CN115893515B - Preparation method of nickel-cobalt-containing hydroxide positive electrode material precursor - Google Patents
Preparation method of nickel-cobalt-containing hydroxide positive electrode material precursor Download PDFInfo
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- 239000002243 precursor Substances 0.000 title claims abstract description 57
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000007774 positive electrode material Substances 0.000 title claims description 29
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 125
- 238000006243 chemical reaction Methods 0.000 claims abstract description 100
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 58
- 238000000034 method Methods 0.000 claims abstract description 31
- 239000000463 material Substances 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 29
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 25
- 239000011572 manganese Substances 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 13
- 239000012266 salt solution Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000013078 crystal Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- UUCGKVQSSPTLOY-UHFFFAOYSA-J cobalt(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Co+2].[Ni+2] UUCGKVQSSPTLOY-UHFFFAOYSA-J 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 9
- 239000010405 anode material Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 6
- 230000001276 controlling effect Effects 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 229910052759 nickel Inorganic materials 0.000 description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 9
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 229910001873 dinitrogen Inorganic materials 0.000 description 9
- 229910052748 manganese Inorganic materials 0.000 description 9
- 239000002002 slurry Substances 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 229940099596 manganese sulfate Drugs 0.000 description 8
- 239000011702 manganese sulphate Substances 0.000 description 8
- 235000007079 manganese sulphate Nutrition 0.000 description 8
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 8
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 8
- 229940053662 nickel sulfate Drugs 0.000 description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 8
- 229940044175 cobalt sulfate Drugs 0.000 description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 7
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000011437 continuous method Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 229910016739 Ni0.5Co0.2Mn0.3(OH)2 Inorganic materials 0.000 description 1
- 229910017223 Ni0.8Co0.1Mn0.1(OH)2 Inorganic materials 0.000 description 1
- 229910017270 Ni0.8Co0.2(OH)2 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
- 230000009286 beneficial effect Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000010586 diagram 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
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052744 lithium 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
- 238000001000 micrograph Methods 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000011164 primary particle Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a nickel-cobalt-containing hydroxide anode material precursor, which comprises the steps of controlling the solid content of a reaction material to be 20% -40% in a reaction stage, and reducing the ammonia value to be 1-3 g/L lower than the growth control ammonia value and/or improving the offline pH value of the growth control to be 0.1-0.25 higher than the offline pH value of the growth control when the D50 is more than 1 mu m of a process standard; and further comprises the step of increasing the ammonia value to be 1-3 g/L higher than the growth control ammonia value and/or reducing the off-line pH value of the growth control to be 0.1-0.25 lower than the off-line pH value of the growth control when the D50 is smaller than the process standard by more than 1 mu m. The advantages are that: can obviously reduce micro powder, improve the morphology of small particles and increase the tap density of the precursor.
Description
Technical Field
The invention relates to a production technology of a battery anode material, in particular to a production method of an anode material precursor.
Background
In recent years, power products such as new energy automobiles are being used more and more widely, and as a power source for driving these devices, the requirements for the capacity, charge and discharge rate, and the like of secondary batteries are becoming higher. Under such circumstances, lithium ion batteries with high tap density, wide particle size distribution, good particle morphology, and low production cost are attracting attention.
The anode material is an important component of a lithium ion battery, the current commercial anode material mainly comprises lithium iron phosphate, lithium manganate, lithium cobaltate and ternary materials, and particularly the multi-element material has the characteristic of nickel, cobalt, manganese and aluminum, so that the multi-element material becomes a hot spot for researching the anode material of the current power battery.
The general preparation methods of the positive electrode material precursor are divided into a continuous method and an intermittent method, wherein the continuous method has the advantages of good production continuity, high tap density, more micro powder, poor shape of small particles, no micro powder, good sphericity, narrow particle size distribution, low tap and discontinuous production. How to reduce micro powder, improve the morphology of small particles and obtain low-cost precursors with wide distribution and high tap density is a research hot spot for the development of new energy industries.
