CN106029575B - Utilize the continuous preparation method of the nickel cobalt manganese composite precursor of Couette Taylor's reactor - Google Patents

Utilize the continuous preparation method of the nickel cobalt manganese composite precursor of Couette Taylor's reactor Download PDF

Info

Publication number
CN106029575B
CN106029575B CN201480075219.6A CN201480075219A CN106029575B CN 106029575 B CN106029575 B CN 106029575B CN 201480075219 A CN201480075219 A CN 201480075219A CN 106029575 B CN106029575 B CN 106029575B
Authority
CN
China
Prior art keywords
reactor
presoma
couette
taylor
precipitation
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
CN201480075219.6A
Other languages
Chinese (zh)
Other versions
CN106029575A (en
Inventor
权纯谟
权五祥
文畅晙
姜东玖
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.)
E&d CO Ltd
Original Assignee
E&d CO Ltd
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 E&d CO Ltd filed Critical E&d CO Ltd
Publication of CN106029575A publication Critical patent/CN106029575A/en
Application granted granted Critical
Publication of CN106029575B publication Critical patent/CN106029575B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/18—Stationary reactors having moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G51/00—Compounds of cobalt
    • 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
    • H01M4/139—Processes of manufacture
    • H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • 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
    • 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
    • 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

Abstract

The present invention is the nickel cobalt manganese composite precursor Ni for being related to a kind of mixed in nickel secondary batteries with lithium and being used as positive active materialxCoyMn1‑x‑y(OH)2Continuous preparation method technology, in particular, being co-precipitated to prepare Ni by first time of Couette Taylor's reactorxCoyMn1‑x‑y(OH)2Presoma seed crystal, and launch in the batch reactor with overflow the presoma seed crystal and metal co-precipitation liquid and pass through second of co-precipitation and can finally prepare uniformly and sphericity and crystallinity is high, size is about 3~4 μm NixCoyMn1‑x‑y(OH)2Presoma.

