CN113421617B - Method for calculating solid content in process of preparing solid material by batch method and application thereof - Google Patents
Method for calculating solid content in process of preparing solid material by batch method and application thereof Download PDFInfo
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- G16C20/00—Chemoinformatics, i.e. ICT specially adapted for the handling of physicochemical or structural data of chemical particles, elements, compounds or mixtures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
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- 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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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention relates to the technical field of battery material preparation, in particular to a method for calculating solid content in a process of preparing a solid material by an intermittent method and application thereof. The solid content comprises a calculated value M of the solid content or a corrected value R of the solid content; the calculation method of the calculation value M comprises the following steps: m ═ C [ (n-1) T)0+T](ii) a Wherein the content of the first and second substances,
the correction value R is AxM, wherein A is a correction coefficient, and A is 0.883-1.002. The calculation method has the advantages of simple and convenient calculation, short required time, small error, good timeliness and the like; and the calculated value M or the corrected value R can provide online comparison for the pH value, the ammonia water concentration and the particle size increasing trend in the reaction process, and is favorable for improving the performance of the material.
Description
Technical Field
The invention relates to the technical field of battery material preparation, in particular to a method for calculating solid content in a process of preparing a solid material by an intermittent method and application thereof.
Background
Lithium ion batteries are widely used due to their advantages of high working voltage, high energy density, long cycle life, and the like, and the types of the lithium ion batteries that are mature at present include: lithium cobaltate, lithium manganate, lithium iron phosphate, lithium nickel cobalt manganese oxide and the like. The specific capacity and the energy density of the ternary positive electrode material are higher than those of positive electrode products such as lithium iron phosphate, lithium manganate, lithium cobaltate and the like, the energy density of the power battery is greatly improved, and the advantages of the ternary positive electrode material are obvious. The ternary cathode material is formed by mixing and sintering a ternary precursor with a specific molar ratio and a lithium source, and the physical and chemical properties of the precursor have a large influence on the performance of the cathode material. The existing reaction for synthesizing the ternary precursor comprises a coprecipitation method, a spray synthesis method, a hydrothermal method and the like, wherein the coprecipitation method is a commonly used method in the current industrial production.
The influencing factors in the process of preparing the precursor by coprecipitation reaction comprise: system temperature, pH, NH4+ concentration, stirring speed and solid content, etc. Wherein, the reaction temperature and the system pH can be monitored in real time by adopting an online measuring instrument; NH (NH)4 +The concentration is relatively stable under the condition that the flow of the ammonia water and the process scheme are not changed; the stirring speed can be monitored by a tachometer at any time. The solid content is the ratio of the mass of the solid to the mass of the liquid in the precursor slurry, and is used as an important factor influencing the physicochemical property of the precursor, the solid content can influence the granularity and the tap density of precursor particles, and the battery capacity can be influenced when the tap density is lower.
The crystal growth mode and particle size distribution of the ternary precursor are classified into a continuous method, a batch method and a semi-continuous semi-batch method. The continuous process is a process in which the feed and the product output are carried out simultaneously, and the solid content of the process is stable when the reaction is stable. The batch method is a method of continuously flowing salt, alkali and ammonia water solution into a reaction kettle for reaction, separating out mother liquor through standing and settling after the granularity of particles meets the set requirement, and then starting the reaction. In the process of preparing the ternary precursor by the batch coprecipitation reaction, the solid content can change constantly. In the prior art, the solid content determination method needs to be carried out through the processes of sampling, suction filtration, drying and the like. However, such a measurement method is long in time consumption, data has no timeliness, production efficiency is reduced, and process production is affected; meanwhile, in the suction filtration process, part of particles can be adhered to the filter paper, so that errors are easily generated in calculation. Furthermore, this measurement method does not allow to compare the nucleation rate over time with other parameters; in the later stage of the process of producing large-particle precursors, the particle size and tap density are greatly influenced by solid content, and if the control is improper, the particles can be broken, so that the product quality is influenced.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a method for calculating the solid content in the process of preparing a solid material by an intermittent method, wherein the method has the advantages of simple and convenient calculation, short required time, small error, good timeliness and the like; the calculated value M or the corrected value R can provide online comparison for the pH value, the ammonia concentration and the particle size increasing trend in the reaction process, and is beneficial to improving the performance of the material.
