CN106571464A - Ni-Co-Al-Mg composite hydroxide, preparation method and application thereof - Google Patents

Ni-Co-Al-Mg composite hydroxide, preparation method and application thereof Download PDF

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Publication number
CN106571464A
CN106571464A CN201610937959.7A CN201610937959A CN106571464A CN 106571464 A CN106571464 A CN 106571464A CN 201610937959 A CN201610937959 A CN 201610937959A CN 106571464 A CN106571464 A CN 106571464A
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nickel cobalt
nickel
magnalium
aluminium
complex hydroxide
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许开华
李军秀
张云河
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Jingmen GEM New Material Co Ltd
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Jingmen GEM New Material Co Ltd
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00Compounds of nickel
    • C01G53/04Oxides; Hydroxides
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of, or comprising, active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/01Particle morphology depicted by an image
    • C01P2004/03Particle morphology depicted by an image obtained by SEM
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/30Particle morphology extending in three dimensions
    • C01P2004/32Spheres
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00Particle morphology
    • C01P2004/60Particles characterised by their size
    • C01P2004/61Micrometer sized, i.e. from 1-100 micrometer
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention provides a preparation method of a Ni-Co-Al-Mg composite hydroxide, wherein the method includes the steps of: performing a reaction to a raw material being a mixed salt solution of nickel, cobalt, aluminum and magnesium with urea as a precipitation and complexation agent in a hydrothermal reaction kettle at 100-180 DEG C for 12-48 h to prepare Ni-Co-Al-Mg composite hydroxide; and washing and drying the Ni-Co-Al-Mg composite hydroxide. By means of the method, aluminum ions can be uniformly co-precipitated with nickel, cobalt and magnesium ions within the same pH range, thus producing the a Ni-Co-Al-Mg precursor having stable ingredient and distribution and used for a lithium ion battery.

Description

A kind of nickel cobalt magnalium complex hydroxide and its preparation method and application
Technical field
The invention belongs to battery material preparing technical field, more particularly to a kind of nickel cobalt magnalium complex hydroxide and its system Preparation Method and application.
Background technology
Lithium-ion-power cell has the superperformance such as high-energy-density, high security, renewable because of it, causes people's Greatly concern.Particularly development of the auto industry in the whole world is popularized, and the development for electric automobile provides wide prospect, so as to Will be that power lithium-ion battery positive electrode that it is used and presoma bring great demand.Vehicular dynamic battery material Material will as far as possible being consistent property (as different batches of product element composition difference it is little, the difference such as particle diameter distribution, tap density It is little), the small difference of power battery material can all cause the difference of its performance, be unfavorable for that the later stage constitutes power battery module (mould Block requires the consistency of performance of battery core higher).Because the positive electrode of lithium battery decides the performance of lithium-ion-power cell, This uniformity to lithium ion power battery cathode material proposes high requirement.The performance of the tertiary cathode material of electrokinetic cell It is largely dependent upon presoma.
At present nickel cobalt aluminium tertiary cathode material, is prepared by nickel cobalt aluminium presoma and lithium source sintering process.Before nickel cobalt aluminium Drive body typically to prepare by coprecipitation, because aluminium hydroxide belongs to amphoteric hydroxide, its special precipitability causes it to sink Starch typically exhibits out cotton-shaped pattern, adds aluminium and differs larger with the solubility product of nickel and cobalt ions, cause aluminium can not equably with Nickel cobalt ion forms co-precipitation, reduces the uniformity of nickel cobalt aluminium presoma.Additionally, in order to make lithium ion in positive electrode The ability of diffusion inside strengthens, and can adulterate the elements such as Mg, Ti, Zr in sintering process.But the mode of this solid phase mixing doping Normally result in that doped chemical is distributed in positive electrode is uneven, and this will also affect the uniformity of positive electrode.
Therefore, it is necessary to provide preferable positive electrode of a kind of homogeneity of product and preparation method thereof.
The content of the invention
In consideration of it, the invention provides a kind of technique of employing hydro-thermal method preparation nickel cobalt magnalium presoma, can make nickel cobalt The content of magnalium element can stability contorting, presoma uniformity is good.
In a first aspect, the invention provides a kind of preparation method of nickel cobalt magnalium complex hydroxide, comprises the following steps:
(1) it is n (Ni according to the molar concentration rate of nickel, cobalt, aluminium, magnesium metal ion2+):n(Co2+):n(Al3+):n(Mg2+) =x:y:z:Nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to w the mixing salt solution of nickel cobalt magnalium, wherein, the salt-mixture is molten The total mol concentration of metal ion is between 1~5mol/L in liquid;
(2) add precipitation and complexation agent, stirring to form mixed solution in the mixing salt solution, the mixed solution is turned In moving to hydrothermal reaction kettle, react 12~48 hours at 100~180 DEG C;Wherein, the mole of the precipitation and complexation agent and institute The ratio for stating the integral molar quantity of metal ion is 5~20:1, the precipitation and complexation agent is urea, acetamide, acrylamide, bicarbonate One or more in ammonium and ammonium carbonate;
(3) after question response terminates, resulting material after reaction is carried out to be filtrated to get solid product, and to the solid product After washing, drying, nickel cobalt magnalium complex hydroxide is obtained.
Preferably, in step (1), the nickel salt includes one or more in nickel chloride, nickel sulfate and nickel nitrate.
Preferably, in step (1), the cobalt salt includes one or more in cobalt chloride, cobaltous sulfate and cobalt nitrate.
Preferably, in step (1), the aluminium salt includes one or more in aluminium chloride, aluminum sulfate and aluminum nitrate.
Preferably, in step (1), the magnesium salts includes one or more in magnesium chloride, magnesium sulfate and magnesium nitrate.
In the application, metal ion (nickel ion, cobalt ions, aluminium ion and magnesium ion) always rubs in the mixing salt solution Your concentration is 0.5~2.5mol/L.Preferably 0.8~1.5mol/L.
In the application, in step (1), nickel, cobalt, aluminium, the mol ratio of magnesium ion are x in the mixing salt solution:y:z: w。
Preferably, < z≤0.05 of 0 < x <, 1,0 < y < 1,0,0 < w≤0.05, x+y+z+w=1.
It is further preferred that < z≤0.05 of 0.7≤x <, 1,0 < y < 0.25,0,0 < w≤0.05.
In the application, the mole of the precipitation and complexation agent is (5~20) with the ratio of the integral molar quantity of the metal ion: 1.Preferably (8~15):1.
In the application, the complex precipitant had both possessed the effect of complexing, but also with precipitation, the precipitation and complexation agent In alkalescence, under its heating condition ammonia is can release.
In the ternary that nickel and cobalt containing aluminium is prepared using coprecipitation and polynary presoma, Al3+Property is special, not with other CO3 2-、C2O4 2-Deng precipitation is formed, Al (OH) is can be only generated3Precipitation, and need strictly to control alkali in precipitation generating process to contain Amount, increased the difficulty of presoma preparation;On the other hand, due to the sedimentation equilibrium constant and nickel hydroxide, hydrogen-oxygen of aluminium hydroxide Changing cobalt, magnesium hydroxide has larger difference, it is impossible to co-precipitation is realized in the range of same pH, and aluminium hydroxide is both sexes hydroxide Thing, when base excess, aluminium hydroxide dissolving generates meta-aluminate.This is all unfavorable for aluminium element shape in ternary and polynary co-precipitation Into stable composition and distribution.
In the present invention, using one or more in urea, acetamide, acrylamide, ammonium hydrogen carbonate, ammonium carbonate as heavy Shallow lake complexing agent, in sealed reactor, carries out hydrothermal deposition reaction, in heating response mistake with the mixed solution of nickel, cobalt, aluminium, magnesium Cheng Zhong, sealed reactor provides sealing, HTHP reaction environment for the reaction of complex precipitant and metal ion, has Helping each reaction raw materials can fully dissolve and react, reduce chemical reaction potential energy, under this kind of environment, precipitation and complexation agent gradually by Decomposition discharges ammonia;A small amount of ammonia forms complex with complexing of metal ion;With the carrying out of reaction, excessive ammonia hydrolysis life Into NH4 +And hydroxide ion;Hydroxide ion generates precipitate metal hydroxides with metal ion reaction.Because ammoniacal liquor is weak Alkali, aluminium hydroxide is to be slightly soluble in ammoniacal liquor, and the aluminum hydroxide precipitation of generation can not be converted into meta-aluminate.Overcome existing co-precipitation Aluminium content is difficult a difficult problem for stability contorting in technique.Additionally, magnesium elements prepare nickel cobalt aluminium hydroxide during just Doping is entered, and is equably precipitated with nickel cobalt aluminium, overcomes the doping that the magnesium elements that adulterate again in later stage sintering process are brought Uneven problem.Higher (the element composition of uniformity of the nickel cobalt magnalium complex hydroxide, nickel cobalt magnalium composite oxides It is little with distributional difference), be conducive to the conforming raising of nickel cobalt magnalium positive electrode, so as to be conducive to electrokinetic cell monomer uniformity Raising, be conducive to the later stage constitute electrokinetic cell module.
Preferably, the precipitation and complexation agent is urea.
Urea liquid can form uniform solution at room temperature in neutrality with metal ion.The temperature liter of question response system After up to 60 DEG C, urea starts hydrolysis generation carbon dioxide and ammonia, and reaction equation is (NH2)2CO+H2O→ CO2↑+2NH3↑.A small amount of NH3Can be complexed with metal ion.Question response continues, and discharges a large amount of ammonias, hydrothermal system Reaction solution is in alkalescence (pH is 10.0~12.0), NH3With water generating ammoniacal liquor, NH3·H2O→NH4 ++OH-.The hydrogen-oxygen for being generated Root OH-React to form co-precipitation with the metal ion such as nickel, cobalt, aluminium, magnesium.
It is further preferred that the molar concentration of the urea liquid for being added is 5~19mol/L.
Preferably, in step (3), the solid product is washed after being neutral to filtrate pH, then it is dried.
Preferably, step (4) is also included after the step (3):
(4) the nickel cobalt magnalium complex hydroxide is calcined, is obtained nickel cobalt magnalium composite oxides.
Preferably, in step (4), the calcining is to carry out at 300~650 DEG C 2~8 hours, in the calcination process Heating rate be 5~25 DEG C/min.The nickel cobalt magnalium composite oxides that calcining is obtained, as lithium-ion-power cell nickel cobalt Aluminium presoma.
Second aspect, the invention provides a kind of nickel cobalt magnalium complex hydroxide, the nickel cobalt magnalium is combined hydroxide Thing is that the method by described in first aspect present invention is prepared.
The structural formula of the nickel cobalt magnalium complex hydroxide is NixCoyAlzMgw(OH)z+2, wherein the < y of 0 < x < 1,0 < z≤0.05 of < 1,0,0 < w≤0.05, x+y+z+w=1.
Preferably, 0.7≤x < 1,0 < y < 0.25,0 < z≤0.05,0 < w≤0.05.
The third aspect, present invention also offers a kind of nickel cobalt magnalium composite oxides, the nickel cobalt magnalium composite oxides Method by described in first aspect present invention is prepared.
Preferably, the molecular formula of the nickel cobalt magnalium composite oxides is NixCoyAlzMgwO0.5z+1, wherein 0 < x < 1,0 < z≤0.05 of < y < 1,0,0 < w≤0.05, and x+y+z+w=1.
It is further preferred that < z≤0.05 of 0.7≤x <, 1,0 < y < 0.25,0,0 < w≤0.05.
Preferably, the nickel cobalt magnalium composite oxides are regular spherical, and its apparent density is 0.6-1.6g/cm3, jolt ramming Density is 1.0-2.4g/cm3, average grain diameter is at 3.0-12.5 μm.
The present invention has the advantages that:
The method process is simple that the present invention is provided, controllability is high, and can control aluminium ion can be with nickel, cobalt, magnesium ion same Realize equably being co-precipitated in the range of pH, advantageously form uniform particle sizes, morphology controllable, metallic element composition and be distributed stable Nickel cobalt magnalium presoma.Overcome in prior art coprecipitation and prepare aluminium content in nickel cobalt aluminium presoma and be difficult stability contorting, The uppity problem of product pattern.Additionally, the present invention is doped with magnesium elements in ternary nickel cobalt aluminium presoma is prepared, it is this Adulterate first in presoma the mode of magnesium elements, overcome and directly mix magnesium source with presoma, lithium source in later stage sintering process The solid-phase sintering mode of conjunction, magnesium elements are distributed more uniform in positive electrode.Nickel cobalt magnalium forerunner's bodily form that the present invention is obtained Looks are controllable, narrow diameter distribution, uniformity are good, the content of four kinds of metallic elements can by stability contorting and different batches of product unit Cellulose content difference is little, can be used for preparing lithium-ion-power cell module.
Advantages of the present invention will be illustrated partly in the following description, and a part is apparent according to specification , or can be known by the enforcement of the embodiment of the present invention.
Description of the drawings
Fig. 1 is the preparation method flow chart of nickel cobalt magnalium composite oxides in the embodiment of the present invention;
Fig. 2 is the stereoscan photograph of obtained nickel cobalt magnalium complex hydroxide in the embodiment of the present invention 1.
Specific embodiment
Described below is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as Protection scope of the present invention.
Fig. 1 is refer to, Fig. 1 is the preparation method flow chart of nickel cobalt magnalium composite oxides during the present invention one is implemented, including Following steps:
S101, according to nickel, cobalt, aluminium, magnesium metal ion molar concentration rate be n (Ni2+):n(Co2+):n(Al3+):n(Mg2 +)=x:y:z:Nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to w the mixing salt solution of nickel cobalt magnalium;
S102, the addition precipitation and complexation agent in the mixing salt solution, stirring forms mixed solution, by the mixed solution In being transferred to hydrothermal reaction kettle, react 12~48 hours at 100~180 DEG C;Wherein, the precipitation and complexation agent is urea, second One or more in acid amides, acrylamide, ammonium carbonate and ammonium hydrogen carbonate;
After S103, question response terminate, resulting material after reaction is carried out to be filtrated to get solid product, and the solid is produced Thing obtains nickel cobalt magnalium complex hydroxide after washing, drying;
S104, the nickel cobalt magnalium complex hydroxide is calcined, obtained nickel cobalt magnalium composite oxides.
Multiple embodiments are divided to be further detailed the embodiment of the present invention below.The embodiment of the present invention be not limited to Under specific embodiment.In the range of constant principal right, can be appropriate carry out change enforcement.
Embodiment 1
A kind of preparation method of nickel cobalt magnalium composite oxides, comprises the following steps:
Molar concentration rate according to nickel, cobalt, aluminium, magnesium metal ion is n (Ni2+):n(Co2+):n(Al3+):n(Mg2+)= 0.7:0.2:0.05:0.05, nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to into certain density nickel cobalt magnalium mixing salt solution, institute The total mol concentration for stating metal ion in mixing salt solution is 1mol/L;
The urea liquid of 40mL, 10mol/L is prepared, itself and the above-mentioned mixing salt solution of 40mL are stirred to form uniform mixed Solution is closed, the mixed solution is transferred in ptfe autoclave, reacted 24 hours at 120 DEG C;
After question response terminates, reactor is taken out, after it is cooled to room temperature, resulting material after reaction is filtered, washed Wash, and wash until filtrate pH is neutrality;Obtain nickel cobalt magnalium complex hydroxide;
Above-mentioned nickel cobalt magnalium complex hydroxide calcined at 500 DEG C 3 hours, wherein the heating rate in calcination process For 20 DEG C of min, lithium-ion-power cell nickel cobalt magnalium presoma (nickel cobalt magnalium composite oxides) is obtained.
Repeat the method in the present embodiment 1, prepare the nickel cobalt magnalium complex hydroxide product of tri- batches of A, B, C, point It is other that ICP constituent analyses are carried out to it.According to analysis result, it is known that the corresponding nickel cobalt magnalium complex hydroxide knot of A batch products Structure formula is Ni0.695Co0.203Al0.049Mg0.053(OH)2, the corresponding nickel cobalt magnalium complex hydroxide structural formula of B batch products is Ni0.698Co0.201Al0.049Mg0.052(OH)2, the corresponding nickel cobalt magnalium complex hydroxide structural formula of C batch products is Ni0.703Co0.206Al0.045Mg0.046(OH)2, the metal element content of three batch products is more or less the same, it was demonstrated that hydro-thermal method is certain The good nickel cobalt magnalium complex hydroxide of element composition uniformity can be obtained.
Meanwhile, to same batch A nickel cobalt magnalium complex hydroxide product, take zones of different (as upper strata, lower floor, left side, Right side etc.) three samples E, F, G, respectively ICP constituent analyses are carried out to it, according to analysis result, derive the knot of E, F, G sample Structure formula.Respectively corresponding nickel cobalt magnalium complex hydroxide product structure formula is to be derived by E, F, G institute Ni0.701Co0.200Al0.049Mg0.050(OH)2、Ni0.698Co0.199Al0.051Mg0.052(OH)2、Ni0.697Co0.202Al0.050Mg0.051 (OH)2.It follows that the element composition of same batch zones of different sample is more or less the same.(remove and weighing sample and testing Human error, instrument error in journey)
Electron microscope (SEM) sign is scanned to gained nickel cobalt magnalium complex hydroxide, it can be seen that nickel cobalt aluminium Magnesium complex hydroxide is shaped as regular spherical, and sphericity is higher, and particle diameter is more uniform, average grain diameter is about 3.0 μm.
Meanwhile, equipped with Energy Dispersive X-ray spectrometer (EDX) on SEM equipment, to occurring in ESEM picture in Different spherical compounds, 4 different locis 1,2,3,4 of same spherical compound carry out energy spectrum analysis, gained Ni/Co/ The element proportion of Al/Mg is more or less the same.1st, the Ni/Co/Al/Mg corresponding to 2,3,4 four points is respectively 0.699: 0.200:0.047:0.054;0.698:0.201:0.048:0.053;0.699:0.200:0.047:0.054;0.703: 0.201:0.050:0.046.Further proved the method for offer of the present invention can obtain really element composition uniformity it is good Nickel cobalt magnalium complex hydroxide.
The A batches of the present embodiment 1 are obtained nickel cobalt magnalium complex hydroxide simultaneously carries out calcining the nickel cobalt aluminium for obtaining Magnesium coumpoud oxide A ' carries out ICP constituent analyses, and the structural formula for being as a result nickel cobalt magnalium composite oxides A ' is Ni0.695Co0.202Al0.049Mg0.054O1.0245;Nickel cobalt magnalium composite oxides A's ' is shaped as regular spherical, and sphericity is higher, grain Footpath is more uniform, and average grain diameter is about 2.95 μm.In addition, apparent density is 0.6g/cm3, tap density is 1.1g/cm3
Embodiment 2
A kind of preparation method of nickel cobalt magnalium composite oxides, comprises the following steps:
Molar concentration rate according to nickel, cobalt, aluminium, magnesium metal ion is n (Ni2+):n(Co2+):n(Al3+):n(Mg2+)= 0.75:0.15:0.05:0.05, nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to into certain density nickel cobalt magnalium mixing salt solution, The total mol concentration of metal ion is 1.5mol/L in the mixing salt solution;
The urea liquid of 80mL, 15mol/L is prepared, itself and the above-mentioned mixing salt solution of 80mL are stirred to form uniform mixed Solution is closed, the mixed solution is transferred in ptfe autoclave, reacted 36 hours at 150 DEG C;
After question response terminates, reactor is taken out, after it is cooled to room temperature, resulting material after reaction is filtered, washed Wash, and wash until filtrate pH is neutrality;Obtain nickel cobalt magnalium complex hydroxide;
Above-mentioned nickel cobalt magnalium complex hydroxide calcined at 500 DEG C 3 hours, wherein the heating rate in calcination process For 10 DEG C of min, lithium-ion-power cell nickel cobalt magnalium presoma (nickel cobalt magnalium composite oxides) is obtained.
Embodiment 3
A kind of preparation method of nickel cobalt magnalium composite oxides, comprises the following steps:
Molar concentration rate according to nickel, cobalt, aluminium, magnesium metal ion is n (Ni2+):n(Co2+):n(Al3+):n(Mg2+)= 0.7:0.2:0.05:0.05, nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to into certain density nickel cobalt magnalium mixing salt solution, institute The total mol concentration for stating metal ion in mixing salt solution is 1mol/L;
The urea liquid of 100mL, 12mol/L is prepared, itself and the above-mentioned mixing salt solution of 80mL are stirred to form uniform Mixed solution, the mixed solution is transferred in ptfe autoclave, is reacted 24 hours at 120 DEG C;
After question response terminates, reactor is taken out, after it is cooled to room temperature, resulting material after reaction is filtered, washed Wash, and wash until filtrate pH is neutrality;Obtain nickel cobalt magnalium complex hydroxide;
Above-mentioned nickel cobalt magnalium complex hydroxide calcined at 450 DEG C 4 hours, wherein the heating rate in calcination process For 20 DEG C of min, lithium-ion-power cell nickel cobalt magnalium presoma (nickel cobalt magnalium composite oxides) is obtained.