Disclosure of Invention
The invention provides a preparation method of a nickel-cobalt-containing hydroxide positive electrode material precursor, which aims to reduce micro powder, improve the morphology of small particles and improve the tap density of the precursor.
The technical scheme adopted by the invention is as follows: the preparation method of the nickel-cobalt-containing hydroxide positive electrode material precursor comprises the steps of controlling the solid content of a reaction material to be 20% -40% in a reaction stage, and reducing the ammonia value to be 1-3 g/L lower than the growth control ammonia value and/or increasing the offline growth control pH value to be 0.1-0.25 higher than the offline growth control pH value when the D50 is more than 1 mu m of a process standard; and further comprises the step of increasing the ammonia value to be 1-3 g/L higher than the growth control ammonia value and/or reducing the off-line pH value of the growth control to be 0.1-0.25 lower than the off-line pH value of the growth control when the D50 is smaller than the process standard by more than 1 mu m.
The invention can be implemented according to the following steps:
s1, introducing an alkali solution with the concentration of 2-10 mol/L and a complexing agent with the concentration of 2-11 mol/L into a reaction container, and introducing inert gas;
s2, introducing a metal salt solution with the concentration of 1-2.5 mol/L into the reaction container at the flow rate of 1-20L/min for precipitation reaction to synthesize a precursor crystal of the positive electrode material; in the precipitation process, the temperature in the reaction vessel is kept at 40-80 ℃ and the stirring speed is 300-1000 r/min;
s3, in the reaction stage, adjusting the offline pH value of the growth control to 10-12.5, adjusting the ammonia value of the growth control to 3-15 g/L, and starting overflow grafting after the D50 meets the process requirement;
in the reaction stage, controlling the solid content of the reaction materials to be 20% -40%, and when D50 is more than 1 mu m of the process standard, reducing the ammonia value to be 1-3 g/L lower than the growth control ammonia value and/or increasing the offline pH value of the growth control to be 0.1-0.25 higher than the offline pH value of the growth control; when D50 is smaller than the process standard by more than 1 mu m, the ammonia value is increased to be 1-3 g/L higher than the ammonia value of the growth control and/or the off-line pH value of the growth control is reduced to be 0.1-0.25 lower than the off-line pH value of the growth control.
As a further improvement of the invention, the chemical formula of the nickel-cobalt-containing hydroxide positive electrode material precursor is Ni x Co y Mn z Al d (OH) 2 Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and x+y+z+d=1.
As a further improvement of the present invention, the alkali solution is one or more selected from potassium hydroxide, lithium hydroxide and sodium hydroxide.
As a further improvement of the invention, the complexing agent is selected from one or any of ammonium carbonate, citric acid, ammonia water, ammonium bicarbonate and disodium ethylenediamine tetraacetate.
As a further improvement of the invention, the metal salt solution comprises one or any of nickel salt solution, manganese salt solution, cobalt salt solution and aluminum salt solution; in particular, a sulfate, nitrate, chloride solution or the like of the above metal can be used.
The invention also discloses a nickel-cobalt-containing hydroxide positive electrode material precursor, which is prepared by the preparation method of the nickel-cobalt-containing hydroxide positive electrode material precursor.
The invention also discloses a positive electrode material which is characterized by comprising the nickel-cobalt-containing hydroxide positive electrode material precursor.
The invention also discloses a lithium ion battery which is characterized by comprising the positive electrode material.
The beneficial effects of the invention are as follows: the precursor prepared by the method can obviously reduce micro powder, improve the morphology of small particles and increase the tap density of the precursor.
Drawings
Fig. 1 is a process flow diagram of the present invention.
Fig. 2 is an electron microscope image of the precursor product of the third embodiment.
Fig. 3 is an electron micrograph of the precursor product of comparative example one.
Detailed Description
The invention is further illustrated below with reference to examples.