The second purpose of the invention is to provide the application of the calculation method in the adjustment of the reaction process in the preparation process of the ternary lithium ion battery precursor material by the batch coprecipitation reaction, and the calculation value or the correction value of the solid content can be obtained in time by calculation, so that the process parameters can be adjusted in time; meanwhile, the dynamic change rule of the solid content of the material in the production process can be obtained through the calculated value or the corrected value, so that the production process of the reaction is controlled, and the material with more excellent appearance and performance is obtained.
In order to achieve the above purpose of the present invention, the following technical solutions are adopted:
a method for calculating the solid content in the process of preparing solid materials by a batch method, wherein the solid content comprises a calculated value M of the solid content or a corrected value R of the solid content;
the calculation method of the calculation value M comprises the following steps: m ═ C [ (n-1) T)0+T]；
Wherein the content of the first and second substances,
m is a calculated value of solid content, and the unit is g/L;
csalt (salt)The unit mol/L is the molar concentration of the salt solution in the reaction kettle;
a is the feeding speed of the salt solution, and the unit is L/h;
Mris the relative molecular mass of the material;
Vfis the effective volume of the reaction kettle and has the unit of m3；
T0The unit is h, which is the reaction time of each kettle;
t is the residual time except the integral multiple of the full-kettle reaction time, and the unit is h;
Tmthe total reaction time in the preparation process of the material is h;
n is the number of reaction kettles, n is 1, 2, …, Tm/T0The integer part of (1);
the correction value R is AxM, wherein A is a correction coefficient, and A is 0.883-1.002.
The method for calculating the solid content in the process of preparing the solid material by the batch method has the advantages of simple calculation, high calculation speed, short required time, small error and the like, and has good timeliness. Meanwhile, according to the invention, a correction coefficient is obtained through a large amount of statistics (800-1000 groups of data are counted), a correction value can be obtained through the correction coefficient, the correction value is closer to an actual solid content value in a system, online comparison can be provided for the increasing trend of pH, ammonia water concentration and granularity in the reaction process, and the performance of the product is further improved. In addition, when the solid content in the system is low, the calculation error is small; meanwhile, the calculation error is small in the production process of large-particle materials.
The solid content refers to the ratio of the solid mass to the liquid mass in the precursor slurry in the precursor reaction process, and is an important factor influencing the physicochemical property of the precursor.
The intermittent method for producing the ternary precursor is that a metal salt solution, an alkali solution and an ammonia water solution are continuously fed into a reaction kettle for coprecipitation reaction until the granularity and the physicochemical property meet the requirements and then are discharged at one time. By designing the reaction times and the reaction time, matching the corresponding material concentration and the reaction time, and when the reaction kettle is full, continuously adding the metal salt solution, the ammonia water solution and the alkali solution for reaction after standing and settling until the reaction granularity is reached.
The coprecipitation reaction of the precursor is a neutralization reaction, namely, a hydroxide precipitate is generated by using a salt solution with a certain concentration and an alkali solution with a certain concentration under the condition that ammonia water is used as a complexing agent according to a certain reaction condition.
Known from the law of conservation of mass: the reaction coefficient for the conversion of the salt solution into a hydroxide precipitate is 1:1, the mass of the hydroxide precipitate formed at time t is atcSalt (salt)Mrg, the solid content M (t) in the reaction kettle at the moment t has the following relation with the time t:
when the chemical composition of the designed precursor material is determined, the solid content in the reaction kettle and the time t present a direct proportional function relationship before the first kettle is fully filled. When the first kettle is exceeded (below the critical solids content), the solids content in the reaction kettle is generally a function of the reaction time. Assuming that the total reaction time of a certain experimental design is TmReaction time per kettle is T0The number of reaction kettle is n (n is 1, 2, …, T)m/T0The integer portion of (a).
When the number of the reaction kettles is n-1, M-CT;
when the number of reaction kettles is n-2, M-C (T)0+T)；
When the number of reaction kettles is n-3, M-C (2T)0+T)；
When the number of reaction kettles is n-4, M-C (3T)0+T)；
By the way of analogy, the method can be used,
when the number of reaction kettles is n ═ Tm/T0When the integer part of (a) is (b), M ═ C [ (n-1) T)0+T]；
Wherein the content of the first and second substances,
wherein, VfThe effective volume of the reaction kettle is obtained by subtracting the volume occupied by the stirring shaft and the stirring shaft from the volume of the reaction kettle, which is called the effective volume, because the stirring shaft and the stirring shaft exist in the reaction kettle and occupy a part of space.