Description

It is prepared using the continous way of the nickel cobalt manganese composite precursor of Couette Taylor's reactor Method
Technical field
It is used as the nickel-cobalt-of positive active material the present invention relates to a kind of mixed in the lithium secondary battery with lithium Manganese composite precursor NixCoyMn1-x-y(OH)2Preparation method, in particular, Couette Taylor's reactor can be utilized by being related to one kind The dual structure of (couette taylor reactor) and batch reactor and by be co-precipitated twice prepare uniformly and The high small particle Ni of sphericityxCoyMn1-x-y(OH)2The technology of presoma.
Background technology
With the universal and diffusion of portable small-sized electric appliance and electronic equipment, Ni-MH battery or lithium secondary battery etc. novel two The exploitation of primary cell just actively carries out.Wherein, lithium secondary battery is that the carbon such as graphite are used as negative electrode active material, will contain lithium Metal oxide is used as positive active material, and nonaqueous solvents is used as to the battery of electrolyte.Lithium is the big metal of ionization tendency, It can realize high voltage, therefore, be attracted attention in the high field of batteries of energy density.
The lithium transition-metal oxide containing lithium is mainly used for the positive active material of lithium secondary battery, more than 90% Use the layered lithium transition metals composite oxides such as cobalt system/nickel system/ternary system (cobalt, nickel and manganese coexist).
For example, to Li2CO3And NixCoyMn1-x-y(OH)2It is that presoma carries out mixed calcining processing and as positive electrode. This NixCoyMn1-x-y(OH)2The particle size and specific surface area of presoma are to electric vehicle (HEV, PHEV, EV) with medium-and-large-sized The high-power realization of lithium battery generates big influence.NixCoyMn1-x-y(OH)2The particle of positive electrode is smaller, and specific surface area is got over Increase, the diffusion length of lithium ion is with regard to smaller, therefore, lithium ion is made smoothly and promptly to spread and come in and go out, excellent so as to show Battery behavior, therefore, in order to increase specific surface area to the maximum extent, it is necessary to presoma carry out quenching hardening.
Under normal circumstances, NixCoyMn1-x-y(OH)2Presoma is prepared using coprecipitation, that is, by nickel salt, manganese salt and Then salt solubility is thrown to instead together in distilled water with ammonia spirit (chelating agent), NaOH aqueous solutions (alkaline aqueous solution) It answers in device, so as to synthesize NixCoyMn1-x-y(OH)2After precipitate.
In addition, this coprecipitation mainly uses common batch reactor (batch type), still, by existing The discontinuous coprecipitation using batch reactor easily prepare the presoma of uniform grading, but due to discontinuous Characteristic, there are production capacity in terms of limitation.Certainly, continous way is realized by overflow in batch reactor, but this In the case of, can large-sized presoma be prepared by adjusting reaction time (residence time), still, however, it is difficult to by The continous way mode of the overflow of formula of having a rest reactor prepares the presoma of the small particle of 3~5 μm of sizes.
Another example of continous way mode is, is disclosed in registered patent the 10-1275845th and utilizes Couette Taylor The positive active material for lithium secondary battery presoma preparation facilities the relevant technologies of reactor (with reference to Fig. 1).With intermittent anti- It answers and presoma is continuously prepared by overflow manner in device compares, Couette Taylor reactor as described above can be in the short time Small particle presoma is inside easily prepared, still, prepared small particle presoma is noncrystalline state, and sphericity reduces, therefore, when When being mixed with lithium and calcining and be used as positive electrode, electric characteristic is not so good.
Invention content
(1) technical problems to be solved
Ni is prepared by continuous processing the purpose of the present invention is to provide one kindxCoyMn1-x-y(OH)2The method of presoma, In particular, the purpose of the present invention is to provide a kind of NixCoyMn1-x-y(OH)2The preparation method of presoma, the NixCoyMn1-x-y (OH)2Presoma had both kept uniform spherical form (morphology), and passed through in batch reactor with existing Ni prepared by coprecipitationxCoyMn1-x-y(OH)2Presoma is compared, prepared NixCoyMn1-x-y(OH)2The grain of presoma Son is small and uniform.
(2) technical solution
To achieve the above object, the present invention provides following method.
