CN111072076A - Positive electrode material precursor preparation device and positive electrode material precursor preparation method - Google Patents
Positive electrode material precursor preparation device and positive electrode material precursor preparation method Download PDFInfo
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- CN111072076A CN111072076A CN201911311590.9A CN201911311590A CN111072076A CN 111072076 A CN111072076 A CN 111072076A CN 201911311590 A CN201911311590 A CN 201911311590A CN 111072076 A CN111072076 A CN 111072076A
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- 239000002243 precursor Substances 0.000 title claims abstract description 109
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000007774 positive electrode material Substances 0.000 title claims description 58
- 238000006243 chemical reaction Methods 0.000 claims abstract description 149
- 239000002002 slurry Substances 0.000 claims abstract description 117
- 239000007788 liquid Substances 0.000 claims abstract description 56
- 238000001914 filtration Methods 0.000 claims abstract description 49
- 239000010406 cathode material Substances 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims description 47
- 239000012528 membrane Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 12
- 238000007599 discharging Methods 0.000 claims description 11
- 230000000712 assembly Effects 0.000 claims description 9
- 238000000429 assembly Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 7
- 238000004891 communication Methods 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 3
- 239000012527 feed solution Substances 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 1
- 239000010405 anode material Substances 0.000 abstract description 33
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 12
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 15
- 239000007787 solid Substances 0.000 description 9
- 239000002245 particle Substances 0.000 description 8
- 239000012266 salt solution Substances 0.000 description 8
- 238000003756 stirring Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000003513 alkali Substances 0.000 description 6
- 239000008139 complexing agent Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 5
- 229910052744 lithium Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 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
- 230000000052 comparative effect Effects 0.000 description 3
- 229940099596 manganese sulfate Drugs 0.000 description 3
- 235000007079 manganese sulphate Nutrition 0.000 description 3
- 239000011702 manganese sulphate Substances 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
- 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
- 150000003839 salts Chemical class 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- -1 nickel-cobalt-aluminum Chemical compound 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018060 Ni-Co-Mn Inorganic materials 0.000 description 1
- 229910018209 Ni—Co—Mn Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 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
- 238000010276 construction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 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 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002904 solvent Substances 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
- C01G53/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/80—Compounds containing nickel, with or without oxygen or hydrogen, and containing one or more other elements
- C01G53/82—Compounds containing nickel, with or without oxygen or hydrogen, and containing two or more other elements
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to the technical field of lithium ion battery anode materials, and discloses an anode material precursor preparation device and an anode material precursor preparation method, wherein the anode material precursor preparation device (10) comprises a reaction unit (12) and a filtering unit (14) communicated with the reaction unit, and the reaction unit is arranged to be capable of receiving reaction liquid and enabling the reaction liquid to generate slurry containing an anode material precursor; the filter unit is configured to receive the slurry discharged from the reaction unit and discharge the filtered slurry into the reaction unit. The device for preparing the precursor of the cathode material can improve the production efficiency of preparing the precursor of the cathode material and the sphericity of the precursor of the cathode material. The preparation method comprises the following steps: step S10, reacting the reaction feed liquid of the anode material to generate slurry containing the precursor of the anode material; step S20, filtering the slurry obtained in the step S10 and returning the filtered slurry to the step S10 for continuous reaction.
Description
Technical Field
The invention relates to the technical field of lithium ion battery anode materials, in particular to a device and a method for preparing an anode material precursor.
Background
With the double increase of the production and sales volume of new energy automobiles in recent years, the whole upstream and downstream industrial chain is driven to develop rapidly, and especially the demand for power batteries is continuously increased. The manufacturing cost of the power battery of the new energy vehicle is about 30-40%, so that the new energy vehicle has more price advantage and the cost of the power battery needs to be reduced. Among the construction costs of power batteries, the cost of the positive electrode material exceeds 40%, and therefore, how to reduce the cost of the positive electrode material becomes a key issue.
The precursor can be regarded as an intermediate product of the target product, i.e., a preceding product of the target product can be realized through some steps. In the cost constitution of the positive electrode material, the cost of the precursor exceeds 50%, so that the cost of the positive electrode material can be directly reduced by reducing the cost of the precursor.
Taking the lithium ion battery anode material as an example, at present, a coprecipitation method is mainly adopted to prepare an anode material precursor. In order to obtain a precursor product with proper particle size, compact particles, good sphericity and good crystallization, the residence time of the reaction liquid of the precursor in the reaction kettle is often increased, however, the increase of the residence time reduces the production efficiency and increases the production cost.