The calculation method provided by the invention is not only suitable for the preparation process of the nickel-cobalt-manganese hydroxide precursor material, but also suitable for the preparation process of other precursor materials. When preparing the nickel-cobalt-manganese hydroxide precursor material, the salt solution is a nickel-cobalt-manganese salt solution.
Preferably, in calculating the solids content, the following assumptions are made:
the solid contents of all parts in the reaction kettle are consistent;
after the reaction kettle is full, standing for precipitation, and then discharging supernatant in an overflow mode, wherein the volume of the raw material liquid fed is equal to the volume of the discharged supernatant;
the mass of solid particles in the clear liquid is zero;
the volume of the mother liquor extracted after the kettle is filled every time is VnWherein n is 1, 2, …, Tm/T0The integer part of (2).
The influence of nucleation rate and residence time is mainly considered in the process of batch coprecipitation reaction, and for the convenience of calculation, the following assumptions are made: (1) the stirring strength in the reaction kettle is enough, so that the consistency of solid contents at all positions can be ensured; (2) after the reaction kettle is full, the reaction kettle is stoppedDischarging supernatant in an overflow mode after precipitation, wherein the volume of the raw material liquid fed is equal to the volume of the discharged supernatant; (3) the mass of the discharged solid particles in the clear liquid after precipitation is regarded as zero; (4) the volume of the mother liquor extracted after the kettle is filled every time is VnWherein n is 1, 2, …, Tm/T0The volume of mother liquor extracted each time will be the effective space in the reaction kettle.
In particular embodiments, T is designed based on material performance requirements in combination with process experiencem、T0And n.
Preferably, the particle size D50 of the material is 2-20 μm.
More preferably, the particle size D50 of the material is 8-18 μm.
The calculation method provided by the invention has smaller error in the production process of the large-particle material.
Preferably, the molar concentration of the salt solution is 1.5-2.5 mol/L, and 1.6mol/L, 1.7mol/L, 1.8mol/L, 1.9mol/L, 2.0mol/L, 2.1mol/L, 2.2mol/L, 2.3mol/L or 2.4mol/L can also be selected.
Preferably, in the process of preparing the material, the molar concentration of the NaOH raw material solution is 8-15 mol/L, and 8.5mol/L, 9mol/L, 9.5mol/L, 10mol/L, 10.5mol/L, 11mol/L, 11.2mol/L, 11.9mol/L, 12.6mol/L, 13.4mol/L, 14.2mol/L or 14.8mol/L can also be selected.
More preferably, in the process of preparing the material, the molar concentration of the NaOH raw material solution is 10-13 mol/L.
Preferably, in the process of preparing the material, the molar concentration of the ammonia water raw material solution is 5-10 mol/L, and 5.5mol/L, 6mol/L, 6.5mol/L, 7mol/L, 7.5mol/L, 8mol/L, 8.5mol/L or 9mol/L can also be selected.
More preferably, in the process of preparing the material, the molar concentration of the ammonia water raw material solution is 7-9 mol/L.
Preferably, in the process of preparing the material, the effective volume of the reaction kettle is 20-10 m3Alternatively, 3m may be selected3、4m3、5m3、6m3、7m3、8m3Or 9m3。
The statistical correction of the present invention is based on the parameter ranges, which is advantageous for reducing errors.
When the critical solid content is exceeded, the nucleation rate and the solid content are in a power exponential function relationship, and the nucleation rate in the system is obviously increased along with the increase of the solid content. Therefore, in order to prevent explosive nucleation caused by too high solid content, it is necessary to control the critical solid content (i.e. the solid content value at supersaturation of the reaction system), which is usually controlled by material distribution, and there is a difference in the production process of large particles and small particles.
The large-particle coprecipitation reaction and the small-particle coprecipitation reaction have certain difference, when small particles with the D50 being less than or equal to 8 mu m are produced, a high nucleation rate is needed, a high rotating speed needs to be maintained in order to keep good dispersity, the solid content is increased, the collision among the particles can be facilitated to modify the particle surfaces to generate products with high sphericity, and the actual solid content is close to the theoretical solid content.
When large particles with the diameter of D50 being more than 8 mu m are produced, the rotation speed needs to be reduced because the particles are larger and the nucleation rate needs to be controlled, and the solid content and the sample dispersion degree at various positions in the reaction kettle also have difference, so that the actual solid content in the reaction kettle is difficult to describe by a calculation method. However, in order to prevent large particles from breaking and maintain good sphericity, a dynamic relationship between solid content and stirring speed and pH needs to be sought.