A kind of Ni using Couette Taylor's reactor is providedxCoyMn1-x-y(OH)2Continuous preparation method, including： First co-precipitation step (1) launches the co-precipitation liquid containing nickel, cobalt and manganese in Couette Taylor's reactor and passes through co-precipitation Method prepares NixCoyMn1-x-y(OH)2Presoma seed crystal, wherein, 0<x<1,0<y<1,0<x+y<1；Second co-precipitation step (2), The Ni that will be discharged from Couette Taylor's reactor of the step (1)xCoyMn1-x-y(OH)2Presoma seed crystal and contain nickel, cobalt And the co-precipitation liquid of manganese is continuously fed into batch reactor together, and is passed through coprecipitation and prepared NixCoyMn1-x-y(OH)2； And separating step (3), by the coprecipitated of overflow (overflow) from the batch reactor of second co-precipitation step (2) Solid-like Ni is detached in the liquid of shallow lakexCoyMn1-x-y(OH)2。
Especially, it is preferable that by being adjusted to process conditions so that prepared in the step (1) NixCoyMn1-x-y(OH)2Particle size for 1~2 μm, the Ni that is prepared in the step (2)xCoyMn1-x-y(OH)2Particle Size is 3~5 μm.
Especially, it is preferable that the process conditions are the time being detained in temperature or reactor.
Especially, it is preferable that the co-precipitation liquid of the step (1) and step (2) includes nickel sulfate, cobaltous sulfate and manganese sulfate.
Especially, it is preferable that the co-precipitation liquid of the step (1) also includes ammonia and sodium hydroxide.
(3) advantageous effect
The small particle that sphericity is low, crystallinity is low can continuously be prepared by existing Couette Taylor reactor NixCoyMn1-x-y(OH)2Presoma still, as the present invention, passes through Couette Taylor reactor and batch reactor Dual co-precipitation can continuously prepare sphericity and the high small particle Ni of crystallinityxCoyMn1-x-y(OH)2Presoma.
Description of the drawings
Fig. 1 is that explanation utilizes Couette Taylor to react as in the Ebrean Registered Patent the 10-1275845th of the prior art Device prepares the figure of the device of positive active material for lithium secondary battery presoma.
Fig. 2 is the system diagram for being used to implement the method for the present invention.
Fig. 3 a to Fig. 3 d are the figures of the experimental result for the presoma for representing to prepare by embodiment 1,
Fig. 3 a and Fig. 3 b are that the SEM under different multiplying measures photo, and Fig. 3 c are particle size distribution figures,
Fig. 3 d are XRD determining photos.
Fig. 4 a to Fig. 4 d are the figures of the experimental result for the presoma for representing to prepare by embodiment 2,
Fig. 4 a and Fig. 4 b are that the SEM under different multiplying measures photo, and Fig. 4 c are particle size distribution figures,
Fig. 4 d are XRD determining photos.
Fig. 5 a to Fig. 5 c are the experimental results for the positive active material for lithium secondary battery for representing to prepare by embodiment 3 Figure, Fig. 5 a and Fig. 5 b are that the different SEM of multiplying power measures photo, and Fig. 5 c are the figures for representing charging and discharging test result.
Specific embodiment
In the following, the present invention will be described, in the following description, " presoma " represents NixCoyMn1-x-y(OH)2Presoma, Wherein, 0<x<1,0<y<1,0<x+y<1.
The present invention provides a kind of Ni using Couette Taylor's reactorxCoyMn1-x-y(OH)2Continuous preparation method, This method includes：First co-precipitation step (1) launches the co-precipitation liquid containing nickel, cobalt and manganese in Couette Taylor's reactor And Ni is prepared by coprecipitationxCoyMn1-x-y(OH)2(wherein, 0<x<1,0<y<1,0<x+y<1) presoma seed crystal；Second Co-precipitation step (2), the Ni that will be discharged from Couette Taylor's reactor of the step (1)xCoyMn1-x-y(OH)2Presoma Seed crystal and co-precipitation liquid containing nickel, cobalt and manganese are continuously fed into batch reactor together, and are passed through coprecipitation and prepared NixCoyMn1-x-y(OH)2；And separating step (3), it is overflow in the batch reactor from second co-precipitation step (2) Flow separation solid-like Ni in the co-precipitation liquid of (overflow)xCoyMn1-x-y(OH)2。
The present invention provides one kind and prepares Ni by continuous processxCoyMn1-x-y(OH)2The method of presoma, feature It is, provides a kind of co-precipitation by two steps continuously to manufacture NixCoyMn1-x-y(OH)2The method of presoma, wherein, Two steps include：It is co-precipitated, is carried out by Couette Taylor reactor for the first time；Second of co-precipitation, intermittent anti- Answer the Ni that will be prepared in device by first time co-precipitationxCoyMn1-x-y(OH)2Presoma carries out again altogether as seed crystal (seed) Precipitation.Similarly continuously supply is co-precipitated liquid and Ni to batch reactorxCoyMn1-x-y(OH)2Presoma seed crystal, by end reaction Object is expelled to outside by overflow system, so as to which whole system be made to realize continous way.
