CN116209639A - Method for preparing electrode active material precursor - Google Patents

Method for preparing electrode active material precursor Download PDF

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CN116209639A
CN116209639A CN202180058941.9A CN202180058941A CN116209639A CN 116209639 A CN116209639 A CN 116209639A CN 202180058941 A CN202180058941 A CN 202180058941A CN 116209639 A CN116209639 A CN 116209639A
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robot
hydroxide
processing device
precursor
sample
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P·哈特曼
H·索默
C·苏林
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BASF SE
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    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D5/00—Control of dimensions of material
    • G05D5/04—Control of dimensions of material of the size of items, e.g. of particles
    • G05D5/06—Control of dimensions of material of the size of items, e.g. of particles characterised by the use of electric means
    • 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
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D21/00—Control of chemical or physico-chemical variables, e.g. pH value
    • G05D21/02—Control of chemical or physico-chemical variables, e.g. pH value characterised by the use of electric means
    • G—PHYSICS
    • G05—CONTROLLING; REGULATING
    • G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
    • G05D22/00—Control of humidity
    • G05D22/02—Control of humidity characterised by the use of electric means
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • 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
    • C01P2006/80—Compositional purity
    • C01P2006/82—Compositional purity water content
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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Abstract

The present invention relates to a method for preparing an electrode active material precursor, comprising the steps of: (a) preparing an oxide, (oxy) hydroxide, hydroxide or carbonate comprising nickel by (co) precipitation in an aqueous medium, (b) separating the oxide, (oxy) hydroxide, hydroxide or carbonate from the aqueous medium by a solid-liquid separation method, (c) optionally drying the solid residue obtained from step (b) in air, (d) extracting at least two samples of 10mg to 10g from the solid material obtained from step (b) or if applicable (c) using a robot, (e) transferring the samples to another robot or another part of the same robot, wherein the respective robot transfers the samples to at least one test unit to perform a measurement of at least one parameter selected from the group consisting of: (e1) Particle diameter, (e 2) elemental distribution, and (e 3) water content, (e 4) crystallographic properties in XRD, or (e 5) specific surface (BET), (e 6) sulfate content.

Description

Method for preparing electrode active material precursor
The present invention relates to a method for preparing an electrode active material precursor, comprising the steps of:
(a) An oxide, (oxy) hydroxide, hydroxide or carbonate comprising nickel is prepared by (co) precipitation in an aqueous medium,
(b) Separating the oxide, (oxy) hydroxide, hydroxide or carbonate from the aqueous medium by a solid-liquid separation process,
(c) Optionally drying the solid residue obtained from step (b) in air,
(d) Extracting at least two samples of 10mg to 10g from the solid material obtained in step (b) or (c) if applicable using a robot,
(e) Transferring the sample to another robot or another part of the same robot, wherein the respective robot transfers the sample to at least one test unit to perform a measurement of at least one parameter selected from the group consisting of:
(e1) The diameter of the particles is set to be the same as the diameter of the particles,
(e2) Element distribution, and
(e3) The water content of the water-based paint,
(e4) Crystallographic properties in XRD, or
(e5) Specific surface (BET),
(e6) Sulfate content.
Furthermore, the invention relates to a device which can be used to carry out the method.
Lithium ion secondary batteries are modern devices that store energy. Many fields of application have been and are being considered, ranging from small devices such as mobile phones and notebook computers to automotive batteries and other batteries for mobile electronics. The various components of the battery have a decisive role for the performance of the battery, such as electrolyte, electrode material and separator. Positive electrode materials are of particular interest. Several materials have been proposed, such as lithium iron phosphate, lithium cobalt oxide and lithium nickel cobalt manganese oxide. Despite extensive research, the solutions found so far have room for improvement.