In order to solve the problems, the invention selects a plurality of groups of data in the production process of the precursor material, adopts a longitudinal sampling mode, and respectively selects samples of the reaction kettle at different longitudinal positions (mainly 2/5, 3/5 and 4/5) through a sampling spoon to carry out solid content determination. Because three assumptions exist in theoretical calculation values in a calculation formula, the actual solid content in the reaction process is measured by adopting a traditional measuring method (namely a sampling-suction filtration-drying method), and statistical correction is carried out. The invention provides correction coefficients under the conditions of different solid content ranges and different particle size ranges, thereby further providing reference basis for controlling the coprecipitation reaction by a batch method.
Preferably, when M <150g/L, A is 0.992-1.002. In this case, the error range is 0.2% to 0.8%.
Preferably, when M is 150-250 g/L, A is 0.973-0.991.
More preferably, when M is 150-250 g/L and the particle size D50 of the material is less than or equal to 8 μ M, A is 0.973-0.988. In this case, the error range is 1.2% to 2.7%.
More preferably, when M is 150 to 250g/L and the particle size D50 of the material is more than 8 μ M, A is 0.985 to 0.991. In this case, the error range is 0.9% to 1.5%.
Preferably, when M is 250 to 350g/L, A is 0.922 to 0.982.
More preferably, when M is 250-350 g/L and the particle size D50 of the material is less than or equal to 8 μ M, A is 0.922-0.954. In this case, the error range is 4.6% to 7.8%.
More preferably, when M is 250 to 350g/L and the particle size D50 of the material is more than 8 μ M, A is 0.945 to 0.982. In this case, the error range is 1.8% to 5.5%.
Preferably, when M >350g/L, A is 0.883-0.965.
More preferably, when M is more than 350g/L and the particle size D50 of the material is less than or equal to 8 μ M, A is 0.883-0.934. In this case, the error range is 6.6% to 11.7%.
More preferably, when M >350g/L and the particle size D50 of the material is >8 μ M, A is 0.936 to 0.965. In this case, the error range is 3.5% to 6.4%.
As can be seen from the above relation, when the solid content is low, at the initial stage of the reaction, the calculated value and the measured value have good corresponding relation, and the error is controlled between 0.2 and 0.8. When the solid content is higher, the reaction is in the later stage, and the calculated value and the measured value of the solid content have larger difference.
When the particle size is larger, in order to avoid particle crushing caused by too high stirring, a lower rotating speed is needed, so that the particles are easily dispersed unevenly, and further the sampling error is increased.
On the other hand, the small-sized particles have relatively large errors because the small particles maintain a high pH and a low ammonia concentration during production, and require a high rotation speed for dispersion, so that many small crystal nuclei are generated during the reaction. When the particle size of the small crystal nuclei is smaller than the minimum particle size range filtered by the filter paper, the measured value is lower than the calculated value, which is also an important reason for the measured value being lower than the calculated value.
The invention also provides application of the calculation method in adjusting the reaction process in the process of preparing the ternary lithium ion battery precursor material by the batch coprecipitation reaction.
In the process of preparing the ternary lithium ion battery precursor material by adopting the intermittent coprecipitation reaction, a calculated value or a corrected value R of solid content is obtained by pre-calculation, so that the process parameters can be adjusted in time, the production process of the reaction can be controlled, and the material with more excellent appearance and performance can be obtained.
The application provided by the invention can pre-calculate the calculated value M or the corrected value R, and then timely adjust the process parameters according to the calculated value M or the corrected value R, thereby controlling the production process of the reaction and obtaining the material with more excellent appearance and performance.
Compared with the prior art, the invention has the beneficial effects that:
(1) the method for calculating the solid content in the process of preparing the solid material by the intermittent method is simple, easy to calculate, short in consumed time, good in timeliness and small in error; meanwhile, the calculated value M or the corrected value R can provide online comparison for the pH value, the ammonia water concentration and the particle size increasing trend in the reaction process, and is favorable for improving the performance of the material.
(2) According to the calculation method provided by the invention, when the solid content in the system is low, the calculation error is small; meanwhile, the calculation error is small in the production process of large-particle materials.