Each step is illustrated separately below.
Utilize the first co-precipitation step (1) of Couette Taylor's reactor
The present invention manufactures Ni in Couette Taylor's reactorxCoyMn1-x-y(OH)2Presoma seed crystal.Couette Taylor is anti- Answering device, Couette Taylor reactor is well known technology in itself, to this no longer using common Couette Taylor's reactor It is specifically described.
The characteristics of Couette Taylor's reactor is can continuously to prepare Ni in a short timexCoyMn1-x-y(OH)2Presoma seed It is brilliant.Preferably, the Ni prepared in Couette Taylor's reactorxCoyMn1-x-y(OH)2The size of presoma seed crystal is 1~2 μ M, it is highly preferred that the service conditions such as residence time in reactor are adjusted, so that its size is 2 μm or so.
Utilize the second co-precipitation step (2) of batch reactor
By about 2 μm or so of the Ni prepared in first co-precipitation step (1)xCoyMn1-x-y(OH)2Presoma conduct Seed crystal prepares the Ni of bigger from the seed crystal againxCoyMn1-x-y(OH)2Presoma.Certainly, it is co-precipitated by second, not only Increase the size of precursor particle, and improve crystallinity, sphericity and the uniformity.
In second co-precipitation step, the Ni that is prepared in the first co-precipitation stepxCoyMn1-x-y(OH)2Presoma It seed crystal and is thrown to the presoma for including the crushing in the co-precipitation liquid of the nickel of batch reactor, chromium and manganese and is total to Precipitation.In the second co-precipitation step, the Ni that will be prepared in Couette Taylor reactorxCoyMn1-x-y(OH)2Presoma is as seed Crystalline substance, particle will be grown.For example, in the second co-precipitation step (2), it will be 2 μm prepared in the first co-precipitation step (1) big Small presoma seed crystal is prepared into the Ni of 3~4 μm of sizesxCoyMn1-x-y(OH)2Presoma.So that the quilt from batch reactor Overflow and realize continuous processing.The Ni of reaction end is mixed in the co-precipitation liquid of overflowxCoyMn1-x-y(OH)2Presoma and Unreacted co-precipitation liquid, therefore, need to be into the Ni for being about to solid-likexCoyMn1-x-y(OH)2The step of presoma is detached.
NixCoyMn1-x-y(OH)2Presoma separating step (3)
Due to being included the Ni of reaction end in the co-precipitation liquid of overflow from the batch reactorxCoyMn1-x-y (OH)2Presoma needs to carry out only to detach the Ni of solid-likexCoyMn1-x-y(OH)2The process of presoma.This separation can be used Simple precipitation or screening (sieve) etc. are used to detach a variety of methods of solid fraction elementary particle from common liquid.Final system Standby NixCoyMn1-x-y(OH)2The size of presoma can be preferably 3~4 μm of degree.
Presoma prepared by the method for the present invention is by elementary particle, therefore not only large specific surface area, but also sphericity Height, so as to as positive element, show high output characteristics.
[embodiment]
[embodiment 1] first is co-precipitated：Ni is prepared using Couette Taylor reactorxCoyMn1-x-y(OH)2Presoma seed crystal
In the following, prepare NixCoyMn1-x-y(OH)2The Ni of middle x=0.8, y=0.10.8Co0.1Mn0.1(OH)2.Adjusting can be passed through The molar fraction of nickel sulfate, cobaltous sulfate and manganese sulfate prepares the presoma of chemical formula as described above.
By nickel sulfate, cobaltous sulfate and manganese sulfate with 0.8:0.1:0.1 molar fraction is mixed to prepare two concentration The aqueous metal solution of 5L for 2.5M, and by 5~7% NH4The NaOH of OH and 12~15% is mixed to prepare the molten of 5L Liquid.Deionized water (D.I water) is filled in the couette-taylor reactor of 1L and is put forward temperature using temperature holding meanss Up to 50~60 DEG C.
The NH that will be prepared in the reactor with metering pump4OH and NaOH mixed solutions are continuous with 7~9mL/ points (min) It launches, with metering pump by ready aqueous metal solution with 4~7mL/ points (min) and 2L/ points of (min) N2Gas mixing and throw It puts.The stirring rpm of reactor is fixed on 800~900, and connects into the reactant quilt with seed crystal effect prepared using overflow It is thrown in the batch reactor of rear end.
[embodiment 2] second is co-precipitated：Ni is prepared by batch reactorxCoyMn1-x-y(OH)2Presoma
The existing sink reactor is the dual sink reactors of 5L, is provided with baffle (baffle) and blender Common vortex device.Fill the distilled water of 2L in the existing reactor, and using temperature holding meanss come in advance will be warm Degree is improved to 50~60 DEG C.Overflow is also provided with, and stirring rpm is fixed as 800~1000 in the reactor.