The positive electrode active material is generally prepared by using a two-stage process. In the first stage, it is prepared by precipitating a sparingly soluble compound of a transition metal, such as a carbonate or hydroxide, from a solution. The sparingly soluble salts are also referred to as precursors in many cases. In the second stage, the precursor is combined with a lithium compound such as Li 2 CO 3 LiOH or Li 2 O is mixed and calcined at an elevated temperature, e.g., 600-1100 ℃.
Several technical fields remain to be solved. Volumetric energy density, capacity fade, cycling stability remain areas of research and development. However, other problems are found in production. Although a constant product quality is required, sometimes the quality and composition vary within wide limits. However, drastic changes in quality may lead to a greater amount of product not meeting specifications, hereinafter also referred to as "off-grade" material, and to increased costs. In many cases, the mass of the precursor is responsible for the non-compliance of the positive electrode active material with the prescribed mass.
It is therefore an object to provide a method which leads to a more uniform product quality in the manufacture of electrode active materials, in particular corresponding precursors, and to a reduction in the amount of off-spec material.
Thus, the method defined at the outset, hereinafter also referred to as "method of the invention" or "method according to the invention" was found. The method of the invention comprises several steps as defined at the outset, hereinafter also defined as the sequence of steps (a), step (b), step (c), etc. The method of the present invention will be described in more detail below. Step (b) is an optional step.
In step (a), a precursor is prepared, said precursor being selected from the group consisting of oxides, (oxy) hydroxides, oxides and carbonates comprising nickel, preferably from the group consisting of complex oxides, complex (oxy) hydroxides and complex carbonates comprising nickel. In embodiments where the precursor is nickel (oxy) hydroxide or nickel oxide, the precursor is preferably prepared by precipitating nickel hydroxide from an aqueous solution of nickel sulfate with an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, followed by drying in air. In embodiments where the precursor comprises at least one metal other than nickel (e.g., cobalt or manganese), the precursor is a complex oxide, complex (oxy) hydroxide, or complex carbonate.
Preferably, the precursor comprises nickel and at least one cobalt and manganese, and optionally at least one Mg, al and Y or transition metal selected from Ti, zr, nb, ta, fe, mo and W.
In one embodiment of the invention, the precursor is obtained by (co) precipitating nickel and at least one cobalt and manganese as carbonate from an aqueous solution comprising nickel and at least one water soluble salt of cobalt and manganese with an alkali metal (bi) carbonate. In the context of the present invention, a water-soluble salt is a salt having a solubility of at least 50g/l at 20 ℃. Examples are nitrates, acetates, halides such as chlorides and bromides, and in particular sulfates. The amounts of nickel and at least one nitrate, acetate or preferably sulfate of cobalt and manganese are applied in a stoichiometric ratio corresponding to TM. The co-precipitation may be achieved by adding an alkali metal (bi) carbonate, such as potassium bicarbonate, potassium carbonate, sodium bicarbonate or an aqueous solution of sodium carbonate, to the above solution in a continuous, semi-continuous or batch process. The mother liquor is then removed after the co-precipitation, for example by filtration, and then the water is removed.
The precursor is preferably obtained by co-precipitation of nickel and at least one of cobalt and manganese as hydroxides from an aqueous solution containing water. Examples are nitrates, acetates, halides such as chlorides and bromides, and in particular sulfates. The amounts of nickel and at least one nitrate, acetate or preferably sulfate of cobalt and manganese are applied in a stoichiometric ratio corresponding to TM. The co-precipitation may be achieved by adding an alkali metal hydroxide, such as an aqueous solution of potassium hydroxide or sodium hydroxide, to the above solution in a continuous, semi-continuous or batch process. The mother liquor is then removed after the co-precipitation, for example by filtration, and then the water is removed.
The precursor is prepared in particulate form. In one embodiment of the invention, the precursor (A) has an average particle diameter (D50) of 2 to 20. Mu.m, preferably 3 to 16. Mu.m, more preferably 7 to 10. Mu.m. In the context of the present invention, the average particle diameter (D50) refers to the median value of the volume-based particle diameters, which can be determined, for example, by light scattering. In one embodiment, the precursor has a unimodal particle diameter distribution. In other embodiments, the particle distribution of the precursor may be bimodal, e.g., one maximum in the range of 1-5 μm and another maximum in the range of 7-16 μm.
The secondary particles of the precursor are preferably spherical in particle shape, i.e. particles having a spherical shape. Spherical spheres should include not only those particles that are perfectly spherical, but also those particles whose maximum and minimum diameters differ by no more than 10% from 90% (number average) of a representative sample.
In one embodiment of the invention, the precursor comprises secondary particles as agglomerates of primary particles. Preferably, the precursor comprises spherical secondary particles as agglomerates of primary particles. Even more preferably, the precursor comprises spherical secondary particles as agglomerates of spherical primary particles or flakes.
In one embodiment of the invention, the precursor may have a particle diameter distribution span of 0.5 to 0.9, the span being defined as [ (D90) - (D10) ]/(D50), all as determined by laser analysis. In another embodiment of the present invention, the precursor may have a particle diameter distribution span of 1.1 to 1.8.
In one embodiment of the invention, the precursor has a specific surface (BET) of 2 to 10m 2 /g or even 15-100m 2 /g, for example by nitrogen adsorption, in accordance with DIN-ISO 9277:2003-05.
In one embodiment of the invention, the precursor may be characterized by crystallographic properties obtainable by X-ray diffraction, for example
Figure BDA0004113617260000041
C value of (c). Typical peaks in the X-ray spectrum (Cu-kα) have the following 2Θ values:
001：19.0-19.4
100：33.0-34.3
101：38.0-39.5
102：52.0-53.2
110：59-61.2
111：62-65.1。
in one embodiment of the invention, the precursor may have a uniform distribution of the transition metals nickel, cobalt and manganese over the particle diameter. In other embodiments of the invention, the distribution of at least two of nickel, cobalt and manganese is non-uniform, e.g. shows a gradient of nickel and manganese, or shows layers of different concentrations of at least two of nickel, cobalt and manganese. Preferably the precursor has a uniform distribution of transition metal over the particle diameter.
In one embodiment of the invention, the precursor may comprise elements other than nickel and at least one of cobalt and manganese, such as at least one Mg, al and Y or a transition metal selected from Ti, zr, nb, ta, fe, mo and W, for example in an amount of 0.1 to 5 mole% relative to TM. However, it is preferred that precursor (a) contains only negligible amounts of elements other than nickel, cobalt and manganese, for example at detection levels of up to 0.05 mole%.
The precursor may contain trace amounts of metal ions as impurities, for example trace amounts of ubiquitous metals such as sodium, calcium, iron or zinc, but such trace amounts will not be considered in the description of the invention. In this regard, trace amounts mean an amount of 0.05 mole% or less relative to the total metal content of TM.
In one embodiment of the invention, the precursor comprises one or more impurities, such as residual sulfate (in the case where the precursor is prepared by co-precipitation from a solution of one or more sulfates of nickel, cobalt, and manganese). The sulfate may be 0.1 to 0.4 wt% relative to the entire precursor.
In one embodiment of the invention, the precursor is an oxide, oxyhydroxide, or hydroxide of TM, where TM has the general formula (I):
(Ni a Co b Mn c ) 1-d M d (I)
wherein:
a is 0.6 to 0.95, preferably 0.6 to 0.9,
b is 0.025 to 0.2, preferably 0.03 to 0.12,
c is 0.025-0.2, preferably 0.04-0.1, and
d is 0 to 0.1, preferably 0.005 to 0.1,
and M is Al, ti, zr or a combination of at least two of the foregoing, an
a+b+c＝1。
Optionally, at least one dopant selected from at least one of Mg, al, Y, ti, zr, nb, ta, fe, mo and W, which is a water-soluble compound, may be added during the co-precipitation.
In one embodiment of the invention, the precursor is an oxide, oxyhydroxide or hydroxide or carbonate of TM, wherein TM has the general formula (I):
(Ni a Co b Mn c ) 1-d M d (I)
wherein:
a is 0.3 to 0.4,
b is 0 to 0.1 of the total weight of the catalyst,
c is 0.6 to 0.7,
d is 0 to 0.1, preferably 0.005 to 0.1,
and M is Al, ti, zr or a combination of at least two of the foregoing, an
a+b+c＝1。
Optionally, at least one dopant selected from at least one of Mg, al, Y, ti, zr, nb, ta, fe, mo and W, which is a water-soluble compound, may be added during the co-precipitation.
By carrying out step (a), an aqueous slurry of the precursor is formed.
In step (b), the oxide, (oxy) hydroxide, hydroxide or carbonate is removed from the aqueous medium by a solid-liquid separation method, for example by filtration or centrifugation. Filtration methods are known per se and may be assisted by a washing step.
In optional step (c), the solid residue (possibly a filter cake in case of filtration) may be dried in air. Suitable drying temperatures are from 80 to 200℃and preferably from 105 to 150 ℃.
In one embodiment of the invention, step (c) may be carried out under reduced pressure, for example 200-500 mbar. In other embodiments, step (c) is performed at ambient pressure.
From step (b) or, if applicable, step (c) a solid material is obtained. The solid material may be used as a precursor.
To implement step (d), a robot is applied. The robot collects at least two samples of 10mg to 10g, preferably 20mg to 5g, even more preferably 100mg to 2g per unit to be analyzed in a continuous process, for example every 30 minutes to every day, or every batch or cake, preferably 3-5 times. The more samples that are collected, the more assurance that the samples will provide a representative average of all precursors. However, if too many samples are collected, too much precursor is required for analysis.
In a preferred embodiment, samples taken from the same batch or cake are robotically combined and thoroughly mixed prior to further analysis.
The robot may assign a number to the combined sample to be analyzed, which may then be combined with the corresponding number of the batch or filter cake, respectively, to enable tracking of the sample.
In other embodiments, no number is assigned to the batch or filter cake, etc., and the trend of the results in step (e) is simply determined. If the trend shows that the sample does not meet the specification, the robot will react as follows.
The robot may collect the sample with a robotic arm that holds a device for collecting the sample, such as a spatula or spoon instrument, etc.
In step (e), the robot transfers the sample to another robot or another part of itself, wherein the respective robot transfers the sample to at least one test unit to perform the measurement. In the context of the present invention, unless explicitly stated otherwise, there is no distinction between "another part" of the same robot that extracts the sample and a second and thus different robot that performs the analysis or transfer to the unit that performs the synthesis.
In a preferred embodiment, the robot performs step (e) with several samples in parallel, e.g. with 2-12 samples.
Another aspect of the invention relates to an apparatus of the device, hereinafter also referred to as the apparatus of the invention, wherein the apparatus comprises a robot, e.g. a synthetic robot, having means for collecting 10mg to 10g of precursor samples, and means (means) for transferring the electrode material mixture to a test unit for performing the test.
In a preferred embodiment of the invention, the device of the invention further comprises a processing means which performs the recording of step (e) of the method of the invention and compares the results of the electrochemical test with the desired results.
In a preferred embodiment of the invention, the apparatus of the invention further comprises a processing device which collects data as input via the input channel and provides an electronic signal to the production control function via the output channel in case at least two consecutive samples show a deviation from the desired result, the term "desired result" being explained above.
In one embodiment of the invention, the precursor is characterized by at least one, preferably at least two parameters selected from the group consisting of:
(e1) The diameter of the particles is set to be the same as the diameter of the particles,
(e2) The distribution of the elements is such that,
(e3) The water content of the water-based paint,
(e4) The crystallographic properties in XRD and,
(e5) Specific surface (BET), or (e 6) sulfate content.
As described herein, particle diameter (e 1) may be defined as the average particle diameter (D50) as determined by dynamic light scattering (preferably using an autosampler) or by laser diffraction or electroacoustic spectroscopy, and refers to the volume-based average.
In one embodiment of the present invention, the particle diameter (e 1) further includes a specification regarding the width of the particle diameter distribution, for example, expressed as [ (D90) - (D10) ]/(D50).
In one embodiment of the invention, the particle diameter (e 1) comprises information about other characteristics of the particle diameter distribution, such as whether the particle diameter distribution is unimodal or bimodal or multimodal.
The elemental distribution may be determined by X-ray fluorescence, atomic emission spectroscopy, atomic absorption spectroscopy, or by scanning electron microscopy and EDS, or by a combination of the above methods. Further details of element distribution (e 2) have been discussed above.
The water content (e 3) comprises physically adsorbed (adsorbed) water, preferably chemically bound water. The knowledge of which is of great importance for the correct calculation of the amount of lithium source before calcination. The water content (e 3) can be determined by karl fischer titration. Preferably, the water content (e 3) is determined by karl fischer titration in an automatic titration apparatus. The water content (e 3) may be 5 to 1,000ppm of water, wherein ppm is weight ppm.
The crystallographic properties (e 4) of XRD, e.g. lattice parameters, depend on elemental composition, secondary particle diameter, primary particle diameter, crystallographic strain, crystallinity, e.g. c-axis, a-axis, impurities. Examples are the width and shape of peaks in the XRD pattern.
The specific surface (BET) (hereinafter also referred to as BET surface (e 5)) of the precursor may be 1 to 80m 2 Preferably 5-80m 2 And/g. The BET surface (e.5) can be determined by an automated device with an autosampler.
The sulfate content (e 6) can be determined by ion chromatography. It may be expressed in weight% and refers to sulfate or S. Preferably the sulphate content is not more than 0.5 wt%, preferably 0.4 wt% of the precursor. A suitable lower limit is 0.1 wt% sulphate relative to the precursor.
In one embodiment of the invention, the method of the invention comprises the additional step of collecting a sample of the filtrate or slurry prior to filtration. The filtrate can be analyzed for, for example, metal ions, especially nickel and, if applicable, cobalt.
Another aspect of the invention relates to an apparatus of a device, hereinafter also referred to as the apparatus of the invention, wherein the apparatus comprises a synthetic robot having means for collecting 10mg to 10g of precursor samples, for transferring the samples to another robot or another part of the same robot, to at least one test unit for performing a measurement of at least one parameter selected from the group consisting of:
(e1) The diameter of the particles is set to be the same as the diameter of the particles,
(e2) Element distribution, and
(e3) Water content (e 4) crystallographic properties in XRD, or (e 5) specific surface (BET),
(e6) Sulfate content.
In a preferred embodiment, the apparatus of the present invention further comprises a processing device which collects data of any one of steps (e 1) to (e 6) as input through an input channel and compares the results of the electrochemical test with target results stored in said processing device. An example of a processing device is a computer. As used herein, the term "computer" may refer to a single computer or a plurality of computers working together to perform the functions described above.
In one embodiment of the invention, the apparatus of the invention further comprises a processing device which collects data as input via the input channel and provides an electronic signal to the production control function via the output channel in case at least two consecutive samples show a significant deviation from the target result stored in said processing device.
In one embodiment of the invention, the device of the invention further comprises a model relating the measurements (e 1) to (e 6) to the process parameters of step (a) based on stored data and thus relating the measured data of any one of (e 1) to (e 6) to at least one of pH, nickel and other metal content, stirring rate and drying parameters such as temperature and drying time. In particular, the processing means in the device of the invention may derive adapted process parameters based on a comparison of the models and appropriate operating conditions when an unacceptable sample has been collected.
The invention is further illustrated by working examples.
I. Providing a precursor
I.1 Synthesis of the precursor TM-OH.1, steps (a.1) to (c.1)
Deionized water was charged into the stirred tank reactor and warmed to 55 ℃ and the pH was adjusted to 12 by adding aqueous sodium hydroxide.
The coprecipitation reaction was started by feeding both the aqueous solution of the transition metal sulfate and the aqueous solution of sodium hydroxide at a flow rate ratio of 1.9 and a total flow rate resulting in an average residence time of 8 hours. The transition metal solution contained Ni, co and Mn in a 6:2:2 molar ratio and a total transition metal concentration of 1.65 mol/kg. The aqueous sodium hydroxide solution is 25% by weight sodium hydroxide solution. The pH was maintained at 11.9 by separate feeding of aqueous sodium hydroxide. After particle size stabilization, the resulting suspension was continuously removed from the stirred vessel. The mixed Transition Metal (TM) oxyhydroxide precursor TM-oh.1 is obtained by filtering the resulting suspension, washing with distilled water, drying in air at 120 ℃ and sieving. The average particle diameter (D50) was 10. Mu.m. I.2 Synthesis of the precursor TM-OH.2, steps (a.2) to (c.2)
Deionized water and 49g of ammonium sulfate/kg of water were charged into a stirred tank reactor. The solution was warmed to 55 ℃ and the pH was adjusted to 12 by adding aqueous sodium hydroxide.
The coprecipitation reaction was started by feeding both the aqueous solution of the transition metal sulfate and the aqueous solution of sodium hydroxide at a flow rate ratio of 1.8 and a total flow rate resulting in an average residence time of 8 hours. The transition metal solution contained Ni, co and Mn in a molar ratio of 8:1:1 and a total transition metal concentration of 1.65 mol/kg. The aqueous sodium hydroxide solution was a 25 wt% sodium hydroxide solution and a 25 wt% ammonia solution in a weight ratio of 6. The pH was maintained at 12 by separate feeding of aqueous sodium hydroxide. The mother liquor was continuously removed from the start of all feeds. After 33 hours, all feed streams were stopped. The mixed Transition Metal (TM) oxyhydroxide precursor TM-oh.2 is obtained by filtering the resulting suspension, washing with distilled water, drying in air at 120 ℃ and sieving. The average particle diameter (D50) was 10. Mu.m.
Step (d.1)
After step (c.1), the robotic arm separately collects several small samples of 1g of TM-OH.1, each from the dry material. For this purpose, the sample is dispensed into the container by one mechanical arm, the other closing the lid of the container to avoid carbon dioxide inhalation. The closed vessel is then transferred to a different section for analysis and electrode processing.
Steps (e 3.1), (e 4.1) and (e 5.1):
a container with 1g TM-oh.1 was transferred to an automatic XRD apparatus to measure the powder diffraction pattern of the sample. Another 1g sample of TM-OH.1 was transferred to an automatic Karl Fischer titration apparatus to measure the moisture content of the TM-OH.1 material, and an additional 5g of TM-OH.1 was used for automatic BET surface measurement.
The computer compares the test results with the specified results. If all parameters are within the required specification, no adaptation of the production process is required.
Step (d.2)
After step (c.2), the robotic arm separately collects several small samples of 1g of TM-OH.2, each from the dry material. For this purpose, the sample is dispensed into the container by one mechanical arm, the other closing the lid of the container to avoid carbon dioxide inhalation. The closed vessel is then transferred to a different section for analysis and electrode processing.
Steps (e 3.2), (e 4.2) and (e 5.2):
a container with 1g TM-oh.2 was transferred to an automatic XRD apparatus to measure the powder diffraction pattern of the sample. Another 1g sample of TM-OH.1 was transferred to an automatic Karl Fischer titration apparatus to measure the moisture content of the TM-OH.1 material, and an additional 5g of TM-OH.2 was used for automatic BET surface measurement.
The computer compares the test results with the specified results. If all parameters are within the required specification, no adaptation of the production process is required.
If there is a significant deviation from specification in at least two consecutive tests, the computer provides an electronic signal to the production control function via the output channel, which can rapidly stop the production of off-grade material.

Claims (15)

1. A method of preparing an electrode active material precursor comprising the steps of:
(a) An oxide, (oxy) hydroxide, hydroxide or carbonate comprising nickel is prepared by (co) precipitation in an aqueous medium,
(b) Separating the oxide, (oxy) hydroxide, hydroxide or carbonate from the aqueous medium by a solid-liquid separation process,
(c) Optionally drying the solid residue obtained from step (b) in air,
(d) Extracting at least two samples of 10mg to 10g from the solid material obtained in step (b) or (c) if applicable using a robot,
(e) Transferring the sample to another robot or another part of the same robot, wherein the respective robot transfers the sample to at least one test unit to perform a measurement of at least one parameter selected from the group consisting of:
(e1) The diameter of the particles is set to be the same as the diameter of the particles,
(e2) Element distribution, and
(e3) The water content of the water-based paint,
(e4) Crystallographic properties in XRD, or
(e5) Specific surface (BET),
(e6) Sulfate content.
2. The method of claim 1, wherein the precursor is selected from the group consisting of complex oxides, complex (oxy) hydroxides, and complex carbonates comprising at least one metal selected from cobalt and manganese.
3. The method of claim 1 or 2, wherein the robot performs step (e) with several samples in parallel.
4. The method according to any one of the preceding claims, wherein in step (e) samples are taken at 1-24 hour intervals.
5. The method according to any one of the preceding claims, wherein in step (e 1) the particle diameter distribution is determined.
6. The method according to any one of the preceding claims, wherein in step (e 2) the elemental distribution is determined by X-ray fluorescence, atomic emission spectroscopy, atomic absorption spectroscopy or by scanning electron microscopy and EDS.
7. The method according to any one of the preceding claims, wherein in step (e 3) the water content is determined by karl fischer titration in an automatic titration apparatus.
8. A method according to any preceding claim, wherein the entire recording of steps (d) to (e) is performed by a processing device and the processing device compares the results of the test with the required results.
9. The method of claim 8, wherein the processing device collects data as input through an input channel and provides an electronic signal to a production control function through an output channel in the event that at least two consecutive samples exhibit an unfavorable deviation from a target result.
10. The method according to claim 8 or 9, wherein the processing device compares the data for the at least one measurement (e 1) to (e 6) of the sample showing an unfavorable deviation from the target result with stored data associated with the process parameters of step (a), thus correlating the data of said measurement (e 1) to (e 6) with at least one of pH, nickel and other metal content and stirring rate.
11. Apparatus of a device comprising a robot having a device for collecting 10mg to 10g of a sample comprising an oxide, (oxy) hydroxide, hydroxide or carbonate of nickel, means for transferring said sample to another robot or another part of the same robot, the latter being used as a test unit to perform a measurement of at least one parameter selected from the group consisting of:
(e1) The diameter of the particles is set to be the same as the diameter of the particles,
(e2) Element distribution, and
(e3) The water content of the water-based paint,
(e4) Crystallographic properties in XRD, or
(e5) Specific surface (BET),
(e6) Sulfate content.
12. The apparatus of claim 11, further comprising a processing device that collects data of any of steps (e 1) through (e 6) as input through an input channel and compares results of the electrochemical test with target results stored in the processing device.
13. The apparatus according to claim 11 or 12, further comprising a processing device that collects data as input through an input channel and provides an electronic signal to a production control function through an output channel in case at least two consecutive samples show a significant deviation from a target result stored in the processing device.
14. The apparatus of any one of claims 11-13, wherein the processing device further comprises a model that correlates measurements (e 1) to (e 6) with the process parameters of step (a) based on stored data and thus correlates the data of measurements (e 1) to (e 6) with at least one of pH, nickel and other metal content, and agitation rate.
15. The apparatus of claim 14, wherein the processing device derives adapted process parameters based on a comparison of the model and appropriate operating conditions when an unacceptable sample has been collected.
CN202180058941.9A 2020-08-31 2021-08-24 Method for preparing electrode active material precursor Pending CN116209639A (en)

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