Embodiment one:
the precursor is prepared as follows:
(1) A10 mol/L sodium hydroxide solution and a 10mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate and manganese sulfate solution with the concentration of 2mol/L (nickel, cobalt and manganese are in a molar ratio of 5:2:3) into a reaction container at a flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging a lower layer blade, controlling the temperature to 55 ℃, and carrying out precipitation reaction at a stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 11, adjusting the ammonia value of the growth control to 7g/L, and starting overflow grafting after the D50 reaches 10 mu m of the technological requirement;
(4) Controlling the solid content of the reaction materials to be 35% -40% in the reaction stage, and increasing the offline pH value of the growth control to 11.25 when the D50 is larger than 11 mu m; reducing the off-line pH of the growth control to 10.80 when D50 is less than 9 μm; when D50 is more than or equal to 9 mu m and less than or equal to 11 mu m, maintaining the offline pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged;
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.5 Co 0.2 Mn 0.3 (OH) 2 。
Embodiment two:
the precursor is prepared as follows:
(1) A sodium hydroxide solution having a concentration of 8mol/L and an aqueous ammonia solution having a concentration of 8mol/L were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate and manganese sulfate solution with the concentration of 1.8mol/L (nickel, cobalt and manganese in the molar ratio of 8:1:1) into a reaction container at the flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging the lower-layer paddles, controlling the temperature to 55 ℃, and carrying out precipitation reaction at the stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 12, adjusting the ammonia value of the growth control to 12g/L, utilizing concentration equipment to improve the solid content of the material to 20-25%, and starting overflow connection after the D50 reaches 10 mu m of the technological requirement;
(4) In the reaction stage, controlling the solid content of the reaction materials to be 20% -25%, and reducing the growth control ammonia value to 9g/L when the D50 is larger than 11 mu m; when D50 is less than 9 mu m, the ammonia value of growth control is increased to 15g/L; when D50 is more than or equal to 9 mu m and less than or equal to 11 mu m, maintaining the offline pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.8 Co 0.1 Mn 0.1 (OH) 2 。
Embodiment III:
the precursor is prepared as follows:
(1) A10 mol/L sodium hydroxide solution and an 8mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate and manganese sulfate solution with the concentration of 1.8mol/L (nickel, cobalt and manganese in the molar ratio of 88:7:5) into a reaction container at the flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging the lower-layer paddles, controlling the temperature to 55 ℃, and carrying out precipitation reaction at the stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 12, adjusting the ammonia value of the growth control to 10g/L, utilizing concentration equipment to improve the solid content of the material to 20-30%, and starting overflow connection after the D50 reaches 10 mu m of the technological requirement;
(4) In the reaction stage, controlling the solid content of the reaction materials to be 20% -25%, and when D50 is larger than 11 mu m, increasing the offline pH value of growth control to 12.2, and reducing the ammonia value of growth control to 8g/L; when D50 is less than 9 mu m, reducing the off-line pH value of the growth control to 11.8, and increasing the ammonia value of the growth control to 13g/L; when D50 is more than or equal to 9 mu m and less than or equal to 11 mu m, maintaining the offline pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.88 Co 0.07 Mn 0.05 (OH) 2 。
Embodiment four:
the precursor is prepared as follows:
(1) A10 mol/L sodium hydroxide solution, a saturated sodium metaaluminate solution and an 8mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate, manganese sulfate solution and sodium metaaluminate solution (molar ratio of nickel, cobalt, manganese and aluminum is 92:1:2:5) with the concentration of 1.8mol/L into a reaction container at the flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging a lower blade, controlling the temperature to be 50 ℃, and carrying out precipitation reaction at the stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 12, adjusting the ammonia value of the growth control to 12g/L, utilizing concentration equipment to improve the solid content of the material to 25-30%, and starting overflow connection after the D50 reaches 15 mu m of the technological requirement;
(4) In the reaction stage, controlling the solid content of the reaction materials to be 20% -25%, and when D50 is larger than 16 mu m, increasing the offline pH value of growth control to 12.2, and reducing the ammonia value of growth control to 10g/L; when D50 is smaller than 14 mu m, reducing the off-line pH value of the growth control to 11.8, and increasing the ammonia value of the growth control to 14g/L; when D50 is more than or equal to 14 mu m and less than or equal to 16 mu m, maintaining the off-line pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.92 Co 0.01 Mn 0.02 Al 0.05 (OH) 2 。
Fifth embodiment:
the precursor is prepared as follows:
(1) A10 mol/L sodium hydroxide solution and a 10mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel nitrate and cobalt nitrate solution (nickel and cobalt in a molar ratio of 8:2) with a concentration of 1.8mol/L into a reaction container at a flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging a lower layer blade, controlling the temperature to be 50 ℃, and carrying out precipitation reaction at a stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 11.8, adjusting the ammonia value of the growth control to 10g/L, utilizing concentration equipment to improve the solid content of the material to 30-40%, and starting overflow connection after the D50 reaches 12 mu m of the technological requirement;
(4) In the reaction stage, controlling the solid content of the reaction materials to be 20% -25%, and when D50 is larger than 13 mu m, increasing the offline pH value of growth control to 12.0, and reducing the ammonia value of growth control to 9g/L; when D50 is smaller than 11 mu m, reducing the off-line pH value of the growth control to 11.6, and increasing the ammonia value of the growth control to 13g/L; when D50 is smaller than or equal to 11 mu m and smaller than or equal to 13 mu m, maintaining the offline pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.8 Co 0.2 (OH) 2 。
Example six:
the precursor is prepared as follows:
(1) A sodium hydroxide solution having a concentration of 8mol/L and an aqueous ammonia solution having a concentration of 8mol/L were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate and manganese sulfate solution (nickel and manganese in a molar ratio of 6:4) with the concentration of 2mol/L into a reaction container at a flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging a lower layer blade, controlling the temperature to 55 ℃, and performing precipitation reaction at a stirring speed of 500r/min to synthesize a precursor crystal of the anode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 11.7, adjusting the ammonia value of the growth control to 8g/L, utilizing concentration equipment to improve the solid content of the material to 20-25%, and starting overflow connection after the D50 reaches 10 mu m of the technological requirement;
(4) In the reaction stage, controlling the solid content of the reaction materials to be 30% -35%, and when D50 is larger than 11 mu m, increasing the offline pH value of growth control to 11.8, and reducing the ammonia value of growth control to 7g/L; when D50 is less than 9 mu m, reducing the off-line pH value of the growth control to 11.6, and increasing the ammonia value of the growth control to 9g/L; when D50 is more than or equal to 9 mu m and less than or equal to 11 mu m, maintaining the offline pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.6 Mn 0.4 (OH) 2 。
Comparative example one:
this comparative example is a control experiment of example three, which was performed in the same procedure and conditions as example three, except that: in the step (4), the offline pH value and the ammonia value of growth control and the solid content of the reaction materials are not adjusted according to the product D50, and the specific steps are as follows:
(1) A10 mol/L sodium hydroxide solution and an 8mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate and manganese sulfate solution with the concentration of 1.8mol/L (nickel, cobalt and manganese in the molar ratio of 88:7:5) into a reaction container at the flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging the lower-layer paddles, controlling the temperature to 55 ℃, and carrying out precipitation reaction at the stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 12, adjusting the ammonia value of the growth control to 10g/L, utilizing concentration equipment to improve the solid content of the material to 20-30%, and starting overflow connection after the D50 reaches 10 mu m of the technological requirement;
(4) During the reaction phase, the reaction mass solids content was not adjusted (at this point the reaction mass solids content was about 7%); maintaining the off-line pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.88 Co 0.07 Mn 0.05 (OH) 2 。
Comparative example two:
this comparative example is a control experiment of example three, which was performed in the same procedure and conditions as example three, except that: in the step (4), the offline pH value and the ammonia value of growth control are not adjusted according to the product D50, and the specific steps are as follows:
(1) A10 mol/L sodium hydroxide solution and an 8mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate and manganese sulfate solution with the concentration of 1.8mol/L (nickel, cobalt and manganese in the molar ratio of 88:7:5) into a reaction container at the flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging the lower-layer paddles, controlling the temperature to 55 ℃, and carrying out precipitation reaction at the stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 12, adjusting the ammonia value of the growth control to 10g/L, utilizing concentration equipment to improve the solid content of the material to 20-30%, and starting overflow connection after the D50 reaches 10 mu m of the technological requirement;
(4) In the reaction stage, the solid content of the reaction materials is controlled to be 20% -25% (the same as that of the embodiment), and the growth control offline pH value and the growth control ammonia value of the step (3) are kept unchanged.