It is launched in the state of being kept stirring, it is anti-to fill the slave Couette Taylor of 4L in batch reactor Answer the Ni with seed crystal effect of device overflow0.8Co0.1Mn0.1(OH)2.At the time point for filling 4L, will be prepared using metering pump The aqueous metal solution (nickel sulfate, cobaltous sulfate and the manganese sulfate mixed aqueous solution of 2.5M concentration) of batch reactor is with 7~9mL/ The N of min and 3L/min2It is mixed and is aspirated.Without separately carrying out pH controls.
The Ni of solid-like is only isolated in from the batch reactor by the reactant of overflow0.8Co0.1Mn0.1 (OH)2Presoma, and warm water washing is repeatedly repeated with filter type, then dry 20 in 120 DEG C of thermostatic drier Hour, so as to obtain nickel-cobalt-manganese ternary system presoma.
[embodiment 3] prepares lithium mixed cathode active material
By LiOH and the Ni prepared in the embodiment 20.8Co0.1Mn0.1(OH)2It is small that presoma calcines 20 at 800 DEG C When, so as to prepare chemical formula as Li [Ni0.8Co0.1Mn0.1]O2Lithium mixed cathode active material.
[experimental example]
Following experiment is carried out to each result object prepared in embodiment 1 to embodiment 3.
Ni after the first co-precipitation that [experimental example 1] is prepared in Couette Taylor's reactor0.8Co0.1Mn0.1(OH)2Before Drive the experiment of the physical property of body
Fig. 3 a and Fig. 3 b are Ni being prepared by embodiment 1, being prepared in Couette Taylor's reactor0.8Co0.1Mn0.1 (OH)2SEM under the different multiplying of presoma measures photo.As shown in the SEM photograph of Fig. 3 a and Fig. 3 b, first can be identified through It is co-precipitated the Ni prepared0.8Co0.1Mn0.1(OH)2Sphericity it is not so good.Fig. 3 c are the Ni prepared by embodiment 10.8Co0.1Mn0.1 (OH)2The particle size distribution figure of presoma, it is 1.953 μm that can confirm middle size.
Fig. 3 d are the Ni prepared by embodiment 10.8Co0.1Mn0.1(OH)2The XRD determining photo of presoma, peak value is not Significantly, the spike width of measure is wider (broad), from XRD results it has been confirmed that by Couette Taylor's reactor first It is co-precipitated the Ni prepared0.8Co0.1Mn0.1(OH)2Presoma is noncrystalline state (amophous).
It can confirm from the result of Fig. 3 a to Fig. 3 c, the sphericity of presoma prepared in Couette Taylor's reactor It is low, and be prepared to amorphous state, it is unsuitable to use as a positive electrode active material.
Ni after the second co-precipitation that [experimental example 2] is prepared in batch reactor0.8Co0.1Mn0.1(OH)2Presoma Physical property experiment
Fig. 4 a and Fig. 4 b are the Ni prepared by embodiment 20.8Co0.1Mn0.1(OH)2SEM under the different multiplying of presoma Measure photo.As shown in figures 4 a and 4b, it confirms, the Ni prepared by the second co-precipitation0.8Co0.1Mn0.1(OH)2Ball Degree is significantly improved.
Fig. 4 c are by being the Ni of the preparation of embodiment 20.8Co0.1Mn0.1(OH)2The particle size distribution figure of presoma, confirms Middle size is 3.735 μm.That is, become the Ni of 1.953 μm of sizes by first time co-precipitation0.8Co0.1Mn0.1(OH)2Presoma Seed crystal is growing into 3.735 μm by second of co-precipitation.
Fig. 4 d are the Ni prepared by embodiment 20.8Co0.1Mn0.1(OH)2The XRD determining photo of presoma, with Fig. 3 d phases Than peak value becomes apparent, this represents Ni prepared by the first co-precipitation by Couette Taylor's reactor0.8Co0.1Mn0.1(OH)2Before Body is driven in the crystallinity raising after the second co-precipitation.
That is, the second co-precipitation, Ni can be identified through0.8Co0.1Mn0.1(OH)2The sphericity and crystallinity of presoma improve, from And it can confirm, the Ni prepared by the dual co-precipitation of the present invention0.8Co0.1Mn0.1(OH)2Presoma, which has, is suitable as anode The structure of active material.
The experiment of the physical property of [experimental example 3] lithium mixed cathode active material
This experimental example 3 is the lithium blended anode element Li [Ni prepared by the embodiment 30.8Co0.1Mn0.1]O2Reality Test result.
Fig. 5 a and Fig. 5 b are that the SEM under different multiplying measures photo, can confirm and be shown generically as Li [Ni0.8Co0.1Mn0.1] O2The shape of positive electrode.Fig. 5 c are to carry out charging and discharging test as a result, can confirm that display is as follows by preparing button cell Electrology characteristic：Delivery efficiency (2C, 0.1C)：0.8374, initial capacity：162.4.
Industrial applicibility
The present invention is used as the material the relevant technologies of the positive electrode of the secondary cell of such as lithium secondary battery.