Disclosure of Invention
The invention aims to solve the problem that the production efficiency is low due to the fact that the retention time of the anode material precursor in a reaction kettle is increased to improve the sphericity density of the anode material precursor in the prior art, and provides the anode material precursor preparation device.
In order to achieve the above object, an aspect of the present invention provides a positive electrode material precursor preparing apparatus including:
the reaction unit is arranged to receive a reaction feed liquid and enable the reaction feed liquid to generate slurry containing a precursor of the anode material; and
and the filtering unit is communicated with the reaction unit and is arranged to receive the slurry discharged by the reaction unit and discharge the filtered slurry into the reaction unit.
In the technical scheme, by arranging the filtering unit, clear liquid such as water in the slurry containing the anode material precursor discharged by the reaction unit can be filtered out, and the filtered slurry is returned to the reaction unit for continuous reaction, so that the solid content of the slurry containing the anode material precursor in the reaction unit is improved, for example, the solid content of the slurry containing the anode material precursor in the reaction unit can reach more than 900g/L, and thus, mutual collision and friction among anode material precursor particles in the slurry are aggravated, and therefore, the production efficiency is improved, the sphericity and morphology of the anode material precursor particles are greatly improved, the stacking density of the anode material precursor particles is correspondingly improved, and the electrical property of the lithium battery is improved.
Preferably, the filter unit includes a filter assembly, the filter assembly includes a filter housing and a filter membrane installed in the filter housing, the filter housing is provided with a slurry inlet for the slurry to enter, a filtered slurry outlet for the filtered slurry to be discharged and a clear liquid outlet for the clear liquid in the filtered slurry to be discharged.
Preferably, the filter unit comprises a plurality of the filter assemblies, which are connected in parallel.
Preferably, the pore size of the filtration membrane is not more than 0.01 μm; and/or the presence of a gas in the gas,
the filtering membrane is an internal pressure type filtering membrane.
Preferably, the reaction unit comprises:
the first reaction component comprises a reaction kettle and a reaction stirrer arranged in the reaction kettle, and the reaction kettle is provided with a reaction material liquid inlet for the reaction material liquid to enter, a slurry overflow port for the slurry generated by the reaction to overflow and a feed back port which can be communicated with the filtered slurry outlet; and
the second reaction assembly comprises an aging kettle and an aging stirrer arranged in the aging kettle, the aging kettle is provided with an aging feed inlet communicated with the slurry overflow port and an aging discharge port for discharging aged slurry, and the aging discharge port can be communicated with the slurry inlet.
Preferably, the first reaction assembly comprises a baffle plate which is arranged on the inner wall of the reaction kettle and protrudes into the reaction kettle; and/or
The first reaction assembly comprises a heat transfer layer arranged on the outer wall of the reaction kettle, and the heat transfer layer is arranged to be capable of heating the reaction kettle.
Preferably, the positive electrode material precursor preparation device comprises a communication component, wherein the communication component comprises a connecting pipe for connecting the aging discharge port and the slurry inlet, and a control valve arranged on the connecting pipe; and/or
The device for preparing the precursor of the positive electrode material comprises a clear liquid leading-out component, wherein the clear liquid leading-out component comprises a clear liquid leading-out pipe arranged at a clear liquid outlet and an observation window arranged on the clear liquid leading-out pipe.
The second aspect of the present invention provides a method for preparing a precursor of a positive electrode material, including:
step S10, reacting the reaction liquid to generate slurry containing the anode material precursor;
step S20, filtering the slurry obtained in the step S10 and returning the filtered slurry to the step S10 for continuous reaction.
The preparation method has the advantages that the efficiency of preparing the precursor containing the cathode material is high, and the prepared precursor containing the cathode material has high density and better sphericity.
Preferably, in the step S20, the clear solution filtered out when the slurry is filtered is discharged at a speed of 100L/h-1000L/h.
Preferably, the step S10 includes:
step S10a, firstly, reacting the reaction liquid to generate slurry containing the anode material precursor;
step S10b, discharging the slurry containing the positive electrode material precursor obtained in the step S10a and continuing aging; and then, the aged slurry containing the positive electrode material precursor is led out and filtered.
