as shown in FIG. 2, which shows the particle by its cross-sectional view shows the loose porous internal structure.
Comparative example 1
S1, mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 6: 2: 2 preparing 2mol/L nickel-cobalt-manganese metal salt solution, preparing 10.5mol/L sodium hydroxide solution and preparing 12mol/L ammonia water;
s2, sequentially adding pure water, the ammonia water and the sodium hydroxide into the reaction kettle to form a starting-up base solution with the pH value of 11.30 and the ammonia concentration of 4.5 g/L;
s3, introducing mixed gas of nitrogen and air into the reaction kettle, controlling the volume concentration of oxygen in the mixed gas to be less than or equal to 2%, starting stirring at the rotating speed of 350rmp, and heating to 58 ℃;
and S4, adding the nickel-cobalt-manganese metal mixed salt solution prepared in the step S1, ammonia water and sodium hydroxide into a reaction kettle in sequence by using a metering pump, and starting reaction under the atmosphere of mixed gas. Controlling the temperature to be 58 ℃, the pH value to be 10.60-11.20 and the ammonia concentration to be 9-10g/L during the reaction period;
s5, continuing feeding according to the step S4, increasing the volume concentration of oxygen to 3% when D50 reaches 6.0 μm, stopping feeding when D50 reaches 9.5 μm, continuing stirring in the reaction kettle for 0.5h, transferring to an aging kettle, and aging for 4 h.
S6, after solid-liquid separation of the slurry in the aging kettle, washing the slurry with 0.1mol/L liquid alkali at the temperature of 60 ℃ and pure water at the temperature of 60 ℃ in sequence to obtain a washed filter cake;
s7, drying the filter cake washed in the step S6 in a drying machine with a set temperature of 120 ℃, and then sequentially sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with a pore structure inside;
prepared to obtain a chemical formula of Ni0.6Co0.2Mn0.2(OH)2The microstructure of the nickel-cobalt-manganese hydroxide is spheroidal, and the specific surface area is measured to be 7.68m2(g), tap density measured by tap densitometer 2.09g/cm3D50 is 9.38. mu.m. The particle has radial growth inside, and as shown in fig. 3, the particle has a structure with inner pores and outer pores as shown by a cross section of the particle.
Comparative example 2
S1, mixing nickel sulfate, cobalt sulfate and manganese sulfate according to a molar ratio of 6: 2: 2 preparing 2mol/L nickel cobalt manganese metal salt solution, preparing 10.5mol/L sodium hydroxide solution and preparing 12mol/L ammonia water.
S2, sequentially adding pure water, the ammonia water and the sodium hydroxide into the reaction kettle to form a starting-up base solution with the pH value of 11.30 and the ammonia concentration of 4.5 g/L;
s3, introducing nitrogen into the reaction kettle, starting stirring at the rotating speed of 350rmp, and heating to 58 ℃;
s4, adding the nickel-cobalt-manganese metal mixed salt solution prepared in the step S1, ammonia water and sodium hydroxide into a reaction kettle in sequence by using a metering pump, and starting to react in the atmosphere of mixed gas; controlling the temperature to be 58 ℃, the pH value to be 10.60-11.20 and the ammonia concentration to be 9-10g/L during the reaction period;
s5, continuing feeding according to the step S4, stopping feeding when D50 reaches 9.5 mu m, continuing stirring in the reaction kettle for 0.5h, transferring to an aging kettle, and aging for 4 h;
s6, after solid-liquid separation of the slurry in the aging kettle, washing the slurry with 0.1mol/L liquid alkali at the temperature of 60 ℃ and pure water at the temperature of 60 ℃ in sequence to obtain a washed filter cake;
and S7, drying the filter cake washed in the step S6 in a drying machine with a set temperature of 120 ℃, and sequentially sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with a pore structure inside.
Has a chemical formula of Ni0.6Co0.2Mn0.2(OH)2The microstructure of the nickel-cobalt-manganese hydroxide is spheroidal, and the specific surface area is measured to be 6.32m2(g), tap density measured by tap densitometer 2.27g/cm3D50 is 9.75. mu.m. As shown in fig. 4, it was found by the cross section of the particles that the particles did not exhibit an internal structure of loose porosity.
In summary, the chemical formula prepared by the method of the invention is Ni0.6Co0.2Mn0.2(OH)2The specific surface area of the nickel-cobalt-manganese hydroxide is the largest, and as can be seen from fig. 2, fig. 3 and fig. 4, the sectional view of the particle in fig. 2 shows that the particle has an internal structure with loose and porous pores, while the cross section of the particle in comparative example 3 and comparative example 4 has smaller or even no pores and small specific surface area, so that the precursor prepared by the invention has abundant and uniform pores inside and brings relatively high specific surface area. After being sintered with a lithium source, the pores provide abundant and various transmission channels for lithium ions, so that the electrolyte can permeate in the material, the transmission channels can be shortened, and the transmission efficiency can be effectively improved. In addition, due to the existence of the pores, the volume change of the positive electrode material in the charge/discharge process can be buffered, and the effect of stabilizing the structure is achieved, so that the aims of improving the specific capacity and the cycle performance are fulfilled.
Claims (9)
1. A nickel cobalt manganese hydroxide with a porous structure is characterized in that: the chemical formula of the nickel-cobalt-manganese hydroxide is NixCoyMnz(OH)2Wherein x + y + z is 1, x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 0.5, and z is more than 0 and less than 0.5; the particle size D10 of the nickel-cobalt-manganese hydroxide secondary particles with porous structures is more than 2.0 μm; d50 is 4-18 μm; d90 is less than 30 mu m; tap density is more than or equal to 1.50g/cm3The specific surface area is 4-20m2/g。
2. The nickel-cobalt-manganese hydroxide with a porous structure according to claim 1, wherein: the nickel-cobalt-manganese hydroxide particles have abundant and uniform pores inside.
3. A preparation method of nickel-cobalt-manganese hydroxide with a porous structure is characterized by comprising the following steps:
s1: soluble salts of nickel, cobalt and manganese are mixed according to a molar ratio x: y: z is dissolved in pure water to prepare a metal mixed salt solution with a certain concentration, wherein in the molar ratio of the nickel, the cobalt and the manganese, the ranges of x, y and z are respectively that x is more than or equal to 0.5 and less than 1, y is more than 0 and less than 0.5, z is more than 0 and less than 0.5, and x + y + z is equal to 1; preparing a sodium hydroxide solution and ammonia water with certain molar concentration;
s2: adding pure water into the reaction kettle to submerge the bottom layer stirring slurry, and then sequentially adding the ammonia water and the sodium hydroxide solution prepared in the step S1 to serve as a reaction starting bottom solution;
s3: introducing nitrogen and air or mixed gas of nitrogen and oxygen into the reaction kettle, controlling the concentration of oxygen and starting heating;
s4: adding the metal mixed salt solution prepared in the step S1, a sodium hydroxide solution and ammonia water into a reaction kettle by using a metering pump, starting stirring, and controlling the pH value and the reaction temperature in the reaction process;
s5: continuing feeding according to the step S4, gradually adjusting the entering amount of the mixed gas along with the growth of the particle size, and increasing the oxygen concentration; when the granularity of the materials in the reaction kettle reaches the required range, starting to collect the qualified materials through overflow, and aging the collected qualified materials in an aging kettle;
s6: performing solid-liquid separation on the aged material through a filter press, adding dilute alkali for alkali washing, controlling the alkali washing temperature, and adding hot pure water for washing after alkali washing;
s7: and (5) drying the material washed by the water in the step S6, and sequentially sieving and demagnetizing to obtain the nickel-cobalt-manganese hydroxide with the porous structure.
4. The method according to claim 3, wherein the step of preparing the nickel-cobalt-manganese hydroxide with porous structure comprises: in the step S1, the molar concentration of the metal mixed salt solution is 1.0-2.8 mol/L, the molar concentration of the sodium hydroxide solution is 1.0-12.0 mol/L, and the molar concentration of the ammonia water is 1.0-12.0 mol/L.
5. The method according to claim 3, wherein the step of preparing the nickel-cobalt-manganese hydroxide with porous structure comprises: in the step S2, the pH value of the starting-up base solution is 11.0-12.0, and the ammonia concentration is 1.0-14.0 g/L.
6. The method according to claim 3, wherein the step of preparing the nickel-cobalt-manganese hydroxide with porous structure comprises: in the step S3, the volume concentration of the oxygen is less than or equal to 2 percent.
7. The method according to claim 3, wherein the step of preparing the nickel-cobalt-manganese hydroxide with porous structure comprises: in the step S4, the stirring speed is 50-600 rpm, the pH value is 10.0-12.0, the reaction temperature is 50.0-70.0 ℃, and the ammonia water concentration is 1.0-14.0 g/L.
8. The method according to claim 3, wherein the step of preparing the nickel-cobalt-manganese hydroxide with porous structure comprises: in the step S6, the washing step is washing with prepared dilute alkali liquor and then washing with pure water; the concentration of the dilute alkali liquor is 0.1mol/L, and the temperature is 50-70 ℃; the temperature of the pure water is 50-70 ℃.
9. The method according to claim 3, wherein the step of preparing the nickel-cobalt-manganese hydroxide with porous structure comprises: in the step S7, the drying temperature is 100-130 ℃.
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