(3) The calculation method provided by the invention is applied to the adjustment of the reaction process in the process of preparing the ternary lithium ion battery precursor material by the batch coprecipitation reaction, and a calculated value or a corrected value can be obtained in time through calculation, so that the process parameters can be adjusted in time; and the dynamic change rule of the solid content of the material in the production process can be obtained through the calculated value or the corrected value, the production process of the reaction can be controlled, the material with more excellent appearance and performance can be obtained, and support is provided for the design, research and development and industrial popularization of the precursor production process.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a diagram of the appearance of the precursor NCM551530 prepared by the production process of the reaction controlled by a calculation method provided by the invention;
fig. 2 is a topography diagram of the precursor of NCM551530 prepared by the production process of the actual measurement method control reaction provided by the invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings and the detailed description, but those skilled in the art will understand that the following described embodiments are some, not all, of the embodiments of the present invention, and are only used for illustrating the present invention, and should not be construed as limiting the scope of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The following embodiments of the invention obtain the measurement method for the solid content of each kettle, and specifically comprise the following steps:
sampling at different positions of a reaction kettle by using a sampling spoon, and filling the sampling into a beaker, wherein the sampling is respectively carried out at longitudinal 2/5, 3/5 and 4/5 positions of the reaction kettle, and the volume of the obtained feed liquid is 1L; then, the feed liquid is filtered (the beaker is rinsed by deionized water) by a circulating filter to obtain a solid, and the solid is heated for 5 hours at 120 ℃ to obtain a dried product; the content of the dried product was weighed, and the value (g) of the mass of the solid was a measurement value of the solid content since the volume was 1L.
Example 1
Preparing NCM622 type precursor [ Ni ] by intermittent coprecipitation method0.6Co0.2Mn0.2(OH)2]And measuring the solid content in the full kettle. The concentration of the nickel-cobalt-manganese salt solution is designed to be 2.0mol/L, and the effective volume is 6m3The particle size of the precursor is designed to be D50 ═ 10 mu m, the feeding speed of the nickel-cobalt-manganese salt solution is 250L/h, the total reaction time is designed to be 42h, and the reaction time in each reactor is 7 hours, which is 6 reactors in total.
By the formula
The calculated value for solids content was calculated, where C is 7.6657. Then, the measurement of the solid content was obtained by the measurement method, and the error was calculated, wherein the calculated value, the measured value, and the error result are shown in table 1 below.
TABLE 1 comparison of calculated, measured and error values for example 1
As can be seen from table 1, the error of the embodiment 1 conforms to the error range after the statistical correction, which indicates that the error of the calculation method provided by the present invention is small, and the statistical correction coefficient provided by the present invention is reasonable.
Example 2
By batch coprecipitationMethod for preparing NCM622 type precursor [ Ni ]0.6Co0.2Mn0.2(OH)2]And (6) carrying out process solid content determination. The concentration of the nickel-cobalt-manganese salt solution is designed to be 2.0mol/L, and the effective volume is 6m3The particle size of the precursor is designed to be D50 ═ 10 mu m, the feeding speed of the nickel-cobalt-manganese salt solution is 250L/h, the total reaction time is designed to be 42h, and the reaction time in each reactor is 7 hours, which is 6 reactors in total.
By the formula
The calculated values of the solids content at different points in the reaction were obtained by calculation, where C is 7.6657. Then, the measurement of the solid content of each pot was obtained by the measurement method, and the error was calculated, wherein the calculated value, the measured value, and the error result are shown in table 2 below.
Table 2 calculated, measured and error comparisons for example 2
| Reaction time | Calculated value (full kettle, g/L) | Measured value (full kettle, g/L) | Error (%) |
| 6h | 45.99 | 45.72 | 0.59 |
| 16h | 122.65 | 121.71 | 0.77 |
| 26h | 199.31 | 196.68 | 1.32 |
| 36h | 275.97 | 270.82 | 1.87 |
It can also be seen from table 2 that the error of example 2 fits within the error range after statistical correction. This again shows that the error of the calculation method provided by the present invention is small, and the statistical correction coefficient provided by the present invention is reasonable.
Example 3
Preparing NCM811 type precursor [ Ni ] by adopting intermittent coprecipitation method0.8Co0.1Mn0.1(OH)2]And measuring the solid content in the full kettle. The concentration of the nickel-cobalt-manganese salt solution is designed to be 2.5mol/L, and the effective volume is 10m3The particle size of the precursor is designed to be D50 ═ 4 μm, the feeding speed of the nickel-cobalt-manganese salt solution is 380L/h, the total reaction time is designed to be 54h, and the reaction time in each reactor is 6 hours, which is 9 reactors in total.