Drawings
Fig. 1 is a schematic view of the overall configuration of a positive electrode material precursor preparation apparatus according to a preferred embodiment of the present invention;
FIG. 2 is a scanning electron microscope photograph of the precursor of the positive electrode material obtained in example 1 of the present invention;
fig. 3 is a scanning electron microscope photograph of the positive electrode material precursor obtained in comparative example 1 of the present invention.
Description of the reference numerals
10-a positive electrode material precursor preparation device; 12-a reaction unit; 120-a reaction kettle; 121-an aging kettle; 122-a reaction stirrer; 123-an aging stirrer; 124-heat transfer layer; 125-an aging kettle heat-insulating layer; 126-a reaction kettle heat-insulating layer; 127-a second motor; 128-a first motor; 130-an overflow pipe; 132 a-a first feed tube; 132 b-a second feed tube; 132 c-a third feed pipe; 14-a filtration unit; 140-a filter assembly; 141-a filter housing; 143-a filtration membrane; 16-a communicating component; 160-connecting tube; 161-connecting the main pipe; 162-a control valve; 163-manifold; 164-a delivery pump; 18-a baffle plate; 19-a clear liquid lead-out assembly; 190-a clear liquid delivery pipe; 192-a viewing window; 194 — flow meter.
Detailed Description
In the present invention, the use of directional terms such as "upper, lower, left, right" and "above" are generally understood in conjunction with the drawings and the practical application, unless otherwise specified; "inner and outer" refer to the inner and outer contours of the component.
The invention provides a preparation device of a precursor of a positive electrode material, wherein the preparation device 10 of the precursor of the positive electrode material comprises a reaction unit 12, the reaction unit 12 is arranged to receive reaction liquid and enable the reaction liquid to generate slurry containing the precursor of the positive electrode material, and it can be understood that the reaction liquid of the positive electrode material, such as a nickel-cobalt-manganese ternary positive electrode material or a nickel-cobalt-aluminum ternary positive electrode material, can be added into the reaction unit 12 to perform corresponding reaction so as to generate the slurry containing the precursor of the positive electrode material; the anode material precursor preparation device 10 further comprises a filtering unit 14, the filtering unit 14 is communicated with the reaction unit 12, the filtering unit 14 is configured to receive the slurry discharged from the reaction unit 12 and discharge the filtered slurry into the reaction unit 12, it can be understood that the slurry containing the anode material precursor generated in the reaction unit 12 can be discharged into the filtering unit 14 for filtering, the filtered slurry containing the anode material precursor can be discharged into the reaction unit 12 again for continuous reaction, and the filtered clear solution such as water can be discharged out of the anode material precursor preparation device 10. By providing the filtering unit 14, clear liquid such as water in the slurry containing the cathode material precursor discharged from the reaction unit 12 can be filtered out, and the filtered slurry is returned to the reaction unit 12 to continue the reaction, so that the solid content of the slurry containing the cathode material precursor in the reaction unit 12, for example, the solid content of the slurry containing the cathode material precursor in the reaction unit 12 can reach more than 900g/L, and thus, mutual collision and friction among cathode material precursor particles in the slurry are increased, and thus, not only is the production efficiency improved, but also the sphericity and morphology of the cathode material precursor particles are greatly improved, and the stacking density of the cathode material precursor particles is correspondingly improved, and thus, the electrical performance of the lithium battery is improved. The device for preparing the precursor of the cathode material is preferably suitable for preparing the precursor of the cathode material of the lithium battery.
As shown in fig. 1, the filtering unit 14 may include a filtering assembly 140, the filtering assembly 140 may include a filtering housing 141 and a filtering membrane 143 installed in the filtering housing 141, it is understood that the filtering membrane 143 may be installed in the filtering housing 141 by a membrane support, and the filtering housing 141 may be provided with a slurry inlet for the slurry discharged from the reaction unit 12 to enter, a filtered slurry outlet for the filtered slurry to be discharged, and a clear liquid outlet for the clear liquid in the filtered slurry to be discharged. It is noted that the slurry inlet may be formed at the bottom of the filter housing 141, the filtered slurry outlet may be formed at the top of the filter housing 141, and the clear liquid discharge port may be formed at the sidewall of the filter housing 141.
