CN116812991A - Ternary precursor preparation method and device and precursor - Google Patents
Ternary precursor preparation method and device and precursor Download PDFInfo
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- CN116812991A CN116812991A CN202310763740.XA CN202310763740A CN116812991A CN 116812991 A CN116812991 A CN 116812991A CN 202310763740 A CN202310763740 A CN 202310763740A CN 116812991 A CN116812991 A CN 116812991A
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- 239000002243 precursor Substances 0.000 title claims abstract description 127
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 163
- 239000007788 liquid Substances 0.000 claims abstract description 124
- 239000002245 particle Substances 0.000 claims abstract description 44
- 238000000034 method Methods 0.000 claims abstract description 25
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 238000009826 distribution Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims abstract description 11
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 49
- 238000003860 storage Methods 0.000 claims description 48
- 238000003756 stirring Methods 0.000 claims description 28
- 238000005192 partition Methods 0.000 claims description 26
- 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
- 230000001105 regulatory effect Effects 0.000 claims description 17
- 230000001276 controlling effect Effects 0.000 claims description 12
- 239000007787 solid Substances 0.000 claims description 12
- 238000004891 communication Methods 0.000 claims description 10
- 238000011084 recovery Methods 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 5
- 238000012360 testing method Methods 0.000 claims description 5
- 238000005056 compaction Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 239000007774 positive electrode material Substances 0.000 abstract description 8
- 239000000243 solution Substances 0.000 description 58
- 239000003513 alkali Substances 0.000 description 25
- 229910021529 ammonia Inorganic materials 0.000 description 23
- 230000000052 comparative effect Effects 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 239000002562 thickening agent Substances 0.000 description 18
- 238000012546 transfer Methods 0.000 description 16
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000001878 scanning electron micrograph Methods 0.000 description 8
- 230000006911 nucleation Effects 0.000 description 6
- 238000010899 nucleation Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000011164 primary particle Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000011437 continuous method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D36/00—Filter circuits or combinations of filters with other separating devices
- B01D36/04—Combinations of filters with settling tanks
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01F—MIXING, e.g. DISSOLVING, EMULSIFYING OR DISPERSING
- B01F27/00—Mixers with rotary stirring devices in fixed receptacles; Kneaders
- B01F27/80—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis
- B01F27/90—Mixers with rotary stirring devices in fixed receptacles; Kneaders with stirrers rotating about a substantially vertical axis with paddles or arms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/18—Stationary reactors having moving elements inside
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/42—Nickelates containing alkali metals, e.g. LiNiO2
- C01G53/44—Nickelates containing alkali metals, e.g. LiNiO2 containing manganese
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
-
- 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)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The application relates to the technical field of precursor preparation, in particular to a preparation method and device of a ternary precursor and the precursor. The preparation method comprises the following steps: step A), reacting the reaction solution at pH1 for t1 time to generate a preset number of precursor crystal nuclei; step B), in t2 time, the pH1 of the reaction solution is reduced to pH2; step C), reacting the reaction solution at pH2 for t3 time to obtain a precursor with a preset median particle size; wherein the difference between pH1 and pH2 is 0.4-1; at least the reaction solution in the step A) is subjected to solid-liquid separation to obtain clear solution, and the clear solution is returned to the reaction solution in the step C), so that the precursor has high particle size distribution concentration, good morphology and few small-particle precursors, the performance of a positive electrode material and the safety performance of a battery are improved, and the precursor prepared by the method has uniform particle distribution, good sphericity, relatively high tap density and stable product quality.
Description
Technical Field
The application relates to the technical field of precursor preparation, in particular to a preparation method and device of a ternary precursor and the precursor.
Background
The performance of the positive electrode material has a crucial influence on the performance of the battery, wherein the ternary positive electrode material has a remarkable ternary synergistic effect, and has the advantages of high energy density, relatively low cost and good safety function, and becomes the main development direction of the current positive electrode material of the lithium battery. The ternary precursor is a key raw material for preparing the ternary cathode material, and largely determines the performance of the cathode material. The ternary precursor is generally synthesized by reacting ternary liquid, alkali liquor and ammonia water under certain conditions, and then the ternary precursor is prepared into a finished product through the steps of aging, solid-liquid separation and the like. Wherein, the solid-liquid separation step generates a large amount of mother liquor, and each ton of ternary precursor is generated to generate 15m mother liquor 3 . At present, the traditional process for treating the ternary precursor wastewater adopts a gas stripping process to treat, recycle ammonia water, produce hydroxide by heavy metal, and recover salt solution by adopting a freezing crystallization process after the pH value is adjusted by stripping drainage. The wastewater treatment method has more steps, complex process and higher operation cost.
Disclosure of Invention
The application discloses a preparation method and device of a ternary precursor and the precursor, and aims to solve the problems of complex wastewater treatment process and high operation cost in the existing ternary precursor preparation process.
In order to achieve the above purpose, the present application provides the following technical solutions:
in a first aspect, the present application provides a method for preparing a ternary precursor, comprising the steps of:
step A), reacting the reaction solution at pH1 for t1 time to generate a preset number of precursor crystal nuclei;
step B), in t2 time, the pH1 of the reaction solution is reduced to pH2;
step C), reacting the reaction solution at pH2 for t3 time to obtain a precursor with a preset median particle size;
wherein the difference between pH1 and pH2 is 0.4-1; at least the clear liquid obtained by solid-liquid separation of the reaction solution in the step A) is refluxed to the reaction solution in the step C).