By the formula
The calculated value for solids content was calculated, where C is 8.772. Then, the measurement of the solid content was obtained by the measurement method, and the error was calculated, wherein the calculated value, the measured value, and the error result are shown in table 3 below.
Table 3 calculated, measured and error comparisons for example 3
| Number of reaction kettles | Calculated value (full kettle, g/L) | Measured value (full kettle, g/L) | Error (%) |
| First kettle | 52.63 | 52.45 | 0.34 |
| Second kettle | 105.26 | 104.70 | 0.53 |
| Third kettle | 157.90 | 155.83 | 1.31 |
| Fourth kettle | 210.53 | 207.02 | 1.67 |
| Fifth kettle | 263.16 | 250.69 | 4.74 |
| Sixth kettle | 315.79 | 300.38 | 4.88 |
| Seventh kettle | 368.42 | 336.66 | 8.62 |
| Eighth kettle | 421.06 | 383.12 | 9.01 |
| Ninth kettle | 473.69 | 431.67 | 8.87 |
As can be seen from table 3, the error of example 3 corresponds to the error range after statistical correction.
Example 4
Preparing NCM811 type precursor [ Ni ] by adopting intermittent coprecipitation method0.8Co0.1Mn0.1(OH)2]And (6) carrying out process solid content determination. The concentration of the nickel-cobalt-manganese salt solution is designed to be 2.5mol/L, and the effective volume is 10m3The particle size of the precursor is designed to be D50 ═ 4 μm, the feeding speed of the nickel-cobalt-manganese salt solution is 380L/h, the total reaction time is designed to be 54h, and the reaction time in each reactor is 6 hours, which is 9 reactors in total.
By the formula
The calculated values of the solids content at different points in the reaction were obtained by calculation, where C is 8.772. Then, measuring the solid content of each kettle by a measuring method, and calculating errors, wherein the calculated value, the measured value and the errors are combinedThe results are shown in table 4 below.
Table 4 calculated, measured and error comparisons for example 4
| Reaction time | Calculated value (full kettle, g/L) | Measured value (full kettle, g/L) | Error (%) |
| 5h | 43.86 | 43.63 | 0.52 |
| 15h | 113.56 | 112.87 | 0.61 |
| 25h | 223.25 | 217.78 | 2.45 |
| 35h | 311.96 | 291.15 | 6.67 |
| 45h | 401.66 | 367.59 | 8.49 |
As can be seen from table 4, the error of example 4 corresponds to the error range after statistical correction.
Example 5
Preparing NCM551530 type precursor [ Ni ] by adopting intermittent coprecipitation method0.55Co0.15Mn0.30(OH)2]And measuring the solid content in the full kettle. The concentration of the nickel-cobalt-manganese salt solution is designed to be 1.9mol/L, and the effective volume is 2m3The reaction kettle (2) is used for reaction, the granularity of the precursor is designed to be 12 mu m, the feeding speed of the nickel-cobalt-manganese salt solution is 100L/h, the total reaction time is designed to be 42h, and the reaction time in each kettle is 7 hours, which is 6 kettles in total.
By the formula
The calculated value of the full-kettle solid content is obtained by calculation, wherein C is 8.702. Then, a measurement of the full-pot solid content was obtained by measurement, and an error was calculated, wherein the calculated value and the measured value are shown in table 5 below.
TABLE 5 calculated and measured values of example 5
| Number of reaction kettles | Calculated value (full kettle, g/L) | Measured value (full kettle, g/L) |
| First kettle | 60.91 | 60.67 |
| Second kettle | 121.83 | 121.52 |
| Third kettle | 182.74 | 180.09 |
| Fourth kettle | 243.66 | 237.81 |
| Fifth kettle | 304.57 | 295.55 |
| Sixth kettle | 365.48 | 346.28 |
The production process of the two reaction kettles is controlled by calculation and measurement methods respectively, and the product quality is shown in figure 1 and figure 2 respectively. Specifically, as shown in fig. 1, the invention provides a topographic map of the precursor of NCM551530 prepared by controlling the production process of the reaction by a calculation method. As shown in fig. 2, the invention provides a topography of precursor of NCM551530 type prepared by controlling the production process of the reaction by a practical measuring method.