In order to enhance the filtration effect, the pore size of the filtration membrane 143 is preferably not more than 0.01 μm; in addition, an internal pressure type filtering membrane such as an internal pressure type hollow fiber filtering membrane may be selected as the filtering membrane 143, and particularly, a fiber filtering membrane may be selected as the filtering membrane 143, that is, the filtering module 140 may be disposed such that the flow direction and the filtering direction of the slurry entering the filtering case 141 are perpendicular to each other, and the internal pressure type filtering membrane may be selected just to achieve the object, whereby the clogging of the filtering membrane 143 may be reduced, the filtering module 140 may not be required to be cleaned frequently, and thus the production efficiency may be improved.
In addition, a plurality of filter assemblies 140 can be arranged, and the plurality of filter assemblies 140 can be connected in parallel, so that the filtering volume is increased, the filtering efficiency is improved, when one or some of the filter assemblies 140 cannot be used, the rest of the filter assemblies 140 can still ensure the normal operation of the whole device, and in addition, the filter assemblies 140 can be alternately used, so that the service life of the filter unit 14 is prolonged.
As shown in fig. 1, reaction unit 12 may include a first reaction component, where the first reaction component includes a reaction kettle 120 and a reaction stirrer 122 disposed in reaction kettle 120, where reaction stirrer 122 may stir reaction liquid in reaction kettle 120 under the driving action of a first motor 128 mounted outside reaction kettle 120, reaction kettle 120 may be provided with a reaction liquid inlet for reaction liquid to enter, a slurry overflow port for slurry generated by reaction to overflow, and a return port capable of communicating with the filtered slurry outlet for filtered slurry to return to reaction kettle 120, where: the reaction material liquid inlet port may be opened at the top of the reaction kettle 120, and it can be understood that the reaction material liquid may generally consist of a mixed salt solution, an alkali solution and a complexing agent solution, therefore, a plurality of reaction material liquid inlets, such as a first reaction material liquid inlet, a second reaction material liquid inlet and a third reaction material liquid inlet, may be provided at the top of the reaction kettle 120, and correspondingly, a first feeding pipe 132a, a second feeding pipe 132b and a third feeding pipe 132c may be provided at each reaction material liquid inlet so as to facilitate the corresponding material liquid to enter the reaction kettle 120, the slurry overflow port may be opened at the side wall of the reaction kettle 120, the slurry overflow port may be provided at a preset height of the side wall of the reaction kettle 120 according to actual requirements so as to facilitate the slurry overflow in the reaction kettle 120 to flow out, in addition, a first discharge port may be provided at the bottom wall of the reaction kettle 120 so as to facilitate the discharge of the obtained slurry containing the material precursor, thereby discharging the slurry in the reaction tank 120 at the end of the reaction. In order to further optimize the sphericity and morphology of the cathode material precursor, a second reaction component may be provided, where the second reaction component may include an aging kettle 121 and an aging stirrer 123 disposed in the aging kettle 121, the aging stirrer 123 may be driven by a second motor 127 disposed outside the aging kettle 121 to stir, the aging kettle 121 may be provided with an aging feed inlet communicated with the slurry overflow port and an aging discharge port for discharging aged slurry, and the aging discharge port may be communicated with the slurry inlet, that is, the aged slurry may be discharged into the filtering unit 14 to be filtered, and the filtered slurry may be discharged into the reaction kettle 120 to continue to react. Therefore, the density and the sphericity of the obtained precursor of the cathode material can be greatly optimized, the stacking density of the cathode material is correspondingly improved, and the electrical property of the lithium battery is favorably improved. It should be noted that the aging inlet may be disposed on the side wall of aging kettle 121, and in order to facilitate the entering of the slurry, the aging inlet may be lower than the slurry overflow port; the aging discharge port may be provided at a side wall of aging kettle 121, and the position of the aging discharge port is preferably lower than the position of the aging feed port. In addition, a second discharge port may be provided in the bottom wall of aging kettle 121 for discharging the resulting aged slurry.
In addition, the cathode material precursor preparing apparatus 10 may include a communicating member 16, and the communicating member 16 may include a connecting pipe 160 connecting the aging discharge port and the slurry inlet, and a control valve 162 disposed on the connecting pipe 160, wherein the control valve 162 may control a flow state of the fluid in the connecting pipe 160, that is, may adjust a flow rate of the fluid. It is understood that, when a plurality of filter assemblies 140 are provided, the connection pipe 160 may include a connection main pipe 161 connected to the aging discharge port and a plurality of branch pipes 163 connected at both ends thereof to the connection main pipe 161 and the corresponding slurry inlets, respectively, and the control valve 162 may be provided on the branch pipes 163. In order to allow the aged slurry to be discharged into the filtering assembly 140 better, a transfer pump 164 may be provided on the connection pipe 160.