Further, the pH value is more than or equal to 10.7 and less than or equal to 11.5, and the t1 is more than or equal to 1h and less than or equal to 8h; the pH is more than or equal to 10 and less than or equal to 2 and less than or equal to 10.5, the t2 is more than or equal to 10h and less than or equal to 20h, the t3 is more than or equal to 70h and less than or equal to 80h, and t=t1+t2+t3 and t is more than or equal to 100h.
Further, the concentration of ammonia water in the reaction solution in the step A) is C1, and the concentration of ammonia water in the reaction solution in the step C) is C2, wherein C1 is more than or equal to 1g/L and less than or equal to 8g/L, and C2 is more than or equal to 1g/L and less than or equal to 8g/L.
Further, regulating the pH value of the clarified liquid to be pH3, regulating the ammonia water concentration of the clarified liquid to be C3, wherein the pH value is 13-14, and the C3 is 10-15 g/L.
Further, the method also comprises the step of regulating and controlling the feeding flow rate Q of the reaction solution according to the reaction time t:
0h≤t≤8h，100L/h≤Q≤200L/h；
8h＜t≤16h，400L/h≤Q≤600L/h；
16h＜t，800L/h≤Q≤1000L/h。
further, the stirring speed M of the reaction solution is regulated according to the solid content G of the reaction solution:
G≤100g/L，450r/min≤M≤500r/min；
100g/L＜G≤200g/L，350r/min≤Q≤400r/min；
200g/L＜G≤300g/L，250r/min≤Q≤300r/min；
300g/L＜G，150r/min≤Q≤200r/min。
in a second aspect, the present application provides an apparatus for applying the preparation method of the first aspect, the apparatus comprising a reaction vessel, a recovery assembly in communication with the reaction vessel; the reaction kettle is used for preparing the ternary precursor, and the recovery component is used for recovering and treating the reaction solution in the reaction kettle.
Further, the recovery assembly comprises a first liquid storage tank communicated with the reaction kettle and a second liquid storage tank communicated with the first liquid storage tank, and a liquid discharge pipe of the second liquid storage tank is communicated with the reaction kettle; the first liquid storage tank is used for filtering the reaction solution to obtain a clarified liquid, and the second liquid storage tank is used for storing the clarified liquid and regulating and controlling the pH value and the ammonia water concentration of the clarified liquid.
Further, a longitudinally extending partition plate is arranged in the first liquid storage tank, the partition plate divides a cavity of the first liquid storage tank into a left cavity and a right cavity, the left cavity is communicated with the reaction kettle, and the right cavity is communicated with the second liquid storage tank; the division board includes the lower plate body and the last plate body of being connected with the lower plate body, and the last plate body is equipped with a plurality of filtration pore.
Further, the bottom of the left chamber gradually rises from one end far away from the partition plate to the partition plate, and the bottom of the right chamber gradually falls from the partition plate to one end far away from the partition plate.
In a third aspect, the present application provides a precursor prepared by the preparation method of the first aspect, the precursor having a specific surface area of 7 to 15m 2 And/g, the span of the particle size distribution of the precursor is 0.5-0.7.
Further, the tap density of the precursor is 1.9-2.3 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the powder compaction test of the precursor, when the pressure is 0.5T, the ratio of the difference between the median particle diameter before the precursor is compressed and the median particle diameter after the precursor is compressed to the median particle diameter before the precursor is compressed is less than or equal to 3%.
Further, the precursor includes a porous core, a dense layer, and a porous layer in a direction from the core of the precursor to the outer surface of the precursor.
By adopting the technical scheme of the application, the beneficial effects are as follows:
the preparation method of the ternary precursor provided by the application comprises the steps that the pH value (pH 1) of the reaction solution in the step A) is higher, the reaction solution is helped to form crystal nuclei with preset quantity and size, then the pH value of the reaction solution is reduced from pH1 to pH2 in t2, the reaction solution is switched from a nucleation environment to a growth environment, and the particles are converted from nucleation to growth in the process; after nucleation is finished, stabilizing the pH value of the reaction solution at pH2 until the reaction solution grows to a preset median particle diameter, wherein the precursor prepared by controlling the difference value between pH1 and pH2 and the reaction time has uniform particle distribution, good sphericity, relatively high tap density and stable product quality; the concentration of the recovered clear liquid is lower than that of the alkali liquor of the raw materials, the dispersibility of the clear liquid in the reaction solution in the step C) is better, and the phenomenon that the reaction solution generates fine powder due to overhigh local pH can be effectively avoided, so that the concentration of the particle size distribution of the precursor is high, the morphology is good, the number of the precursors of small particles is small, and the performance of the positive electrode material and the safety performance of a battery are improved.