As can be seen from FIG. 1, the reaction process is controlled by a calculation method, and the process parameters are adjusted in time, so that the particle surface morphology of the prepared precursor material is better, and the primary particle morphology is uniform.
And the reaction process is controlled by adopting an actual measurement method, and the defect of poor timeliness of the traditional actual measurement method is obvious because the ammonium ion concentration in a reaction system is higher when large-particle materials are produced. As can be seen from fig. 2, the particle surfaces of the precursor materials prepared by measuring the solid content partially showed adhesion, and the consistency of the materials was poor.
While particular embodiments of the present invention have been illustrated and described, it will be appreciated that the above embodiments are merely illustrative of the technical solution of the present invention and are not restrictive; those of ordinary skill in the art will understand that: modifications may be made to the above-described embodiments, or equivalents may be substituted for some or all of the features thereof without departing from the spirit and scope of the present invention; the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention; it is therefore intended to cover in the appended claims all such alternatives and modifications that are within the scope of the invention.
Claims (17)
1. A method for calculating solid content in a process of preparing solid materials by a batch method is characterized in that a calculated value M of the solid content is calculated firstly, and the calculation method of the calculated value M comprises the following steps:
M=C[(n-1)T0+T]；
wherein the content of the first and second substances,
；
m is a calculated value of solid content, and the unit is g/L;
c salt (salt)The unit mol/L is the molar concentration of the salt solution in the reaction kettle;
athe feeding speed of the salt solution is L/h;
Mris the relative molecular mass of the material;
Vfis the effective volume of the reaction kettle and has the unit of m3；
T0The unit is h, which is the reaction time of each kettle;
t is the residual time except the integral multiple of the full-kettle reaction time, and the unit is h;
Tmfor the preparation of materialsThe total time of the reaction in (1) is h;
n is the number of reaction kettles, n =1, 2, …, Tm/T0The integer part of (1);
and calculating a correction value R, wherein the correction value R = A × M, A is a correction coefficient, and A = 0.883-1.002.
2. The calculation method according to claim 1, wherein in the process of calculating the solid content, the solid content in each part of the reaction kettle is consistent;
after the reaction kettle is full, standing for precipitation, and then discharging supernatant in an overflow mode, wherein the volume of the raw material liquid fed is equal to the volume of the discharged supernatant;
the mass of solid particles in the clear liquid is zero;
the volume of the mother liquor extracted after the kettle is filled every time is VnWherein n =1, 2, …, Tm/T0The integer part of (2).
3. The calculation method according to claim 1, wherein the particle size D50 of the material is 2 to 20 μm.
4. The method of claim 1, wherein the particle size D50 of the material is 8-18 μm.
5. The calculation method according to claim 1, wherein the molar concentration of the salt solution is 1.5-2.5 mol/L.
6. The calculation method according to claim 1, wherein the effective volume of the reaction kettle is 20 to 10m3。
7. The calculation method according to claim 1, wherein when M <150g/L, a is 0.992 to 1.002.
8. The calculation method according to claim 1, wherein when M is 150 to 250g/L, A is 0.973 to 0.991.
9. The calculation method according to claim 1, wherein when M is 150 to 250g/L and the particle size D50 of the material is not more than 8 μ M, A is 0.973 to 0.988.
10. The calculation method according to claim 1, wherein when M is 150 to 250g/L and the particle size D50 of the material is greater than 8 μ M, A is 0.985 to 0.991.
11. The calculation method according to claim 1, wherein when M is 250 to 350g/L, A is 0.922 to 0.982.
12. The calculation method according to claim 1, wherein when M is 250-350 g/L and the particle size D50 of the material is less than or equal to 8 μ M, A is 0.922-0.954.
13. The calculation method according to claim 1, wherein when M is 250 to 350g/L and the particle size D50 of the material is >8 μ M, A is 0.945 to 0.982.
14. The calculation method according to claim 1, wherein when M >350g/L, A is 0.883-0.965.
15. The calculation method according to claim 1, wherein when M >350g/L and the particle size D50 of the material is ≦ 8 μ M, A is 0.883-0.934.
16. The calculation method according to claim 1, wherein a is 0.936-0.965 when M >350g/L and the particle size D50 of the material is >8 μ M.
17. The use of the calculation method of any one of claims 1 to 16 in the adjustment of the reaction progress during the preparation of a ternary lithium ion battery precursor material by batch-wise co-precipitation.
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