Embodiment 4
A kind of preparation method of nickel cobalt magnalium composite oxides, comprises the following steps:
Molar concentration rate according to nickel, cobalt, aluminium, magnesium metal ion is n (Ni2+):n(Co2+):n(Al3+):n(Mg2+)= 0.8:0.15:0.03:0.02, nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to into certain density nickel cobalt magnalium mixing salt solution, institute The total mol concentration for stating metal ion in mixing salt solution is 1mol/L;
The urea liquid of 40mL, 15mol/L is prepared, itself and the above-mentioned mixing salt solution of 40mL are stirred to form uniform mixed Solution is closed, the mixed solution is transferred in ptfe autoclave, reacted 24 hours at 150 DEG C;
After question response terminates, reactor is taken out, after it is cooled to room temperature, resulting material after reaction is filtered, washed Wash, and wash until filtrate pH is neutrality;Obtain nickel cobalt magnalium complex hydroxide;
Above-mentioned nickel cobalt magnalium complex hydroxide calcined at 600 DEG C 2 hours, wherein the heating rate in calcination process For 15 DEG C of min, lithium-ion-power cell nickel cobalt magnalium presoma (nickel cobalt magnalium composite oxides) is obtained.
The above is the preferred embodiment of the present invention, it is noted that for those skilled in the art For, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications are also considered as Protection scope of the present invention.

Claims (10)

1. a kind of preparation method of nickel cobalt magnalium complex hydroxide, it is characterised in that comprise the following steps:
(1) it is n (Ni according to the molar concentration rate of nickel, cobalt, aluminium, magnesium metal ion2+):n(Co2+):n(Al3+):n(Mg2+)=x: y:z:Nickel salt, cobalt salt, aluminium salt, magnesium salts are configured to w the mixing salt solution of nickel cobalt magnalium;
(2) precipitation and complexation agent, stirring is added to form mixed solution, the mixed solution is transferred to in the mixing salt solution In hydrothermal reaction kettle, react 12~48 hours at 100~180 DEG C;Wherein, the precipitation and complexation agent be urea, acetamide, third One or more in acrylamide, ammonium carbonate and ammonium hydrogen carbonate;
(3) after question response terminates, resulting material after reaction is carried out to be filtrated to get solid product, and the solid product is passed through After washing, drying, nickel cobalt magnalium complex hydroxide is obtained.
2. the preparation method described in claim 1, it is characterised in that the mole of the precipitation and complexation agent and the metal ion Integral molar quantity ratio be (5~20):1.
3. the preparation method described in claim 1, it is characterised in that the precipitation and complexation agent is urea.
4. the preparation method described in claim 1, it is characterised in that the total mol concentration of metal ion in the mixing salt solution Between 1~5mol/L.
5. the preparation method described in claim 1, it is characterised in that the structural formula of the nickel cobalt magnalium complex hydroxide is NixCoyAlzMgw(OH)z+2, wherein < z≤0.05 of 0 < x <, 1,0 < y < 1,0,0 < w≤0.05, x+y+z+w=1.
6. the preparation method described in claim 5, it is characterised in that the span of the x, y, z and w is as follows:0.7≤x < < z≤0.05 of 1,0 < y < 0.25,0,0 < w≤0.05.
7. the preparation method described in any one of claim 1-6, it is characterised in that methods described further comprising the steps of (4):
(4) the nickel cobalt magnalium complex hydroxide is calcined, is obtained nickel cobalt magnalium composite oxides.
8. the preparation method described in claim 7, it is characterised in that in step (4), the calcining is entered at 300~650 DEG C Row 2~8 hours, the heating rate in the calcination process is 5~25 DEG C/min.
9. nickel cobalt magnalium complex hydroxide obtained in the method as described in any one of claim 1-6.
10. nickel cobalt magnalium composite oxides obtained in method as claimed in claim 8.
CN201610937959.7A 2016-10-25 2016-10-25 Ni-Co-Al-Mg composite hydroxide, preparation method and application thereof Pending CN106571464A (en)

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CN107913665A (en) * 2017-11-29 2018-04-17 中南大学 A kind of metal-doped boehmite and its preparation method and application
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CN111498910A (en) * 2020-05-26 2020-08-07 宜宾天原海丰和泰有限公司 Resource utilization method of chlorination waste residue
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