Claims (4)

1. a kind of Ni using Couette Taylor's reactorxCoyMn1-x-y(OH)2Continuous preparation method, including：
First co-precipitation step (1) is launched the co-precipitation liquid containing nickel, cobalt and manganese in Couette Taylor's reactor and is passed through altogether The precipitation method prepare NixCoyMn1-x-y(OH)2Presoma seed crystal, wherein, 0<x<1,0<y<1,0<x+y<1；
Second co-precipitation step (2), the Ni that will be discharged from Couette Taylor's reactor of the step (1)xCoyMn1-x-y (OH)2Presoma seed crystal and co-precipitation liquid containing nickel, cobalt and manganese are continuously fed into batch reactor together, and are passed through altogether The precipitation method prepare NixCoyMn1-x-y(OH)2；And
Separating step (3) is detached in the co-precipitation liquid from the batch reactor of second co-precipitation step (2) by overflow Solid-like NixCoyMn1-x-y(OH)2,
Wherein by being adjusted to process conditions so that the Ni prepared in the step (1)xCoyMn1-x-y(OH)2Particle Size is 1~2 μm, the Ni prepared in the step (2)xCoyMn1-x-y(OH)2Particle size be 3~5 μm.
2. the Ni according to claim 1 using Couette Taylor's reactorxCoyMn1-x-y(OH)2Continous way preparation side Method, which is characterized in that the process conditions are the time being detained in temperature or reactor.
3. the Ni according to claim 1 using Couette Taylor's reactorxCoyMn1-x-y(OH)2Continous way preparation side Method, which is characterized in that the co-precipitation liquid of the step (1) and step (2) includes nickel sulfate, cobaltous sulfate and manganese sulfate.
4. the Ni according to claim 1 using Couette Taylor's reactorxCoyMn1-x-y(OH)2Continous way preparation side Method, which is characterized in that the co-precipitation liquid of the step (1) also includes ammonia and sodium hydroxide.
CN201480075219.6A 2014-02-13 2014-02-14 Utilize the continuous preparation method of the nickel cobalt manganese composite precursor of Couette Taylor's reactor Active CN106029575B (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
KR1020140016711A KR101564009B1 (en) 2014-02-13 2014-02-13 Continuously preparing method for Ni-Co-Mn composite precursor using Couette-Taylor vortix reactor
KR10-2014-0016711 2014-02-13
PCT/KR2014/001204 WO2015122554A1 (en) 2014-02-13 2014-02-14 Method for continuously preparing nickel cobalt manganese composite precursor using couette-taylor reactor