Drawings
FIG. 1 is a schematic diagram of an apparatus according to an embodiment of the present application;
FIG. 2 is a schematic structural view of a first liquid storage tank according to an embodiment of the present application;
FIG. 3 is a top view of a reactor provided in one embodiment of the present application;
FIG. 4 is a top view of a reactor provided in accordance with another embodiment of the present application;
FIG. 5 is a top view of a reactor provided in accordance with yet another embodiment of the present application;
FIG. 6 is a top view of a second fluid reservoir provided in accordance with one embodiment of the present application;
FIG. 7 is a 2K SEM image of a ternary precursor prepared according to example 1 of the application;
FIG. 8 is a 10K SEM image of a ternary precursor prepared according to example 1 of the application;
FIG. 9 is a 6K-fold SEM cross-sectional view of a ternary precursor prepared according to example 1 of the application;
FIG. 10 is a 1K-fold SEM image of a ternary precursor prepared according to comparative example 1 of the present application;
FIG. 11 is a 1K SEM image of a ternary precursor of comparative example 3 of the present application.
Reference numerals:
100-reaction kettle; 110-a first feed tube; 120-a first alkali inlet pipe; 130-a first ammonia inlet pipe; 140-a first nitrogen inlet pipe; 150-a first return pipe; 160-a second return line; 170-a guide cylinder; 200-a recovery assembly; 210-a first liquid storage tank; 211-dividing plates; 211 a-upper plate body; 211 b-lower plate body; 220-a second fluid reservoir; 221-a second alkali inlet pipe; 222-a second ammonia inlet pipe; 223-a second inlet pipe; 300-transferring kettle; 400-thickener;
01-left chamber; 02-right chamber; 03-filtration pore; 04-overflow port; 05-a discharge hole; 06-a liquid outlet; 07-liquid inlet; .
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described in further detail below with reference to the accompanying drawings, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The application scenario described in the embodiment of the present application is for more clearly describing the technical solution of the embodiment of the present application, and does not constitute a limitation on the technical solution provided by the embodiment of the present application, and as a person of ordinary skill in the art can know that the technical solution provided by the embodiment of the present application is applicable to similar technical problems as the new application scenario appears. In the description of the present application, unless otherwise indicated, the meaning of "a plurality" is two or more.
The ternary positive electrode material has excellent comprehensive performance and becomes one of key materials for manufacturing lithium batteries. However, the ternary precursor can generate a large amount of wastewater in the coprecipitation preparation process, and the existing wastewater treatment method has more steps, complex process and higher operation cost.
In view of this, the embodiment of the application provides a preparation method of a ternary precursor, which includes the following steps:
step A), reacting the reaction solution at pH1 for t1 time to generate a preset number of precursor crystal nuclei;
step B), in t2 time, the pH1 of the reaction solution is reduced to pH2;
step C), reacting the reaction solution at pH2 for t3 time to obtain a precursor with a preset median particle size;
wherein the difference between pH1 and pH2 is 0.4-1; the difference between pH1 and pH2 may be 0.4, 0.5, 0.6, 0.7, 0.8, 0.9, or 1, but is not limited to the recited values, as other non-recited values within the range of values are equally applicable; at least the clear liquid obtained by solid-liquid separation of the reaction solution in the step A) is refluxed to the reaction solution in the step C).
In one embodiment of the application, the pH is 10.7-11.5, and the t1 is 1-8 h; the pH is more than or equal to 10 and less than or equal to 2 and less than or equal to 10.5, the t2 is more than or equal to 10h and less than or equal to 20h, the t3 is more than or equal to 70h and less than or equal to 80h, and t=t1+t2+t3 and t is more than or equal to 100h. The pH (pH 1) of the reaction solution in the step A) is higher to generate a predetermined number and size of crystal nuclei, and the pH (pH 2) of the reaction solution in the step C) is lower to allow the crystal nuclei to rapidly grow to a predetermined particle size.
In one embodiment of the application, the concentration of ammonia in the reaction solution in step A) is C1 and the concentration of ammonia in the reaction solution in step C) is C2, wherein 1 g/L.ltoreq.C1.ltoreq.8 g/L,1 g/L.ltoreq.C2.ltoreq.8 g/L. The control of the concentration of the ammonia water in the step A) and the step C) is helpful for controlling the complexing strength in the reaction process and regulating and controlling the morphology of primary particles.
In one embodiment of the application, the pH value of the clarified liquid is regulated to be pH3, and the ammonia water concentration of the clarified liquid is regulated to be C3, wherein pH3 is more than or equal to 13 and less than or equal to 14, and C3 is more than or equal to 10g/L and less than or equal to 15g/L. It can be understood that the pH value and the ammonia concentration of the clarified liquid are regulated and controlled so that the clarified liquid can be used as the raw material in the step C), and alkali liquor and ammonia are prevented from being introduced into the reaction kettle, so that alkali and ammonia in waste liquid generated by the reaction can be recycled, the wastewater treatment capacity is reduced, the raw material consumption is reduced, and the cost is reduced.
In one embodiment of the present application, the method further comprises regulating the feed flow rate Q of the reaction solution according to the reaction time t:
0h≤t≤8h，100L/h≤Q≤200L/h；
8h＜t≤16h，400L/h≤Q≤600L/h；
16h＜t，800L/h≤Q≤1000L/h。
it can be understood that in order to ensure the same fluctuation of the crystal nucleus granularity in the reaction process, more feed liquid is needed for growth in the later period of the reaction, so that the feed liquid flow Q needs to be increased in stages according to the reaction time t.