(5) The prepared slurry is filtered, aged, washed and dried to obtain a precursor product Ni 0.88 Co 0.07 Mn 0.05 (OH) 2 。
Comparative example three:
this comparative example is a control experiment of example three, which was conducted in the same steps and conditions as in example except that: in the step (4), the solid content of the reaction materials is not regulated, and the specific steps are as follows:
(1) A10 mol/L sodium hydroxide solution and an 8mol/L aqueous ammonia solution were introduced into the reaction vessel, and nitrogen gas was continuously introduced into the reaction vessel.
(2) Introducing nickel sulfate, cobalt sulfate and manganese sulfate solution with the concentration of 1.8mol/L (nickel, cobalt and manganese in the molar ratio of 88:7:5) into a reaction container at the flow rate of 5L/min, adding 10L of pure water into the reaction container, submerging the lower-layer paddles, controlling the temperature to 55 ℃, and carrying out precipitation reaction at the stirring speed of 600r/min to synthesize a precursor crystal of the positive electrode material;
(3) In the reaction process, adjusting the offline pH value of the growth control to 12, adjusting the ammonia value of the growth control to 10g/L, utilizing concentration equipment to improve the solid content of the material to 20-30%, and starting overflow connection after the D50 reaches 10 mu m of the technological requirement;
(4) During the reaction phase, the reaction mass solids content was not adjusted (at this point the reaction mass solids content was about 7%); when D50 is larger than 11 mu m, the off-line pH value of the growth control is increased to 12.2, and the ammonia value of the growth control is reduced to 8g/L; when D50 is less than 9 mu m, reducing the off-line pH value of the growth control to 11.8, and increasing the ammonia value of the growth control to 13g/L; when D50 is more than or equal to 9 mu m and less than or equal to 11 mu m, maintaining the offline pH value of the growth control and the ammonia value of the growth control in the step (3) unchanged.
(5) The prepared slurry is filtered, aged, washed and dried,obtain a precursor product Ni 0.88 Co 0.07 Mn 0.05 (OH) 2 。
Precursor performance detection:
the D50, tap density, specific surface area of the positive electrode material precursors prepared in the above examples and comparative examples were measured, respectively, and are listed in table 1, respectively.
TABLE 1 precursor Performance detection results Table
As can be seen from the detection results of the first to sixth embodiments in Table 1, the precursor material produced by the method has regular morphology, easily controlled granularity and excellent performance, and the tap density reaches more than 2.30.
As can be seen from comparison of the detection results of the third embodiment and the first comparative embodiment in Table 1 and comparison of the fig. 2 and 3, the particle size is easier to control to be at a required value by combining stepwise adjustment of pH and ammonia value after the solid content is adjusted, the problem of irregular primary particles is obviously improved, the sphericity of the whole material is better, and the tap density is obviously improved.
As can be seen from comparison of the third example with the first comparative example, the second comparative example and the third comparative example in table 1, when the solid content is adjusted only in the reaction stage (the second comparative example) or the pH and the ammonia value are adjusted only in the stage (the third comparative example), the tap density of the precursor material does not significantly change, and it can be seen that the present invention has a significant synergistic effect of increasing the tap density of the precursor material between the technical means of controlling the solid content of the reaction material to 20% -40% in the reaction stage and adjusting the off-line pH value and the growth control ammonia value according to the product D50.