In addition, the positive electrode material precursor preparing apparatus 10 may include a clear liquid lead-out assembly 19, through which the filtered clear liquid, such as water, may be discharged, and the clear liquid lead-out assembly 19 may include a clear liquid lead-out pipe 190 disposed at the clear liquid discharge port and an observation window 192 disposed at the clear liquid lead-out pipe 190, so that a condition of the discharged clear liquid, such as whether the clear liquid is clear or transparent, may be observed. In order to control the flow rate state of the clear liquid in the clear liquid outlet pipe 190, an automatic control valve may be provided on the clear liquid outlet pipe 190, and in addition, a flow meter 194 may be further provided on the clear liquid outlet pipe 190 to better control the flow rate in the clear liquid outlet pipe 190.
In order to increase the stirring strength in the reaction kettle, the first reaction assembly may include a baffle plate 18 disposed on the inner wall of the reaction kettle 120 and protruding into the reaction kettle 120, so as to further improve the sphericity of the precursor of the cathode material and make the morphology of the precursor better; for better turbulence, a plurality of baffles 18 may be provided, and the plurality of baffles 18 may be evenly distributed along the circumferential wall of the reaction vessel 120.
In addition, as shown in fig. 1, a heat transfer layer 124 may be disposed on an outer wall of the reaction kettle 120, and the heat transfer layer 124 may be disposed to be capable of heating the reaction kettle 120, wherein a heating form of the heat transfer layer 124 is not particularly limited as long as the reaction kettle 120 can be heated, wherein the heat transfer layer 124 may include a jacket that is sleeved outside the reaction kettle 120, and the jacket is provided with a heat transfer medium inlet and a heat transfer medium outlet for allowing a heat transfer medium to enter and exit, respectively, so that a reaction solution in the reaction kettle 120 may be heated after the heating medium is introduced into the jacket. In order to reduce energy consumption, a reactor insulation layer 126 can be arranged on the outer wall of the heat transfer layer 124.
In addition, an aging kettle insulating layer 125 may be disposed on an outer wall of the aging kettle 121, so that the slurry in the aging kettle 121 is maintained at a certain temperature, and the aging kettle 121 may not be heated and insulated, thereby reducing energy consumption.
The invention also provides a preparation method of the precursor of the cathode material, which comprises the following steps: step S10, reacting the reaction solution to generate slurry containing the precursor of the positive electrode material, wherein the solution can be obtained by mixing a salt forming the precursor of the positive electrode material, such as nickel, cobalt, manganese, in a solvent, such as water, to form a mixed salt solution, and mixing an alkali solution and a complexing agent solution together, and the reaction solution reacts at a certain temperature, such as 30-90 ℃, and a certain stirring speed, such as 50-500rpm/min, to generate slurry containing the precursor of the positive electrode material, and the reaction can be performed in an inert gas, such as nitrogen, for better reaction; and S20, filtering the slurry obtained in the step S10, returning the filtered slurry to the step S10 for continuous reaction, and filtering to enable the solid content of the slurry to reach over 900 g/L. The preparation method can be used for preparing the nickel-cobalt-manganese ternary cathode material or the precursor of the nickel-cobalt-aluminum ternary cathode material. Preferably, the positive electrode material precursor preparation device provided by the invention can be used for preparing a positive electrode material precursor such as a positive electrode material precursor of a lithium battery.
It should be noted that, the corresponding salt solution can be selected according to the type of the prepared anode material, for example, a mixed salt solution of nickel sulfate, cobalt sulfate and manganese sulfate can be selected; the total molar concentration of solute, namely salt, in the mixed salt solution is preferably 1-3mol/L, wherein the molar ratio among all the salts can be set according to actual requirements, and is not described again; sodium hydroxide solution can be selected as alkali liquor, and the preferable molar concentration of solute in the alkali liquor is 2-8 mol/L; ammonia water can be selected as a complexing agent, and the mass percent of the solute of the complexing agent is preferably 15-30%.
In order to make the reaction better proceed, the step S10 may include: step S10a, firstly, reacting the reaction liquid to generate slurry containing the anode material precursor; step S10b, discharging the slurry containing the positive electrode material precursor obtained in the step S10a and continuing aging; and then, the aged slurry containing the positive electrode material precursor is led out and filtered. It will be appreciated that the filtered slurry may continue to return to the step S10a for continued reaction. It is noted that, in the step S10a, the mixed salt solution is preferably added into the reaction kettle 120 at a feeding rate of 200-400L/h, the alkali solution is preferably added into the reaction kettle 120 at a feeding rate of 150-350L/h, and the complexing agent is preferably added into the reaction kettle 120 at a feeding rate of 15-60L/h.
In addition, in the step S20, the filtered clear solution is discharged at a speed of 100L/h to 1000L/h when the slurry is filtered, so that the reaction can better proceed, which is beneficial to further increase of the solid content of the slurry, further improve the sphericity and morphology of the precursor, correspondingly improve the bulk density of the cathode material, and further preferably, the filtered clear solution is discharged at a speed of 200L/h to 800L/h.
In addition, it should be noted that the discharged slurry is subjected to filter pressing, washing and drying to obtain a solid-state positive electrode material precursor, wherein the positive electrode material precursor can be dried preferably at 100-.
The effects of the present invention will be further described with reference to examples.
Examples
Example 1
The positive electrode material precursor was prepared using the positive electrode material precursor preparation apparatus shown in fig. 1 and the preparation method provided in the present application.
(1) Taking nickel sulfate, cobalt sulfate and manganese sulfate as nickel sulfate according to the molar ratio: cobalt sulfate: adding manganese sulfate to water together at a ratio of 5:2:3 to prepare a mixed salt solution of 2.0mol/L, preparing liquid caustic soda with a mass fraction of 32% to prepare 5mol/L alkali liquor as a precipitant, taking 25% ammonia water as a complexing agent, adding the mixed salt solution into a reaction kettle 120 at an adding speed of 280L/h, 225L/h and 25L/h under a nitrogen atmosphere, and stirring for reaction, wherein: the stirring speed is set to be 100rpm/min, the temperature is set to be 50 ℃, the granularity of the precursor of the anode material is controlled to be 4.0 +/-0.3 mu m, the pH value of a reaction system is 11.6 +/-0.1, and the ammonia value is 4.0g/L in the reaction process;
(2) after the reaction in the reaction kettle 120 is completed, the slurry containing the anode material precursor generated in the reaction kettle 120 overflows into the aging kettle 121, and the aging reaction is continued;
(3) after the aging reaction is finished, discharging the aged slurry into a filtering component 140, adjusting to discharge clear liquid at an outflow speed of 200L/h, and then continuously discharging the filtered slurry into a reaction kettle 120 for continuous stirring reaction;
(4) repeating the steps until the reaction is finished, wherein the solid content of the finally obtained slurry is 840 g/L;
(5) discharging the reacted slurry, press-filtering, washing and drying at 120 deg.C to obtain nickel-cobalt-manganese hydroxide N with D50 of 4.0 μmi0.5Co0.2Mn0.3(OH)2The apparent density of the precursor of the anode material is 1.17g/cm through detection3Tap density of 1.90g/cm3Is toSurface area of 6.5m2The scanning electron micrograph of the positive electrode material precursor is shown in fig. 2.
Comparative example
Comparative example 1
Example 1 was repeated, wherein the slurry was not filtered, but circulated in reaction vessel 120 and aging vessel 121, and the remaining conditions were not changed, to finally obtain a slurry having a solid content of 105g/L, and finally obtain Ni-Co-Mn hydroxide N having a D50 of 4.0. mu.mi0.5Co0.2Mn0.3(OH)2The apparent density of the precursor of the anode material is 0.98g/cm through detection3Tap density of 1.64g/cm3Specific surface area of 8.0m2The scanning electron micrograph of the positive electrode material precursor is shown in fig. 3.
Therefore, the efficiency of preparing the precursor of the cathode material by using the device and the method provided by the invention is higher, and the solid content of the slurry is higher. As can be seen from fig. 2 and 3, the sphericity of the cathode material precursor prepared by the apparatus and method provided by the present invention is better, and the density is higher.
The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, numerous simple modifications can be made to the technical solution of the invention, including combinations of the individual specific technical features in any suitable way. The invention is not described in detail in order to avoid unnecessary repetition. Such simple modifications and combinations should be considered within the scope of the present disclosure as well.
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