In one embodiment of the present application, the method further comprises regulating the stirring speed M of the reaction solution according to the solid content G of the reaction solution:
G≤100g/L，450r/min≤M≤500r/min；
100g/L＜G≤200g/L，350r/min≤Q≤400r/min；
200g/L＜G≤300g/L，250r/min≤Q≤300r/min；
300g/L＜G，150r/min≤Q≤200r/min。
in order to ensure that the final product has high sphericity, the stirring speed is set to 450r/min at the initial stage of the reaction, namely the motor frequency display of the reaction kettle is set to 45Hz, and the stirring speed is reduced in stages along with the increase of the solid content of the slurry as the reaction proceeds, so that the granularity fluctuation is uniform, and the particles in the middle and later stages of the reaction are not cracked and small particles are not generated.
Based on the same inventive concept, the present application provides an apparatus applying the preparation method in various possible embodiments of the present application, and fig. 1 is a schematic structural view of an apparatus according to one embodiment of the present application, and referring to fig. 1, the apparatus includes a reaction vessel 100, and a recovery assembly 200 in communication with the reaction vessel 100; the reaction kettle 100 is used for preparing ternary precursors, and the recovery component 200 is used for recovering and processing the reaction solution in the reaction kettle 100.
Referring to fig. 1, the reaction kettle 100 includes a guide cylinder 170 and a baffle plate arranged in an inner cavity of the reaction kettle 100, wherein the guide cylinder 170 is beneficial to uniform feeding and does not generate turbulent flow on the materials being stirred; the baffle prevents the reaction material from rotating along with the stirring, forms the vortex, causes equipment vibrations.
With continued reference to fig. 1, the recovery assembly 200 includes a first liquid reservoir 210 in communication with the reaction vessel 100 and a second liquid reservoir 220 in communication with the first liquid reservoir 210, the liquid drain of the second liquid reservoir 220 being in communication with the reaction vessel 100; the first liquid storage tank 210 is used for filtering the reaction solution to obtain a clarified liquid, and the second liquid storage tank 220 is used for storing the clarified liquid and regulating the pH value and the ammonia concentration of the clarified liquid.
Fig. 2 is a schematic structural diagram of a first liquid storage tank according to an embodiment of the present application, referring to fig. 2, a longitudinally extending partition plate 211 is disposed in the first liquid storage tank 210, the partition plate 211 divides a chamber of the first liquid storage tank 210 into a left chamber 01 and a right chamber 02, the left chamber 01 is communicated with the reaction kettle 100, and the right chamber 02 is communicated with the second liquid storage tank 220; the partition plate 211 includes a lower plate body 211b and an upper plate body 211a connected to the lower plate body 211b, and the upper plate body 211a is provided with a plurality of filter holes 03. The partition plate 211 serves to filter the reaction solution. The size of the filter holes 03 is set as needed.
With continued reference to fig. 2, the bottom of the left chamber 01 gradually rises from the end far from the partition plate 211 to the partition plate 211 so that the flow rate of the reaction solution gradually becomes smaller from the end far from the partition plate 211 to the partition plate 211, facilitating solid-liquid separation, and facilitating precipitation to accumulate at the end far from the partition plate 211; the bottom of the right chamber 02 gradually decreases from the partition plate 211 to one end far away from the partition plate 211, which is beneficial to the emptying of liquid in the liquid storage tank and the subsequent cleaning work.
With continued reference to fig. 1 and 2, the first liquid storage tank 210 is provided with a liquid inlet 07, a discharge port 05 and a liquid outlet 06, the reaction solution enters the first liquid storage tank 210 from the liquid inlet 07, the clarified liquid after solid-liquid separation is discharged through the liquid outlet 06 and enters the second liquid storage tank 220, and the sediment is discharged out of the first liquid storage tank 210 through the discharge port 05. Wherein, the discharge port 05 is arranged at the lower part of the side wall of the left chamber 01 opposite to the partition plate 211, so that the sediment generated by solid-liquid separation is conveniently discharged from the discharge port 05. The precipitate can be directly dissolved into metal liquid for reuse, and can also be used as seed crystal if the granularity is proper. The liquid discharge port 06 is provided in an upper portion of a side wall of the right chamber 02 opposite to the partition plate 211, so that a clarified liquid generated by solid-liquid separation can flow out from the liquid discharge port 06. The liquid inlet 07 is provided at an upper portion of a side wall of the left chamber 01 opposite to the partition plate 211 so that the reaction solution flows from one end far from the partition plate 211 to the partition plate 211 at a gradually decreasing speed.
Wherein, in order to isolate the solid in the reaction solution from the left chamber, the height of the lower plate body is 50% -80% of the height of the partition plate, and the height of the lower plate body is 50%, 60%, 70% or 80% of the height of the partition plate.
The volume ratio of the first liquid storage tank to the reaction kettle is 2-3, and the first liquid storage tank is specifically set according to the storage capacity of the first liquid storage tank and the reaction requirement of the reaction kettle.
Preferably, the volume of the first reaction kettle is 40m 3 -50m 3 The height is 3m-5m.
Fig. 3 is a top view of a reaction kettle according to an embodiment of the present application, referring to fig. 3, the reaction kettle 100 is provided with a first feed pipe 110, a first alkali inlet pipe 120, a first ammonia inlet pipe 130 and a first nitrogen inlet pipe 140, and the positions and thicknesses of the pipe bodies are reasonably set to promote the full progress of the synthesis reaction of the ternary precursor.
With continued reference to fig. 3, the reaction vessel 100 is provided with a first return pipe 150, and the clarified liquid obtained by the solid-liquid separation is returned to the reaction vessel 100 through the first return pipe 150. In order to improve the dispersibility of the clarified liquid in the reaction vessel 100, the diameter of the first return pipe is larger than the diameters of other feed pipes of the reaction vessel 100. Preferably, the outlet of the first return pipe 150 is close to the stirring blade of the reaction kettle 100, and the number of the first return pipes 150 is 1-4, specifically set according to the flow rate of the feed liquid. The flow rate of the clarified liquid in the first return pipe 150 ranges from 500L/h to 3000L/h.
The quantity and the layout of the feeding pipes of the reactor tube are set according to the requirements of the reaction process on the feeding flow Q and the dispersibility of the feed liquid in the reactor. The method is concretely divided into the following three cases:
first, Q is less than or equal to 300L/h, referring to FIG. 3, the number of the first feeding pipe 110, the first return pipe 150, the first alkali inlet pipe 120, the first ammonia inlet pipe 130 and the first nitrogen inlet pipe 140 is 1;
second, 300L/h.ltoreq.Q.ltoreq.600L/h, FIG. 4 is a top view of a reaction kettle according to another embodiment of the present application, referring to FIG. 4, the number of the first return pipes 150, the first alkali inlet pipes 120, the first ammonia inlet pipes 130 and the first nitrogen inlet pipes 140 is 1, and the number of the first feed pipes 110 is 2;
third, 800L/h.ltoreq.Q.ltoreq.1200L/h, FIG. 5 is a top view of a reaction kettle according to another embodiment of the present application, referring to FIG. 5, the number of the first return pipes 150 and the first nitrogen inlet pipes 140 is 1, the number of the first alkali inlet pipes 120 and the first ammonia inlet pipes 130 is 2, and the number of the first feed pipes 110 is 4.
In order to further enhance the effect of solid-liquid separation of the reaction solution, with continued reference to fig. 1, the apparatus in the embodiment of the present application further includes a thickener 400, where the reaction kettle 100 and the first liquid storage tank 210 are connected by the thickener 400, the thickener 400 is used to perform solid-liquid separation on the reaction solution in the reaction kettle 100, the supernatant after separation flows to the first liquid storage tank 210, and the slurry after separation may flow back to the reaction kettle 100 for continuous reaction. Specifically, referring to fig. 1 and 3, the reaction vessel 100 is provided with a second return pipe 160, and the slurry concentrated by the thickener 400 may be returned into the reaction vessel 100 through the second return pipe 160.
Wherein, in order to facilitate pumping of the reaction solution in the reaction kettle 100, the thickener 400 is connected with the reaction kettle 100 through the transfer kettle 300. In preparing the precursor using a batch process, the transfer pot may perform a transfer function and stabilize the flow of slurry to the thickener. In addition, the volume of the transfer kettle is much smaller than that of the reaction kettle, and slurry can be prevented from overflowing from the transfer kettle through the transfer kettle to the ageing kettle.
In one embodiment of the application, the transfer tank is in communication with the aging tank. When the precursor is prepared by using the continuous method, the device does not comprise a thickener, the precursor in the reaction solution overflows to an unqualified ageing kettle through a transfer kettle before the granularity is qualified or when the performance is not satisfied, and the slurry overflows to the qualified ageing kettle by switching a pipeline after the granularity is qualified and the performance is satisfied.
The reaction solution is processed by a thickener and a first liquid storage tank to obtain pure clarified liquid, the clarified liquid does not contain crystal nucleus of ternary precursor, and the clarified liquid flows to a second liquid storage tank which is used for storing the clarified liquid. Preferably, the second liquid storage tank can be heated so that the temperature of the clarified liquid is the same as the temperature of the reaction solution in the reaction kettle, thereby improving the reaction efficiency.
Fig. 6 is a top view of a second liquid storage tank according to an embodiment of the present application, and referring to fig. 6, a second liquid storage tank 220 is provided with a second alkali inlet pipe 221, a second ammonia inlet pipe 222 and a second water inlet pipe 223. By controlling the pH value of the clarified liquid in the second liquid storage tank 220 and the concentration of the ammonia water so that the clarified liquid can be used as the raw material in the step C), the alkali liquor is prevented from being introduced into the reaction kettle 100 through the first alkali inlet pipe 120 or the ammonia water is prevented from being introduced into the reaction kettle through the first ammonia inlet pipe 130, and the consumption of the raw material is saved.
Based on the same inventive concept, embodiments of the present application provide a ternary precursor. The ternary precursor is prepared by adopting the preparation method in the embodiment of the application.
The primary particles on the surface of the ternary precursor provided by the embodiment of the application are compactly stacked and form short clusters; the specific surface area of the precursor is 7-15 m 2 And/g, the span of the particle size distribution of the precursor is 0.5-0.7.