Publications (2)

Publication Number Publication Date
CN106029575A CN106029575A (en) 2016-10-12
CN106029575B true CN106029575B (en) 2018-06-22

Family

ID=53800285

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201480075219.6A Active CN106029575B (en) 2014-02-13 2014-02-14 Utilize the continuous preparation method of the nickel cobalt manganese composite precursor of Couette Taylor's reactor

Country Status (3)

Country Link
KR (1) KR101564009B1 (en)
CN (1) CN106029575B (en)
WO (1) WO2015122554A1 (en)

Families Citing this family (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2017150756A1 (en) * 2016-03-03 2017-09-08 주식회사 이엔드디 Method for coating hetero atom on nickel-cobalt-manganese composite precursor by using couette-taylor reactor
KR102533157B1 (en) 2016-07-27 2023-05-17 삼성에스디아이 주식회사 Method of fabricating cathode active material of lithum secondary battery
CN106784786B (en) * 2016-12-16 2019-11-15 欣旺达电子股份有限公司 Ternary anode material precursor, synthetic method and lithium ion battery
KR20180112482A (en) 2017-04-04 2018-10-12 주식회사 라미나 Manufacturing method of cathode active material for secondary cell
KR102283095B1 (en) * 2017-11-28 2021-07-29 엑스티씨 뉴 에너지 머티리얼즈(샤먼) 리미티드 Ternary precursor particles and method for preparing the same
CN108031416B (en) * 2017-11-28 2020-03-10 荆门市格林美新材料有限公司 Overflow system for preparing cobalt carbonate
CN109896554A (en) * 2017-12-11 2019-06-18 河南科隆新能源股份有限公司 A kind of multi-element doping type nickel cobalt manganese hydroxide, equipment and preparation method thereof
CN108321426A (en) * 2018-01-22 2018-07-24 北京圣比和科技有限公司 A kind of preparation method and equipment of the nickel manganese cobalt acid lithium material of single-particle pattern
CN110600683B (en) * 2018-06-13 2020-07-31 浙江帕瓦新能源股份有限公司 Preparation method of semi-continuous ternary precursor
KR102256298B1 (en) 2018-06-26 2021-05-26 삼성에스디아이 주식회사 Nickel-based active material precursor for lithium secondary battery, preparing method thereof, nickel-based active material for lithium secondary battery formed thereof, and lithium secondary battery comprising positive electrode including the nickel-based active material
EP3611133A1 (en) 2018-08-14 2020-02-19 Samsung SDI Co., Ltd. Nickel-based active material precursor for lithium secondary battery, preparation method thereof, nickel-based active material for lithium secondary battery formed therefrom, and lithium secondary battery including cathode including the nickel-based active material
KR102069468B1 (en) 2019-04-30 2020-01-22 하임테크(주) Drying device for precursor and drying method Thereof
CN112366308B (en) * 2020-11-11 2021-12-07 江西普瑞美新材料科技有限公司 Method for rapidly synthesizing nickel-cobalt-manganese positive electrode material precursor
CN113603154B (en) * 2021-07-30 2022-08-26 广东佳纳能源科技有限公司 High-voltage nickel-cobalt-manganese ternary precursor and preparation method thereof

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100508255C (en) * 2005-04-01 2009-07-01 Sk能源株式会社 Layered core-shell cathode active materials for lithium secondary batteries, method for preparing thereof and lithium secondary batteries using the same
CN103107325A (en) * 2011-11-11 2013-05-15 Skc株式会社 Cathode active material for a lithium secondary battery containing phosphate fluoride and preparation method thereof
KR20130080565A (en) * 2012-01-05 2013-07-15 한국교통대학교산학협력단 Precursor for cathode active materials for lithiumsecondary battery with core-shell, cathode active materials and lithiumsecondary battery using the same, and preparation method thereof
CN103413926A (en) * 2013-08-31 2013-11-27 张宝 Preparation method of lithium nickel cobalt manganese oxide precursor