Claims (6)
1. The preparation method of the nickel-cobalt-containing hydroxide positive electrode material precursor is characterized by comprising the following steps of: the method comprises the steps of adjusting the offline pH value of growth control to a certain value between 10 and 12.5, adjusting the ammonia value of growth control to a certain value between 3 and 15g/L, and determining the process requirement value of D50 in the reaction stage;
the method also comprises the steps of controlling the solid content of the reaction materials to be 20% -40% in the reaction stage, and reducing the ammonia value to be 1-3 g/L lower than the growth control ammonia value and/or increasing the offline pH value of the growth control to be 0.1-0.25 higher than the offline pH value of the growth control when the D50 is more than the process required value by more than 1 mu m; and (3) when the D50 is smaller than the process required value by more than 1 mu m, increasing the ammonia value to be 1-3 g/L higher than the growth control ammonia value and/or reducing the offline pH value of the growth control to be 0.1-0.25 lower than the offline pH value of the growth control.
2. The method for preparing a nickel-cobalt-containing hydroxide positive electrode material precursor according to claim 1, comprising the steps of:
s1, introducing an alkali solution with the concentration of 2-10 mol/L and a complexing agent with the concentration of 2-11 mol/L into a reaction container, and introducing inert gas;
s2, introducing a metal salt solution with the concentration of 1-2.5 mol/L into the reaction container at the flow rate of 1-20L/min for precipitation reaction to synthesize a precursor crystal of the positive electrode material; in the precipitation process, the temperature in the reaction vessel is kept at 40-80 ℃ and the stirring speed is 300-1000 r/min;
s3, in the reaction stage, adjusting the offline pH value of the growth control to be a certain value between 10 and 12.5, adjusting the ammonia value of the growth control to be a certain value between 3 and 15g/L, determining the process requirement value of D50, and starting overflow connection after the D50 reaches the process requirement value;
in the reaction stage, controlling the solid content of the reaction materials to be 20% -40%, and when D50 is more than the process required value by more than 1 mu m, reducing the ammonia value to be 1-3 g/L lower than the growth control ammonia value and/or increasing the offline pH value of the growth control to be 0.1-0.25 higher than the offline pH value of the growth control; when the D50 is smaller than the process required value by more than 1 mu m, the ammonia value is increased to be 1-3 g/L higher than the growth control ammonia value and/or the off-line pH value of the growth control is reduced to be 0.1-0.25 lower than the off-line pH value of the growth control.
3. The composition according to claim 1The preparation method of the nickel cobalt hydroxide positive electrode material precursor is characterized by comprising the following steps of: the chemical formula of the nickel-cobalt-containing hydroxide positive electrode material precursor is Ni x Co y Mn z Al d (OH) 2 Wherein x is more than or equal to 0 and less than or equal to 1, y is more than or equal to 0 and less than or equal to 1, z is more than or equal to 0 and less than or equal to 1, d is more than or equal to 0 and less than or equal to 1, and x+y+z+d=1.
4. The method for preparing the nickel-cobalt-containing hydroxide positive electrode material precursor according to claim 2, wherein the method comprises the following steps: the alkali solution is selected from one or more of potassium hydroxide, lithium hydroxide and sodium hydroxide.
5. The method for preparing the nickel-cobalt-containing hydroxide positive electrode material precursor according to claim 2, wherein the method comprises the following steps: the complexing agent is one or more selected from ammonium carbonate, citric acid, ammonia water, ammonium bicarbonate and disodium ethylenediamine tetraacetate.
6. The method for preparing the nickel-cobalt-containing hydroxide positive electrode material precursor according to claim 2, wherein the method comprises the following steps: the metal salt solution comprises one or more of nickel salt solution, manganese salt solution, cobalt salt solution and aluminum salt solution.
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