In one embodiment of the application, the precursor has a tap density of 1.9-2.3 g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the powder compaction test of the precursor, when the pressure is 0.5T, the ratio of the difference between the median particle diameter before the precursor is compressed and the median particle diameter after the precursor is compressed to the median particle diameter before the precursor is compressed is less than or equal to 3%.
In one embodiment of the application, the precursor includes a porous core, a dense layer, and a porous layer in a direction from the core of the precursor to the outer surface of the precursor. The porous core has more and irregular pores distributed therein, the dense layer has fewer pores, and the porous layer has a plurality of pores derived from the core of the precursor to the outer surface of the precursor. The above structure is formed because the growth of the precursor is regulated by controlling the pH and the flow in the preparation method of the present application, the pH1 environment in the step A) has a higher supersaturation environment, which is more advantageous for nucleation, and the flow in the step C) is larger, which is more advantageous for rapid growth of nuclei, and therefore, the particle size rise of the step C) is larger than that of the step A) and that of the step B), thereby obtaining a structure from the core of the precursor to the outer surface of the precursor, the precursor including a loose core, a compact layer and a loose layer. Wherein the loose core is a seed crystal that forms rapidly during nucleation. The loose layer at the outermost layer can improve the contact area between the precursor and the electrolyte, so that the lithium ion transmission channels are increased, the diffusion path of lithium ions is shortened, and the electrochemical performance of the lithium ion battery is effectively improved.
The ternary precursor of the present application and the method and apparatus for preparing the same will be described in further detail with reference to specific examples and comparative examples.
Example 1
This embodiment is an apparatus for preparing a ternary precursor, referring to fig. 1, which includes a reaction vessel 100, a transfer vessel 300 communicating with an overflow port 04 of the reaction vessel 100, a thickener 400 communicating with the transfer vessel 300, a first liquid storage tank 210 communicating with the thickener 400, and a second liquid storage tank 220 communicating with the first liquid storage tank 210, the second liquid storage tank 220 communicating with the reaction vessel 100 through a first return pipe 150.
Wherein the volumes of the reaction kettle 100, the transfer kettle 300, the thickener 400, the first liquid storage tank 210 and the second liquid storage tank 220 are respectively 15m 3 、3m 3 、5m 3 、40m 3 、40m 3 ；
The reaction kettle 100 is provided with a first feeding pipe 110, a first alkali inlet pipe 120, a first ammonia inlet pipe 130 and a first nitrogen inlet pipe 140, the outlet of the first feeding pipe 110 is flush with the lower layer stirring blade of the reaction kettle 100, the outlet of the first alkali inlet pipe 120 is flush with the upper layer stirring blade of the reaction kettle 100, the outlet of the first ammonia inlet pipe 130 is below the liquid level of the reaction solution, preferably flush with the lower layer stirring blade of the reaction kettle 100, the distance between the outlet of the first nitrogen inlet pipe 140 and the top cover of the reaction kettle 100 is 10cm, and the outlet of the first return pipe 150 is flush with the lower layer stirring blade of the reaction kettle 100; the distance between the lower stirring blade of the reaction kettle 100 and the bottom wall of the reaction kettle 100 is 0.8m, and the distance between the upper stirring blade of the reaction kettle 100 and the lower stirring blade is 1.5m; the bottom opening of the guide cylinder 170 is aligned with the height of the stirring blade at the lower layer, and a guide port is arranged at a position, which is 0.5m away from the top cover of the reaction kettle 100, of the guide cylinder 170. Referring to fig. 5, the number of the first return pipes 150 and the first nitrogen inlet pipes 140 is 1, the number of the first alkali inlet pipes 120 and the first ammonia inlet pipes 130 is 2, and the number of the first feed pipes 110 is 4.
The distance between the stirring blade of the transfer kettle and the bottom wall of the transfer kettle is 0.3m, the distance between the lower stirring blade of the thickener and the bottom wall of the thickener is 0.5m, the distance between the upper stirring blade of the thickener and the lower stirring blade of the thickener is 1m, and the distance between the stirring blades of the first liquid storage tank and the second liquid storage tank and the bottom wall is 0.5m.