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101038232B1 (en) * 2010-06-23 2011-05-31 (주) 라미나 Apparatus for reaction capable of performing batch type and continuous type reaction
KR101275845B1 (en) * 2011-09-21 2013-06-17 에스케이씨 주식회사 Apparatus using couette-taylor vortice reaction equipment for preparing precursor of cathode material for lithium secondary battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100508255C (en) * 2005-04-01 2009-07-01 Sk能源株式会社 Layered core-shell cathode active materials for lithium secondary batteries, method for preparing thereof and lithium secondary batteries using the same
CN103107325A (en) * 2011-11-11 2013-05-15 Skc株式会社 Cathode active material for a lithium secondary battery containing phosphate fluoride and preparation method thereof
KR20130080565A (en) * 2012-01-05 2013-07-15 한국교통대학교산학협력단 Precursor for cathode active materials for lithiumsecondary battery with core-shell, cathode active materials and lithiumsecondary battery using the same, and preparation method thereof
CN103413926A (en) * 2013-08-31 2013-11-27 张宝 Preparation method of lithium nickel cobalt manganese oxide precursor

Also Published As

Publication number Publication date
KR20150095428A (en) 2015-08-21
KR101564009B1 (en) 2015-10-28
WO2015122554A1 (en) 2015-08-20
CN106029575A (en) 2016-10-12

Similar Documents

Publication Publication Date Title
CN106029575B (en) Utilize the continuous preparation method of the nickel cobalt manganese composite precursor of Couette Taylor&#39;s reactor
KR102553596B1 (en) Nickel manganese-containing composite hydroxide and method for producing the same
CN102725232B (en) Nickel-cobalt-manganese complex hydroxide particles and method for producing same, positive electrode active material for nonaqueous electrolyte secondary battery and method for producing same, and nonaqueous electrolyte secondary battery
CN103688396B (en) Anode for nonaqueous secondary cell active material and preparation method thereof and use the non-water system electrolyte secondary battery of this positive active material
US7771877B2 (en) Electrode active material powder with size dependent composition and method to prepare the same
CN107001071B (en) The manufacturing method of nickel cobalt aluminum complex hydroxide and the manufacturing method of non-aqueous electrolyte secondary battery positive active material
CN112151790B (en) High-nickel ternary cathode material precursor, crystal face controllable growth method thereof, ternary cathode material and lithium ion battery
JP5758743B2 (en) Cobalt hydroxide and method for producing the same, and cobalt oxide and method for producing the same
KR102353263B1 (en) Lithium Metal Composite Oxide Powder with Suppressed Outgassing
CN108602689A (en) The cathode active material for secondary battery for preparing the method for cathode active material for secondary battery and thus preparing
CN107021528A (en) The manufacture method and manufacture device of nickel cobalt complex hydroxide
CN104037401B (en) Nickel-cobalt-lithium manganate ternary anode material suitable for application under high voltage
CN104600285B (en) Method for preparing spherical lithium nickel manganese oxide positive pole material
CN103746110A (en) Preparation method of nickel-cobalt-manganese ternary material and anode material for lithium ion battery
CN106660826A (en) Manganese-cobalt compound hydroxide, method for producing same, cathode active material, method for producing same, and non-aqueous electrolyte secondary battery
CN110088950A (en) The method for preparing the cathode material of secondary cell
JP6614202B2 (en) Cathode active material for non-aqueous electrolyte secondary battery and method for producing the same
CN101867039A (en) Method for preparing nano-scale lithium ion battery anode material
KR20090012187A (en) A process for preparing lithium iron phosphorus based composite oxide carbon complex and a process for preparing coprecipitate comprising lithium, iron and phosphorus
CN110863245B (en) Ternary cathode material, preparation method thereof, lithium ion battery and electric automobile
JP2021114407A (en) Mixed powder for all-solid-state lithium-ion battery, mixed paste for all-solid-state lithium-ion battery, electrode, and all-solid-state lithium-ion battery
CN107406274A (en) The manufacture method of lithium-metal composite oxides with Rotating fields
JP4066472B2 (en) Plate-like nickel hydroxide particles, method for producing the same, and method for producing lithium / nickel composite oxide particles using the same as a raw material
CN108025927A (en) The composite oxides of spinel-type nickel containing lithium manganese
CN106660825A (en) Manganese composite hydroxide and method for producing same, positive electrode active material and method for producing same, and nonaqueous electrolyte secondary battery

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant