CN109311696B - Scalable precipitation synthesis method for battery materials with adjustable particle size distribution - Google Patents

Scalable precipitation synthesis method for battery materials with adjustable particle size distribution Download PDF

Info

Publication number
CN109311696B
CN109311696B CN201780038592.8A CN201780038592A CN109311696B CN 109311696 B CN109311696 B CN 109311696B CN 201780038592 A CN201780038592 A CN 201780038592A CN 109311696 B CN109311696 B CN 109311696B
Authority
CN
China
Prior art keywords
reactor
particle size
particles
precipitation
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201780038592.8A
Other languages
Chinese (zh)
Other versions
CN109311696A (en
Inventor
R·金加斯
L·H·科林
O·B·克里斯滕森
A·斯塔尔
S·H·奥尔森
S·达尔
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Topso Battery Materials Co ltd
Original Assignee
Haldor Topsoe AS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Haldor Topsoe AS filed Critical Haldor Topsoe AS
Publication of CN109311696A publication Critical patent/CN109311696A/en
Application granted granted Critical
Publication of CN109311696B publication Critical patent/CN109311696B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/06—Preparation of sulfates by double decomposition
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • 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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/50—Agglomerated particles
    • 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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

A metal carbonate material comprising nickel and manganese in an atomic ratio of 0.ltoreq.ni: mn.ltoreq.1/3 is prepared by a precipitation synthesis process wherein seed particles are continuously generated, agglomerated and grown in a first reactor, a specific amount of the product suspension is intermittently or continuously transferred to a stirred second reactor, and additional continuous raw material feed is added in a fixed ratio to the second reactor to grow the particles. This step is optionally repeated one or more times, and the final product is then collected intermittently or continuously from the final reactor.

Description

Scalable precipitation synthesis method for battery materials with adjustable particle size distribution
The present invention relates to a scalable precipitation synthesis process for preparing a material having an adjustable Particle Size Distribution (PSD) and consisting essentially of spherical particles as precursors for synthesizing cathode materials for batteries, more particularly by precipitating a metal carbonate material having an adjustable PSD comprising nickel and manganese in an atomic ratio of 0.ltoreq.Ni: mn.ltoreq.1/3.
Limited petroleum reserves and increasing efforts to reduce carbon dioxide emissions have led not only to a shift in the production of electrical energy to renewable energy forms, but also to an increase in research into alternative engines in the automotive industry. In addition, the growing demand for robust high power storage media in the consumer electronics and telecommunications fields has prompted improvements in existing energy storage systems and the development of new energy storage systems that are primarily concerned with efficiency, cost reduction, and safety. Because of its high weight energy storage capability, lithium ion batteries (libs) are a promising system for not only current and future energy storage, but also for automobiles and various other applications.
The first commercialized LiB was based on LiCoO 2 Graphite as a cathode and Li/Li as a cathode + 3.8V. However, since cobalt is relatively expensive and toxic, alternative cathode materials are continually being sought and more combinations of other materials are being tested and partially commercialized. One possibility to increase the energy density of LiB is to increase the operating voltage of the battery. This can be accomplished by using a cathode material having a higher electrode potential (e.g., liNi 0.5 Mn 1.5 O 4 Spinel, which provides a relative Li/Li + 4.7V) of the voltage of the power supply.
Spinel refers to a crystalline lattice in which oxide anions are arranged in a cubic close-packed lattice, and cations occupy some or all of the octahedral and tetrahedral sites in the lattice. Symmetry of spinel lattice through P4 for ordered phase 3 32 space groups and Fd-3m for the disordered phase. The spinel material may be a single disordered or ordered phase, or a mixture of both (adv. Mater.24 (2012), pp 2109-2116).
Another important factor in the selection of materials in LiB is that its components are abundant in the crust, ensuring long-term availability and cost reduction, as iron and manganese based materials are of great interest. In particular manganese oxide constitutes a promising group of cathode materials, since manganese is a cheap and non-toxic element. Furthermore, oxides of manganese have a rather high electron conductivity and a suitable electrode potential. In lithium manganese oxide, layered LiMnO 2 And spinel type LiMn 2 O 4 (LMO) is the most prominentTernary phase. The latter has the advantage over the layered phase that + About 4.0V, while LiMnO 2 On average only 3.0V was provided. LiMn 2 O 4 The lattice provides three-dimensional lithium diffusion, thereby absorbing and releasing the ions more rapidly. In doped LMO spinel, li + The diffusion of (c) is equally fast in all three dimensions.
LiMn doped with transition metal 2 O 4 In spinel electrodes, liNi y Mn 2- yO 4 (wherein 0.ltoreq.y.ltoreq.0.5) is a very promising material: due to Ni 2+ /Ni 4+ Electrochemical activity of redox couple, relative to Li/Li + Has additional capacity at a relatively high voltage of 4.7V. LiNi 0.5 Mn 1.5 O 4 Is 147mAh/g, so an attractive theoretical energy density is 4.7v x 147ah/kg = 691Wh/kg active material, referring to lithium metal. By substituting 25% of the manganese ions with nickel, no Mn is theoretically left in the structure 3+ . For charge balance reasons, ni 2+ The incorporation forces all manganese ions to be in their tetravalent state. If less than 25% of the manganese is replaced by Ni, some Mn 3+ Will remain in the structure. For LiNi y Mn 2-y O 4 Theoretically Mn 3+ :Mn 4+ The ratio is equal to (0.5-y). It should be noted that in practice, there is usually a small deviation of the theoretical composition and the average oxidation state when synthesizing materials. This is probably due to LiNi y Mn 2-y O 4 Defects and inhomogeneities in the structure or the presence of impurity phases that alter the composition of the main phase lead to deviations from the exact stoichiometry. For example, it is well known that when synthesizing LiNi 0.5 Mn 1.5 O 4 There is a small amount of rock salt phase present, which affects the stoichiometry of the spinel phase and starves the total material of oxygen (j.cabana et al Chemistry of Materials (2012), 2952).
The LNMO material is Ni-doped LiMn 2 O 4 Spinel-phase dominant lithium positive electrode active materials, which more specifically may be composed of the general formula Li x Ni y Mn 2-y O 4 Characterization, which is typical ofx and y have values of 0.9.ltoreq.x.ltoreq.1.1 and 0.ltoreq.y.ltoreq.0.5, respectively. The formula represents the composition of the spinel phase of the material. These materials are useful, for example, in portable electrical devices (US 8,404,381 B2), electric vehicles, energy storage systems, auxiliary Power Units (APUs), and Uninterruptible Power Supplies (UPS). Lithium positive electrode active materials based on LNMO are considered as current lithium secondary battery cathode materials (e.g., liCoO 2 ) As they have a high voltage and a high energy density and have a lower material cost.
Electrode active materials for lithium ion battery materials are described in great numbers in the literature. Thus, US 5.631.104 describes a lithium ion battery having formula Li x+1 M z Mn 2-y-z O 4 Wherein the crystal structure is spinel-like, which can be expressed relative to Li/Li + A significant amount of Li is reversibly inserted at potentials greater than 4.5V. M is a transition metal, in particular Ni and Cr, 0.ltoreq.x.ltoreq.1, 0.ltoreq.y<0.33, and 0<z<1。
US 2015/0041710 A1 relates to a cathode active material for a lithium secondary battery. More particularly, it relates to a method for preparing 3V spinel oxide having a composition of Li by carbonate coprecipitation 1+x [M y Mn (2-y) ]O 4-z S z (0.ltoreq.x.ltoreq.0.1; 0.01.ltoreq.y.ltoreq.0.5 and 0.01.ltoreq.z.ltoreq.0.5; M=Mn, ni or Mg). It describes the use of nickel and manganese sulphates for the preparation of Li 1.06 Ni 0.5 Mn 1.5 O 4 。
In addition to the elemental composition and crystal structure of the electrode material, it is known to those skilled in the art that controlling the shape and microstructure of the particles is critical if a battery with good cycling behavior and high performance is desired. For example, cinal et al (Solid State Ionics, 179 (2008) 1788) show that powder morphology has a significant impact on the electrochemical performance of LMO spinel when tested in half cells where Li metal is used as the anode. In particular, spherical LMO particles were found to have significantly higher capacity retention after 100 charge-discharge cycles than irregularly shaped particles. According to the authors, the improvement in performance is due to the reduced stress of the particles during the circulation, since the local Jahn-Teller distortion on one side of the spherical particles is counteracted by the same distortion on the opposite side of the particles.
One method of quantifying the particle size in a slurry or powder is to measure the size of a large number of particles and calculate the characteristic particle size as a weighted average of all measurements. Another way to characterize particle size is to plot the overall particle size distribution, i.e., the volume fraction of particles having a certain size as a function of particle size. In such a distribution, D10 is defined as the particle size where 10% of the population is below the value of D10, D50 is defined as the particle size where 50% of the population is below the value of D50 (i.e., the median), and D90 is defined as the particle size where 90% of the population is below the value of D90. Common methods for determining particle size distribution include laser diffraction measurement and scanning electron microscope measurement, and image analysis.
Also, there are several methods by which the sphericity and shape of particles can be characterized and quantified. Several form factors that have been proposed in the literature for assessing sphericity are listed in the literature by Almeida-Prieto et al, j.pharmaceutical sci., 93 (2004) 621: heywood factor, aspect ratio, roughness, pellis, rectangle, divergence, elongation, circularity, roundness, and Vp and Vr factors as set forth in this article. The circularity of the particles is defined as 4. Pi. (area)/(perimeter) 2 . Thus, an ideal spherical particle would have a circularity of 1, while particles with other shapes would have a circularity value between 0 and 1. The particle shape may be further characterized using an aspect ratio, which is defined as the ratio of the particle length to the particle width, where length is the maximum distance between two points on the perimeter and width is the maximum distance between two perimeter points connected by a line perpendicular to the length.
For most battery applications, space is at a premium and high energy densities are desired. Powders with high tap density electrode materials tend to result in electrodes with higher active material loading (and thus higher energy density) than powders with low tap density. Geometric-based demonstration may be used to show that materials composed of spherical particles have a higher theoretical tap density than particles with irregular shapes.
In addition to the shape of the spinel particles, surface microstructure and roughness are believed to play a key role in determining the cycling behavior and rate capability of high voltage electrode materials (e.g., LNMO) in a battery. Ni in LNMO 2+ /Ni 4+ Redox potential of redox couple relative to Li/Li + About 4.75V, which is above the stability limit of common liquid carbonate-based electrolytes (typically between 4.0 and 4.3V). This results in oxidation of the electrolyte on the positive electrode during operation of the cell and in the formation of a resistive cathode/electrolyte interface layer on the electrode. The rougher the surface of the active powder in the electrode (i.e., the greater its specific surface area), the more electrolyte is lost due to oxidation and the formation of a resistive cathode/electrolyte layer at the interface between the LNMO and the electrolyte. The rougher the surface of the active powder in the electrode (i.e., the greater its specific surface area), the more electrolyte is lost due to oxidation and formation of the cathode/electrolyte interface layer. Accordingly, there is a need for positive electrode active materials having low specific surface areas (i.e., smooth and non-porous surface topography) to avoid capacity fade during long term battery operation.
The lithium positive electrode active material may be prepared from a precursor obtained by mechanically mixing starting materials to form a uniform mixture, and then calcining. For example, in US 8,404,381 B2, an intimate mixture of nickel carbonate, manganese carbonate and lithium carbonate is prepared by milling in the presence of hexane. The mixture was dried and treated at 600 ℃ (10 hours) and then 900 ℃ (15 hours) to form LNMO. It is critical that the LNMO material prepared according to this method is not spherical, which has a significant negative impact on the cycling behavior of a battery using such LNMO as a positive electrode and on the tap density of the LNMO powder.
As used herein, a "precursor" is a composition prepared by mixing starting materials to obtain a homogeneous mixture (see, e.g., journal of Power Sources, 238 (2013) pp.245-250) or a composition prepared by mixing a lithium source with a composition prepared by precipitating starting materials (see, e.g., electrochromic. Acta, 115 (2014) pp.290-296).
Another method of preparing a positive electrode active material for LiB is to usePrecipitation method followed by calcination/lithiation. In precipitation, two or more solutions are mixed and reacted under controlled conditions to form insoluble products, which can then be separated from the remaining mixture. When precipitation is used in battery material synthesis, the process generally begins with precipitation of transition metal species at the desired elemental ratio. Examples of such transition metal species include, but are not limited to, ni (OH) 2 、NiCO 3 、Ni 2 CO 3 (OH) 2 、Ni(HCO 3 ) 2 、Ni 3 CO 3 (OH) 4 、Mn(OH) 2 、MnCO 3 、Ni 0.25 Mn 0.75 (OH) 2 、Ni 0.25 Mn 0.75 CO 3 、Ni 0.5 Mn 0.5 (OH) 2 、Ni 0.5 Mn 0.5 CO 3 、Ni 1/3 Mn 1/3 Co 1/3 (OH) 2 And Ni 1/3 Mn 1/3 Co 1/3 CO 3 . Such transition metal hydroxides, carbonates or hydroxycarbonates are generally referred to as precursor materials. After the precursor materials are obtained, they are typically mixed with Li-containing materials and calcined to elevated temperatures to ensure that the correct crystalline phase is formed. Li-containing materials include, but are not limited to, lithium hydroxide, lithium carbonate, and lithium nitrate. It is generally believed that the shape and size of the powder particles of the final active material will depend to a large extent on the morphology and size of the precursor particles. It is important that spherical precipitated particles can be obtained when the reaction parameters are properly controlled.
The precursor material for the LNMO type LiB positive electrode material can be prepared by using a mixture of Ni and Mn as hydroxide, i.e., ni y Mn 2-y (OH) 4 Precipitation, wherein y is more than or equal to 0 and less than or equal to 0.5. Such precipitation generally uses the corresponding transition metal sulfates and NaOH as starting materials and ammonia (NH) 3 、NH 4 OH or NH 3 ·H 2 O) as chelating agent. Other commonly used chelating agents include, but are not limited to NH 4 CO 3 Citric acid, glycolic acid, oxalic acid, polyacrylic acid, malonic acid, and EDTA.
Another method of preparing a precursor material for an LNMO type LiB positive electrode material is to precipitate a mixture of Ni and Mn as carbonAcid salts, i.e. Ni y Mn 2-y (CO 3 ) 2 Wherein y is more than or equal to 0 and less than or equal to 0.5. Such precipitation is generally carried out using the corresponding transition metal sulphates and Na 2 CO 3 As starting material and ammonia (NH) 3 、NH 4 OH or NH 3 ·H 2 O) as chelating agent. For example, in US 2014/0341797A1, niSO is described 4 、MnSO 4 、Na 2 CO 3 And NH 4 OH was fed to the particular reactor system at molar flow rates of 3.25mol/hr, 6.5mol/hr, 10.8mol/hr and 1.1 mol/hr. Spherical nickel manganese carbonate particles can be obtained but only when a continuous stirred tank reactor is combined with a centrifugal distributor and a particle size separator. A first disadvantage of the above-described process is that a complex reactor design is required to obtain spherical carbonate particles. A second disadvantage of the above method is the use of a chelating agent (in this case ammonia).
It is an object of the present invention to prepare high quality LNMO precursor products with tunable Particle Size Distribution (PSD) using a scalable precipitation synthesis process.
Continuous precipitation in a stirred tank reactor is commonly used as a synthetic method for mass production of spherical precursors for battery materials. In such a continuous precipitation setup, there is a continuous raw material feed and continuous product extraction from the stirred tank reactor. There is a steady state between the formation of new seeds, the growth of the particles and the partial removal of all particles. The synthesis may follow the following reaction scheme:
0.5NiSO 4 (aq)+1.5MnSO 4 (aq)+2Na 2 CO 3 (aq)->
2Na 2 SO 4 (aq)+Ni 0.5 Mn 1.5 (CO 3 ) 2 (s)
if the process is carefully designed, a product based on spherical particles will be produced, but with a broad PSD. PSD is broad because there are all stages of development of particles (seeds, agglomerated seeds, agglomerates that have grown a bit, and agglomerates that have grown a lot) in the product (see FIG. 1).
Batch precipitation in stirred tank reactors is also well known in the art. Here, if the method is carefully designed, spherical precursor particles with very narrow PSD can be prepared, as seed formation can be limited to the beginning of the precipitation process. A disadvantage of this process is that the same reactor is used in both the early and late stages of the process, and a very different reactor design would be advantageous.
The present invention relates to a scalable precipitation synthesis process that provides high quality products with tunable PSD (in both D50 and D90/D10 distributions). In this synthetic method, seed formation is separated in time and space from the final growth and polishing of the particles.
More specifically, the present invention relates to a scalable precipitation synthesis process as a production step in the preparation of battery materials, wherein:
(1) Seed particles are continuously formed, agglomerated and grown to a certain extent in a first reactor by continuously feeding and mixing raw materials, i.e., a metal ion solution and a solution containing carbonate ions, in a fixed ratio,
(2) Transferring the specified amount of product suspension produced in step (1) intermittently or continuously to a stirred second reactor and adding additional continuous feedstock feed to the second reactor in a fixed ratio to grow particles;
(3) Step (2) is optionally repeated one or more times by intermittently or continuously transferring a specified amount of the product of the previous step to a subsequent stirred tank reactor, wherein a fixed proportion of fresh continuous feedstock feed is added to further grow the particles, and
(4) The final product is collected from the final reactor intermittently or continuously for further processing,
wherein the desired size characteristics of the agglomerated particles in the final product are obtained without particle size separation and/or particle size selection.
The optimal rate of seed formation in step 1 is achieved by adjusting process parameters such as temperature, concentration and feed rate of metal ions and carbonate solution (pH), reactor design and optional agitation speed. The particles from the previous step should grow and only a very small amount of new seeds should be formed in step 2 and any subsequent steps. This can also be achieved by adjusting process parameters such as temperature, acid and base feed rates, reactor design and agitation speed.
The desired size characteristics of the agglomerated particles in the final product are obtained without particle size separation and/or particle size selection. In particular, no back flow of the product suspension, for example after particle size separation, takes place in the process of the invention. Thus, no reflux is required, for example part of the product suspension obtained in the first, second or third reactor is returned to the first, second or third reactor. Thus, the process of the present invention provides a simple method of obtaining metal carbonate materials having specific dimensional characteristics.
The preferred synthesis reaction is carbonate precipitation
y NiSO 4 (aq)+(2-y)MnSO 4 (aq)+(2+x)A 2 CO 3 (aq)->
2A 2 SO 4 (aq)+x A 2 CO 3 (aq)+Ni y Mn 2-y (CO 3 ) 2 (s)
Wherein NiSO 4 (aq) and MnSO 4 (aq) as a Metal ion solution, A 2 CO 3 (aq) as carbonate solution, a=na or K,0<y.ltoreq.0.5 and x.gtoreq.0, and x and y may optionally be different in different reactors.
When three reaction steps are used, the principle of the invention is shown in fig. 2, where a and B are the metal ion solution stream and the carbonate solution stream, respectively, and P represents the final precipitated product. Note that reactor 1 need not be a stirred reactor and in its mechanical design it may be significantly different from the other two reactors, for example it may be a tee-piece reactor, for example similar to the reactor described in US 2013/013687 A1.
Generally, as shown in FIG. 1, ni y Mn 2-y (CO 3 ) 2 The precipitation and growth steps of the precursor materials are as follows:
1. nucleation
2. Aggregation
3. Agglomeration
4. Growth and polishing.
An important advantage of the present invention is that in each reactor, the precipitation conditions can be tailored to accommodate the different steps of the above-described process. For example, the agglomeration step is inhibited by adjusting the ratio between the acid and base feeds to precipitate at a pH <8, which is preferred in the first precipitation reactor. A high pH (alkali excess) is preferred in the later steps, as this facilitates the growth and polishing of agglomerates of new small seed particles and ensures that most of the metal ions precipitate.
Another advantage relates to the uniformity and size distribution of the particles or agglomerates formed. Continuous precipitation using a single stirred reactor, which has heretofore been the preferred method in the art, results in a relatively broad particle size distribution. A narrower particle size distribution will minimize the stress experienced by the particles during charging and discharging of the battery, thereby increasing the life of the battery. The process of the present invention produces a narrower PSD than previously obtainable in continuous precipitation. This is shown in fig. 1.
Continuous preparation is a production process by which a dynamic balance between seed formation and precipitate growth is obtained. A continuous chemical feed is delivered to the reactor and the product is continuously removed.
In contrast, the process of the present invention comprises a semi-batch reaction. The only seeds in the reaction are added as starting solution, these seeds being prepared in a controlled continuous process, wherein a special reactor is used. If the batch reaction starts from multiple identical seeds at low pH (pH <8 for carbonate precipitation) to limit agglomeration, ideally the particles will grow equally as more feedstock is added. When the reactor is full, the product is obtained. The product should then be collected and a new batch reaction may be started.
Another advantage of the process according to the invention is that it results in a product with spherical particles having a narrower PSD (i.e. lower D90/D10 ratio) compared to standard continuous precipitation processes using one stirred reactor.
Such batch precipitation is a known technique and it will result in a narrow PSD. An advantage of the method of characterizing the invention is reproducibility, which is improved by controlling seed formation in the individual reactors and by adjusting the pH to allow stable growth of the particle size. Smaller particles require a lower pH to limit agglomeration.
The invention also allows a narrower PSD to be obtained by limiting mainly the continuous process of seed formation to the first reactor.
Another advantage of the multiple sequential reactor concept is that it provides the possibility to change the radial chemical composition of the agglomerates by changing the composition of the metal ion solution.
Comprises Ni y Mn 2-y (CO 3 ) 2 Wherein 0.ltoreq.y.ltoreq.0.5, may differ from the exact chemical formula and still be used for the production of LNMO material. A difference may occur because not all Ni and Mn are in oxidation state +2, which may be due to oxygen oxidation from the atmosphere. Another difference may be due to contamination of the feedstock. Yet another difference may be due to intentional doping of the precursor material, which is caused by the addition of other elements to the raw material (which remain in the precipitated precursor) during all or part of the precipitation process. Possible elements include, but are not limited to Mg, co, cr, fe, al, ti. These differences are included in the present invention.
The invention is further described in the following examples.
Example 1 (comparative example)
By mixing 281g of NiSO 4 ·7H 2 O and 507g MnSO 4 ·H 2 O was dissolved in 1757g of water to prepare NiSO having an atomic ratio of Ni to Mn of 1:3 4 And MnSO 4 Is a metal ion solution of (a). In another flask, by placing 424g Na 2 CO 3 A carbonate solution was prepared by dissolving in 1939g of water. The metal ion solution and the carbonate solution were added to a vigorously stirred (450 rpm) reactor at 35℃respectively. The flow rates of the two solutions were chosen so that the molar ratio of metal ions to carbonate ions was 1:1.1 and a constant pH between 7.5 and 7.6 was produced throughout the precipitation process. Of reactorsThe volume was 1 liter.
According to NiSO 4 (aq)、MnSO 4 (aq) and Na 2 CO 3 The synthesis proceeds by a simple reaction between (aq):
0.5NiSO 4 (aq)+1.5MnSO 4 (aq)+2.2Na 2 CO 3 (aq)->
4.4Na + (aq)+2SO 4 -(aq)+0.2CO 3 2 -(aq)+Ni 0.5 Mn 1.5 (CO 3 ) 2 (s)
the product was continuously removed from the reactor, leaving the reactants in the reactor for a residence time of 60 minutes. FIG. 3 shows Ni collected after 3 residence times 0.5 Mn 1.5 (CO 3 ) 2 Scanning Electron Microscope (SEM) images of the particles. Both agglomerated seed particles and larger agglomerates are evident in the precipitated product. The corresponding PSD is shown in FIG. 4, and the PSD data demonstrates the trend shown in FIG. 3. The particle size distribution was broad and bimodal, with D10 of 6.3 μm, D50 of 10 μm and D90 of 14.1. Mu.m. Thus, the D90/D10 ratio was 2.24.
Example 2
First, niSO with an atomic ratio of Ni to Mn of 1:3 was prepared 4 And MnSO 4 Metal ion solution and Na of (2) 2 CO 3 Substantially the same as used in example 1. The carbonate solution was diluted 10-fold with deionized water before starting the precipitation process. Precipitation was performed in a tee reactor consisting of a Swagelok 1/8 "stainless steel joint tee with a 1/16" stainless steel inlet for metal ion solution and a 1/8 "inlet for carbonate solution. The metal ion solution stream enters the reactor from the top, the carbonate solution stream enters the reactor from the side, and the product exits the reactor from the bottom. The flow rate was chosen such that the residence time of the product in the reactor was about 0.2 seconds. Precipitation was performed at room temperature. The product was collected in a stirred beaker.
The molar ratio of metal ions to carbonate ions was varied to investigate the effect of seed stability or agglomeration on pH. Agglomeration was investigated by storing the samples in closed glass bottles at room temperature for up to 14 days without stirring. The PSD evolution of 5 different samples is summarized in fig. 5. The particles precipitated and stored at a relatively low pH (pH.ltoreq.8.17, samples D and E) were substantially more stable to agglomeration than the particles precipitated at a higher pH (samples A, B and D).
Example 3 (batch precipitation)
This example describes a semi-batch process with 3 reactors for preparing LNMO precursor particles with a narrow PSD. First, seeds and agglomerated particles were prepared in a T-piece reactor using the same procedure used to prepare sample a particles in example 2. The flow rate was chosen such that the residence time of the product in the reactor was about 0.2 seconds. The product was collected in a stirred beaker. To avoid agglomeration, dilute H is used 2 SO 4 The pH of the product was adjusted to about 7.9.
A 300 ml sample of the product from the first reactor was transferred to the second reactor and used as starting solution for the next step, which was batch precipitation. The second reactor is mechanically substantially different from the first reactor and is a1 liter stirred reactor with a heating jacket. 300 ml of the starting solution from the first reactor was mixed with 200 ml of water and heated to 36℃and then another continuous stream of the same metal ion solution and carbonate solution as used in example 1 was introduced. The flow of the solution was monitored and controlled so that the pH remained between 8.1 and 8.6 during precipitation. During the entire 1 hour batch precipitation, the mixture in the reactor was stirred at 450 rpm. Subsequently, the above procedure was repeated 3 times, yielding 3 liters of product from the second reactor.
The 3 liters are transferred from the second reactor to the third reactor and used as starting solution for the next step (another batch precipitation). The third reactor was a stirred reactor having a heating jacket with an internal volume of 8 liters. The starting solution was heated to above 35 ℃ and then additional continuous streams of metal ion solution and carbonate solution were introduced, which in this example was the same as the solution used in example 1. The flow of the solution was monitored and controlled to maintain the pH between 8.79 and 9.42 during precipitation. After 2.5 hours of batch precipitation, the product in the reactor was collected. The corresponding PSD is shown in FIG. 6. The particle size distribution is significantly narrower than example 1 and is a unimodal distribution with a D10 of 10.00 μm, a D50 of 14.15 μm and a D90 of 19.96 μm. The D90/D10 ratio was thus 1.996. The final product was thoroughly washed, dried in a drying oven and stored for further processing (lithiation/calcination).
Example 4 (continuous precipitation)
This example describes a continuous process with 2 reactors for preparing LNMO precursor particles with a narrow PSD. By mixing 480g of NiSO 4 ·6.3H 2 O and 1051g MnSO 4 ·1.14H 2 O was dissolved in 3577g of water to prepare NiSO having an atomic ratio of Ni to Mn of 1:3 4 And MnSO 4 Is a solution of a first metal ion. In another flask, by placing 1106 and 1106g K 2 CO 3 A first carbonate solution was prepared by dissolving in 3762g of water. By diluting the first metal ion solution with demineralized water twice, niSO was prepared 4 And MnSO 4 Is a solution of a second metal ion. The second carbonate solution is prepared by diluting the first carbonate solution twice with demineralized water.
The second metal ion solution and the second carbonate solution were separately added to a vigorously stirred (2000 rpm) reactor at room temperature (about 20 ℃). The flow rates of the two solutions were chosen so that the molar ratio of metal ions to carbonate ions was 1:1.05 and a steady state pH of about 7.5 was produced. The volume of the reactor was 750 ml. The product was continuously removed from the reactor so that the residence time of the reactants in the reactor was 7.5 minutes. PSD after 7 hours of precipitation is shown in FIG. 7a, and the evolution of D10, D50 and D90 during precipitation is shown in FIG. 7 b. According to fig. 7b, steady state in the first reactor was obtained at the latest after 4 hours of precipitation, while other experiments (not included herein for the sake of brevity) showed that steady state could be obtained faster (after about 30 minutes of precipitation). The particle size distribution of the product from the first reactor was bimodal, with D10 of 0.6 μm, D50 of 3.5 μm and D90 of 7.5. Mu.m. The D90/D10 ratio was thus 12.5.
Part of the product from the first reactor was continuously pumped to the second reactor using peristaltic pumps. The second reactor was a stirred reactor with an internal volume of 8 liters of heating jacket maintained at a temperature above 35 ℃. Additional successive streams of the first metal ion solution and the first carbonate solution are added separately to the second reactor while introducing the product stream from the first reactor. The flow rates of the metal ions and carbonate solution were chosen such that the molar ratio of metal ions to carbonate ions was 1:1.16, resulting in a steady state pH of about 9.3. The stirring rate in the second reactor was 500rpm. The product was continuously removed from the second reactor, leaving a residence time of 43 minutes for the reactants in the reactor. PSD after 6.5 hours of precipitation is shown in FIG. 8a, and the evolution of D10, D50 and D90 during precipitation is shown in FIG. 8 b. According to fig. 8b, steady state in the second reactor is obtained after about 5 hours of precipitation. The particle size distribution of the product from the second reactor was bimodal with a D10 of 1.5 μm, a D50 of 8.6 μm and a D90 of 14.9. Mu.m. The ratio of D90/D10 of the product from the second reactor was 9.93, which is lower than the D90/D10 from the first reactor, which is desirable. Importantly, the volume fraction of the smallest particles (size less than 1 μm) in the products from the first and second reactors was reduced from 16 to 8% by volume, respectively. If more reactors are connected in series, a narrower product particle size distribution is expected.
The final product was thoroughly washed, dried in a drying oven and stored for further processing (lithiation/calcination).
It will be appreciated by those skilled in the art that changes could be made to the embodiments described above without departing from the broad inventive concept thereof. It is understood, therefore, that this invention is not limited to the particular embodiments disclosed, but it is intended to cover modifications within the spirit and scope of the present invention as defined by the appended claims.

Claims (17)

1. A precipitation synthesis process for producing a metal carbonate material comprising nickel and manganese in an atomic ratio of 0.ltoreq.ni: mn.ltoreq.1/3, wherein:
(1) Seed particles are continuously formed, agglomerated and grown to a certain extent in a first reactor by continuously feeding and mixing raw materials, i.e., a metal ion solution and a solution containing carbonate ions, in a fixed ratio,
(2) Transferring the specified amount of product suspension produced in step (1) intermittently or continuously to a stirred second reactor and adding additional continuous feedstock feed to the second reactor in a fixed ratio to grow particles;
(3) Step (2) is optionally repeated one or more times by intermittently or continuously transferring a specified amount of the product of the previous step to a subsequent stirred tank reactor, wherein a fixed proportion of fresh continuous feedstock feed is added to further grow the particles, and
(4) The final product is collected from the final reactor intermittently or continuously for further processing,
wherein the desired size characteristics of the agglomerated particles in the final product obtained in step (4) above are obtained without particle size selection, or a combination of particle size separation and particle size selection, in steps (1) to (4).
2. The method of claim 1, wherein the synthesis reaction is
y NiSO 4 (aq)+(2-y)MnSO 4 (aq)+(2+x)M 2 CO 3 (aq)->
2M 2 SO 4 (aq)+Ni 0.5 Mn 1.5 (CO 3 ) 2 (s)+x M 2 CO 3 (aq)，
Wherein NiSO 4 (aq) and MnSO 4 (aq) as a metal ion solution, M 2 CO 3 (aq) as carbonate solution, wherein m=na or K,0<y.ltoreq.0.5 and x.gtoreq.0, where x and y are optionally different in different reactors.
3. The process according to claim 1 or 2, wherein agglomeration is avoided by adjusting the pH to a value below 8 in the first reactor.
4. The process according to claim 1 or 2, wherein the process is carried out in batch precipitation in all reaction steps after step 1, wherein a specific amount of product from the pre-reactor is used as a starting material for the subsequent batch precipitation.
5. The process of claim 1 or 2, wherein all reactors are continuously operated and in steady state.
6. The method of claim 1 or 2, wherein the mechanical design of the first reactor is different from the mechanical design of a subsequent reactor.
7. The method of claim 6, wherein the first reactor is not a stirred reactor.
8. The method of claim 1 or 2, wherein the ratio between metal ions in the metal ion solution is different in all reaction steps.
9. The method of claim 1 or 2, wherein the metal carbonate material has a Ni to Mn atomic ratio of 0< Ni: mn +.1/3.
10. The method of claim 1 or 2, wherein the metal carbonate material has an atomic ratio of Ni to Mn of 1/4-Ni to Mn-1/3.
11. The method of claim 1 or 2, wherein the metal carbonate material has a Ni to Mn atomic ratio of 9/31+.ni to mn+.1/3.
12. The process according to claim 1 or 2, wherein the agglomerated particles in the final product are characterized by an average circularity of greater than 0.90 and at the same time an average aspect ratio of less than 1.50.
13. The process according to claim 1 or 2, wherein the D50 of agglomerated particles in the final product is from 3 to 50 μm, wherein the D50 of the volume-based particle size distribution is defined as the median particle size.
14. The process of claim 13, wherein the D50 of agglomerated particles in the final product is from 8 to 40 μιη, wherein the D50 of the volume-based particle size distribution is defined as the median particle size.
15. The process of claim 13, wherein the distribution of the size of agglomerated particles in the final product is characterized by a ratio between D90 and D10 of less than or equal to 4, wherein D10 is 10% by volume of the population having a particle size less than the value of D10 and D90 is the particle size wherein 90% by volume of the population is less than the value of D90.
16. The process of claim 14, wherein the distribution of the size of agglomerated particles in the final product is characterized by a ratio between D90 and D10 of less than or equal to 4, wherein D10 is 10% by volume of the population having a particle size less than the value of D10 and D90 is the particle size wherein 90% by volume of the population is less than the value of D90.
17. The method of claim 1 or 2, wherein agglomerated particles in the final product are used as precursors for the preparation of a lithium ion battery cathode material.
CN201780038592.8A 2016-07-20 2017-07-11 Scalable precipitation synthesis method for battery materials with adjustable particle size distribution Active CN109311696B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DKPA201600436 2016-07-20
DKPA201600436 2016-07-20
PCT/EP2017/067388 WO2018015210A1 (en) 2016-07-20 2017-07-11 A method for upscalable precipitation synthesis of battery materials with tunable particle size distribution

Publications (2)

Publication Number Publication Date
CN109311696A CN109311696A (en) 2019-02-05
CN109311696B true CN109311696B (en) 2023-06-02

Family

ID=60992860

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201780038592.8A Active CN109311696B (en) 2016-07-20 2017-07-11 Scalable precipitation synthesis method for battery materials with adjustable particle size distribution

Country Status (3)

Country Link
EP (1) EP3487813A1 (en)
CN (1) CN109311696B (en)
WO (1) WO2018015210A1 (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FI3652754T3 (en) * 2017-07-15 2023-05-04 Microvast Power Systems Co Ltd Method for producing cathode particles
US20220013771A1 (en) 2018-12-19 2022-01-13 Haldor Topsøe A/S Lithium positive electrode active material
JP2022514405A (en) 2018-12-19 2022-02-10 ハルドール・トプサー・アクチエゼルスカベット Lithium positive electrode active material
EP3898525A1 (en) 2018-12-19 2021-10-27 Haldor Topsøe A/S Lithium positive electrode active material
JP7384540B2 (en) * 2019-10-02 2023-11-21 エルジー・ケム・リミテッド Method for producing positive electrode active material precursor for lithium secondary battery
JP7506161B2 (en) * 2019-12-30 2024-06-25 ▲荊▼▲門▼市格林美新材料有限公司 A method for preparing high-nickel ternary precursors with preferential growth of crystal faces regulated and controlled by the amount of added seed crystals
CN111883767B (en) * 2020-07-31 2021-10-29 合肥国轩高科动力能源有限公司 Preparation process of particle high-dispersion nickel-cobalt-manganese ternary precursor
CN112194203A (en) * 2020-10-29 2021-01-08 格林爱科(荆门)新能源材料有限公司 Preparation method of nickel-cobalt oxide material
CN113860394B (en) * 2021-09-30 2023-12-26 中伟新材料股份有限公司 Manganese-rich carbonate binary precursor, preparation method thereof, positive electrode material and lithium battery
CN114180651B (en) * 2021-12-22 2023-10-27 天齐创锂科技(深圳)有限公司 Method for peaking ternary precursor material with wide particle size distribution
CN115650315A (en) * 2022-09-30 2023-01-31 巴斯夫杉杉电池材料有限公司 Manganese-rich oxide precursor and preparation method and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016055910A1 (en) * 2014-10-08 2016-04-14 Umicore Carbonate precursors for lithium nickel manganese cobalt oxide cathode material and the method of making same
WO2016055911A1 (en) * 2014-10-08 2016-04-14 Umicore Impurity containing cathode material with preferred morphology and method to prepare from impurity containing metal carbonate

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103165878B (en) * 2013-03-25 2016-03-30 安徽亚兰德新能源材料股份有限公司 A kind of preparation method of spherical nickel-manganese binary material
CN105377765B (en) * 2013-05-08 2018-01-26 巴斯夫欧洲公司 Spheric granules, it is prepared and purposes
US9446967B2 (en) * 2013-05-14 2016-09-20 Uchicago Argonne, Llc Method for producing size selected particles
CN103682323B (en) * 2013-12-31 2017-02-15 湖南汇通科技有限责任公司 Lithium nickel manganese oxide cathode material, precursor thereof and preparation method thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2016055910A1 (en) * 2014-10-08 2016-04-14 Umicore Carbonate precursors for lithium nickel manganese cobalt oxide cathode material and the method of making same
WO2016055911A1 (en) * 2014-10-08 2016-04-14 Umicore Impurity containing cathode material with preferred morphology and method to prepare from impurity containing metal carbonate

Also Published As

Publication number Publication date
EP3487813A1 (en) 2019-05-29
CN109311696A (en) 2019-02-05
WO2018015210A1 (en) 2018-01-25

Similar Documents

Publication Publication Date Title
CN109311696B (en) Scalable precipitation synthesis method for battery materials with adjustable particle size distribution
Chen et al. A review on cathode materials for advanced lithium ion batteries: microstructure designs and performance regulations
CN109686938B (en) Magnesium ion doped gradient nickel cobalt lithium manganate positive electrode material and preparation method thereof
US10297825B2 (en) Process for producing nickel cobalt aluminum composite hydroxide and process for producing positive electrode active material for non-aqueous electrolyte secondary batteries
CN101426728B (en) Lithium-metal composite oxides and electrochemical device using the same
US9553313B2 (en) 3V class spinel complex oxides as cathode active materials for lithium secondary batteries, method for preparing the same by carbonate coprecipitation, and lithium secondary batteries using the same
KR101313575B1 (en) Manufacturing method of positive active material precursor and lithium metal composite oxides for lithium secondary battery
JP6895105B2 (en) A method for producing nickel-manganese composite hydroxide particles and a method for producing a positive electrode active material for a non-aqueous electrolyte secondary battery.
US11952287B2 (en) Method for the precipitation of particles of a metal carbonate material without use of a chelating agent
KR20150115831A (en) Nickel-cobalt composite hydroxide and process for manufacturing same
WO2007094644A1 (en) Preparation method of lithium-metal composite oxides
CN113540436A (en) Tungsten ion doped high nickel gradient ternary positive electrode material and preparation method thereof
KR20120017004A (en) Positive electrode materials combining high safety and high power in a li rechargeable battery
CN107567666A (en) Anode active material and the secondary cell for including it
WO2012020769A1 (en) Method for producing nickel-containing complex compound
CN109879333B (en) Method for preparing lithium battery anode material with core-shell structure by secondary molten salt method
WO2010139142A1 (en) Positive electrode materials of secondary lithium battery and preparation methods thereof
KR101375704B1 (en) Precursor of cathode active material for lithium secondary battery and preparation method thereof
CN113614954A (en) High-power lithium ion battery anode material
WO2018234112A1 (en) Beta-nickel hydroxide doped with aluminum
KR100668051B1 (en) Manganese Oxides by co-precipitation method, Spinel type cathode active material for lithium secondary batteries using thereby and Preparation of the same
JP7273260B2 (en) Positive electrode active material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery
KR100668050B1 (en) Manganese Oxides, Spinel type cathode active material for lithium secondary batteries using thereby and Preparation of the same
CN115650318A (en) Doped P2 type layered sodium nickel manganese oxide cathode material and preparation method thereof
JP2018181836A (en) Method of preparing positive electrode active material precursor for secondary battery

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant
TR01 Transfer of patent right
TR01 Transfer of patent right

Effective date of registration: 20240417

Address after: Denmark than the city of Denmark

Patentee after: Topso Battery Materials Co.,Ltd.

Country or region after: Denmark

Address before: Denmark than the city of Denmark

Patentee before: HALDOR TOPSOE A/S

Country or region before: Denmark