The method for preparing the ternary precursor by using the device comprises the following steps of:
1) Adding clear water into the reaction kettle, the transfer kettle and the thickener, wherein the addition amount of the clear water reaches an overflow port of the reaction kettle, and submerges a stirring paddle of the transfer kettle and a stirring paddle of an upper layer of the thickener;
2) Introducing 1000L of ammonia water with the concentration of 5mol/L and 10L of alkali liquor with the concentration of 10mol/L into a reaction kettle to form a reaction base solution with the pH value of 10.8-10.9 and the concentration of C1 of 3-3.5 g/L, wherein the reaction time t1 is 4 hours, the nucleation stage is the stage, and the starting granularity (granularity of a precursor during the reaction for 1 hour after the salt solution is introduced) corresponding to the pH value of 1 is 2.8-3.2 um;
3) In 12h, the pH1 of the reaction solution is reduced to pH2, and the pH2 is 10.2-10.3; c2 is 3 to 3.5g/L;
4) Reacting for 70-75 h at pH2 to obtain a precursor with a preset median particle diameter;
wherein, in the step 3) and the step 4), the first alkali inlet pipe and the first ammonia inlet pipe are closed, and the pH value and the ammonia water concentration of the reaction solution are regulated through the second alkali inlet pipe and the second ammonia inlet pipe; the pH3 of the clarified liquid in the second liquid storage tank is 13-14, and the concentration C3 of ammonia water is 4g/L;
regulating and controlling the stirring speed of the reaction solution according to the solid content G of the reaction solution:
setting the frequency display of the motor of the reaction kettle to 45Hz (stirring speed is 450 r/min) on the premise of not overload current at the initial stage of the reaction kettle, setting the frequency display of the motor of the reaction kettle to 45Hz (stirring speed is 450 r/min) when the solid content G is less than or equal to 100G/L, setting the frequency display of the motor of the reaction kettle to 35Hz (stirring speed is 350 r/min) when the solid content G is less than or equal to 200G/L, setting the frequency display of the motor of the reaction kettle to 25Hz (stirring speed is 250 r/min) when the solid content G is less than or equal to 300G/L, and setting the frequency display of the motor of the reaction kettle to 15Hz (stirring speed is 150 r/min) when the solid content G is more than 300G/L;
regulating and controlling the feeding flow Q of the reaction solution according to the reaction time t:
0h≤t≤8h，Q＝100L/h；
8h＜t≤16h，Q＝400L/h；
16h＜t，Q＝800L/h。
the temperature of the reaction process is fixed at 60 ℃, the concentration of ammonia water is 3-3.5 g/L, and the flow of nitrogen is fixed for 7m 3 And/h, wherein the main content Ni is Co, mn=83:11:6, the concentration of the feed liquid is 1.8mol/L, and the granularity of the final precursor is 13.6um.
The ternary precursor prepared by the method has a median particle diameter of 13.6um, a span of particle size distribution of 0.6 and a specific surface area of 8m 2 Per gram, tap density of 2g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the powder compaction test of the precursor, at the pressure of 0.5T, the ratio of the difference between the median particle diameter before the precursor is compressed and the median particle diameter after the precursor is compressed to the median particle diameter before the precursor is compressed is 2%.
Fig. 7 is a 2K-time SEM image of the ternary precursor prepared in example 1 of the present application, fig. 8 is a 10K-time SEM image of the ternary precursor prepared in example 1 of the present application, and referring to fig. 7 and 8, primary particles of the precursor are compactly stacked, and fig. 9 is a 6K-time SEM cross-sectional image of the ternary precursor prepared in example 1 of the present application, and referring to fig. 9, the precursor includes a loose core, a compact layer, and a loose layer in a direction from the core of the precursor to the outer surface of the precursor.
Examples 2 to 8 and comparative examples 1 to 3
Examples 2-8 and comparative examples 1-3 are ternary precursors, respectively, which can be prepared by referring to example 1, except that the reaction conditions are different, and the first alkali inlet pipe and the first ammonia inlet pipe are used to control the pH and the ammonia concentration in the reaction system in step 3) and step 4) in comparative example 3, and the specific differences are shown in Table 1.
TABLE 1
Wherein, the concentration of the concentrated alkali is 10.8mol/L, and the concentration of the concentrated ammonia is 10mol/L.
The ternary precursors of the above examples and comparative examples, and batteries prepared therefrom, were subjected to performance tests, and the specific test results are shown in table 2.
TABLE 2
Referring to Table 2, the difference between pH1 and pH2 in examples 1-8 was 0.4-1, the difference between pH1 and pH2 in comparative examples 1-2 was greater than 1, and the specific surface area of the precursor in examples 1-8 was 8.5m or greater 2 And/g, the specific surface area of the precursor in the comparative examples 1-3 is smaller than 7, and the specific surface area of the precursor in the examples 1-8 is obviously higher than that of the precursor in the comparative examples 1-3, so that the transfer of lithium ions is facilitated, and the rate performance of the prepared battery is improved. The particle size distribution of the precursors in examples 1-8 is between 0.6 and 0.7, the particle size distribution of the precursors in comparative examples 1-3 is greater than 0.9, the particle size distribution of the precursors in examples 1-8 is more concentrated, and the cycle performance and the rate performance are improved.
With continued reference to Table 2, examples 1-8 and comparative examples 1-2 exhibited significantly improved discharge capacity, initial efficiency, and cycle performance.
FIG. 10 is a 1K SEM image of a ternary precursor prepared according to comparative example 1, and referring to FIG. 10 and Table 2, the precursor has significant cracks on the surface of particles because the pH1 of comparative example 1 is high, the corresponding seed particles are small in size and large in number, the post-reaction period is slow, the reaction time is 125 hours, the final solid content is 530g/L, the collision strength between particles is large, so that cracks are generated on the surface, and the side reaction with electrolyte is increased, resulting in reduced battery performance; in addition, the reaction solution in comparative example 1 has high solid content, high viscosity of the reaction system, difficult dispersion of solute ions, small particles generated locally, small particle size of the precursor, excessive sintering during sintering, excessive delithiation of the prepared positive electrode material, and reduced electrical performance of the battery prepared from the positive electrode material.
Comparative example 2 and comparative example 1 have the same problems and are not described here again.
Fig. 11 is a 1K-time SEM image of the ternary precursor prepared in comparative example 3 according to the present application, and referring to fig. 11 and table 2, the concentration of the particle size distribution of the precursor prepared in comparative example 3 is low because the comparative example 3 uses the first alkali inlet pipe and the first ammonia inlet pipe to regulate the pH and the concentration of ammonia water in the reaction system in the reaction steps 3) and 4), the inside of the first alkali inlet pipe is concentrated alkali, and the concentrated alkali is not timely dispersed in the reaction kettle to cause local pH to be high, so that the precursor with small particle size is easily generated, thereby causing the performance of the battery prepared therefrom to be reduced.
The foregoing is merely illustrative embodiments of the present application, but the scope of the present application is not limited thereto, and any person skilled in the art can easily think about variations or substitutions within the technical scope of the present application, and the application should be covered. Therefore, the protection scope of the application is subject to the protection scope of the claims.
Claims (13)
1. The preparation method of the ternary precursor is characterized by comprising the following steps of:
step A), reacting the reaction solution at pH1 for t1 time to generate a preset number of precursor crystal nuclei;
step B), in t2 time, the pH1 of the reaction solution is reduced to pH2;
step C), reacting the reaction solution at pH2 for t3 time to obtain a precursor with a preset median particle size;
wherein the difference between pH1 and pH2 is 0.4-1; at least the clear liquid obtained by solid-liquid separation of the reaction solution in the step A) is refluxed to the reaction solution in the step C).
2. The method according to claim 1, wherein pH1 is 10.7.ltoreq.11.5, t1 is 1 h.ltoreq.8 h; the pH is more than or equal to 10 and less than or equal to 2 and less than or equal to 10.5, the t2 is more than or equal to 10h and less than or equal to 20h, the t3 is more than or equal to 70h and less than or equal to 80h, and t=t1+t2+t3 and t is more than or equal to 100h.
3. The process according to claim 1, wherein the concentration of aqueous ammonia in the reaction solution in the step A) is C1 and the concentration of aqueous ammonia in the reaction solution in the step C) is C2, wherein 1 g/L.ltoreq.C1.ltoreq.8 g/L,1 g/L.ltoreq.C2.ltoreq.8 g/L.
4. The process according to any one of claims 1 to 3, wherein the pH of the clarified liquid is adjusted to pH3, and the concentration of aqueous ammonia in the clarified liquid is adjusted to C3, wherein pH3 is 13.ltoreq.14, and C3 is 10 g/L.ltoreq.15 g/L.
5. The method according to claim 4, further comprising controlling a feed flow rate Q of the reaction solution according to a reaction time t:
0h≤t≤8h，100L/h≤Q≤200L/h；
8h＜t≤16h，400L/h≤Q≤600L/h；
16h＜t，800L/h≤Q≤1000L/h。
6. the method according to claim 4, further comprising controlling a stirring speed M of the reaction solution according to a solid content G of the reaction solution:
G≤100g/L，450r/min≤M≤500r/min；
100g/L＜G≤200g/L，350r/min≤Q≤400r/min；
200g/L＜G≤300g/L，250r/min≤Q≤300r/min；
300g/L＜G，150r/min≤Q≤200r/min。
7. an apparatus for applying the production method according to any one of claims 1 to 6, comprising a reaction vessel, a recovery assembly in communication with the reaction vessel;
the reaction kettle is used for preparing the ternary precursor, and the recovery component is used for recovering and treating the reaction solution in the reaction kettle.
8. The apparatus of claim 7, wherein the recovery assembly comprises a first liquid reservoir in communication with the reaction vessel and a second liquid reservoir in communication with the first liquid reservoir, a drain of the second liquid reservoir in communication with the reaction vessel;
the first liquid storage tank is used for filtering the reaction solution to obtain the clarified liquid, and the second liquid storage tank is used for storing the clarified liquid and regulating and controlling the pH value and the ammonia water concentration of the clarified liquid.
9. The device of claim 8, wherein a longitudinally extending partition plate is arranged in the first liquid storage tank, the partition plate divides a chamber of the first liquid storage tank into a left chamber and a right chamber, the left chamber is communicated with the reaction kettle, and the right chamber is communicated with the second liquid storage tank;
the division board include the lower plate body and with the last plate body of lower plate body coupling, it is equipped with a plurality of filtration pore to go up the plate body.
10. The apparatus of claim 9, wherein the bottom of the left chamber is gradually raised from an end distal from the divider plate to the divider plate, and the bottom of the right chamber is gradually lowered from the divider plate to an end distal from the divider plate.
11. A precursor prepared by the preparation method according to any one of claims 1 to 6, wherein the specific surface area of the precursor is 7 to 15m 2 And/g, wherein the span of the particle size distribution of the precursor is 0.5-0.7.
12. The precursor of claim 11, wherein the precursor has a tap density of 1.9 to 2.3g/cm 3 The method comprises the steps of carrying out a first treatment on the surface of the In the powder compaction test of the precursor, when the pressure is 0.5T, the ratio of the difference value between the median particle diameter before the precursor is compressed and the median particle diameter after the precursor is compressed to the median particle diameter before the precursor is compressed is less than or equal to 3%.
13. The precursor according to claim 11 or 12, wherein the precursor comprises a porous core, a dense layer and a porous layer in a direction from the core of the precursor to the outer surface of the precursor.
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