CN106558695A - A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof - Google Patents

A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof Download PDF

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CN106558695A
CN106558695A CN201610937957.8A CN201610937957A CN106558695A CN 106558695 A CN106558695 A CN 106558695A CN 201610937957 A CN201610937957 A CN 201610937957A CN 106558695 A CN106558695 A CN 106558695A
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nickel
nickel cobalt
aluminum
cobalt
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
    • 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
    • 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
    • H01M4/485Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • 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
    • H01M4/525Selection 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
    • 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 kind of preparation method of nickel cobalt aluminum complex hydroxide, including:(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt is prepared, the mol ratio of nickel, cobalt and aluminum metal ion is x in mixing salt solution:y:(1 x y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;(2) precipitation and complexation agent is added in mixing salt solution, be mixing uniformly to form mixed solution, mixed solution is transferred in hydrothermal reaction kettle, react 12 48 hours at 100 DEG C 180 DEG C;Wherein, precipitation and complexation agent is at least one in carbamide, acetamide, acrylamide, ammonium carbonate and ammonium hydrogen carbonate;(3), after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain nickel cobalt aluminum complex hydroxide.The present invention adopts one step hydro thermal method to prepare nickel cobalt aluminum ternary precursor, and method process is simple, controllability are high, advantageously forms uniform particle sizes, morphology controllable, metallic element composition and is distributed stable nickel cobalt aluminum presoma.

Description

A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof
Technical field
The present invention relates to battery material preparing technical field, and in particular to a kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminum Composite oxides and preparation method thereof.
Background technology
The high-end electric automobile that endurance reaches 300-400 kilometers is proposed using nickel cobalt aluminum cell based on tesla, Domestic enterprise has also started the research to nickel cobalt aluminum tertiary cathode material in succession.
The technique of existing production nickel cobalt aluminum tertiary cathode material mainly includes:(1) nickel cobalt aluminum ternary forerunner is prepared first Body (i.e. nickel cobalt aluminium composite oxide), is then sintered with lithium source;(2) nickel cobalt binary presoma is prepared first, then with lithium Source, silicon source are sintered.In the first technique, nickel cobalt aluminum ternary precursor generally adopts Co deposited synthesis, specifically:With , used as chelating agent, alkali liquor is used as precipitant for ammonia;Or using certain chelating agent first by aluminium salt complexation, then again with nickel salt, cobalt Salt carries out coprecipitation reaction together.But, as aluminium hydroxide belongs to amphoteric hydroxide, the particularity of its precipitation causes aluminum not Can equably be deposited in nickel cobalt aluminium hydroxide, cause three kinds of element ratios of nickel cobalt aluminum to be difficult to stability contorting, this is unfavorable for The very high nickel cobalt aluminum presoma product of commercial production concordance (the elementary composition difference such as different batches of product is little, particle diameter distribution, The differences such as tap density are little).Second technique first prepares nickel cobalt binary presoma using coprecipitation, although nickel cobalt content and ratio Example more accurately can be controlled, but need to seal continuous sintering furnace using pure oxygen atmosphere in follow-up sintering technique, to equipment requirements Height, it is domestic at present to be also unable to reach such equipment requirements.
Therefore, it is necessary to provide preferable nickel cobalt aluminum of a kind of homogeneity of product and preparation method thereof.
The content of the invention
To solve the above problems, the invention provides a kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and Its preparation method.Nickel cobalt aluminum complex hydroxide of the present invention, nickel cobalt aluminium composite oxide homogeneity of product are preferable.
First aspect present invention provides a kind of preparation method of nickel cobalt aluminum complex hydroxide, including:
(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt, nickel, cobalt and aluminum metal in the mixing salt solution are prepared The mol ratio of ion is x:y:(1-x-y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;
(2) precipitation and complexation agent is added in the mixing salt solution, be mixing uniformly to form mixed solution, by the mixing Solution is transferred in hydrothermal reaction kettle, and 12-48 hours are reacted at 100 DEG C -180 DEG C;Wherein, the precipitation and complexation agent is urine At least one in element, acetamide, acrylamide, ammonium carbonate and ammonium hydrogen carbonate;
(3), after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain nickel cobalt aluminum multiple Close hydroxide.
Wherein, the scope of the x is 0.7≤x < 1, and the scope of the y is 0 < y < 0.3.
Wherein, in the mixing salt solution, nickel, the total mol concentration of three metal ion species of cobalt and aluminum are 0.5mol/L- 3mol/L。
Wherein, the mole of the precipitation and complexation agent and the nickel, the cobalt and three metal ion species of the aluminum always rub The ratio of your amount is 5-20:1.
Wherein, the mole of the precipitation and complexation agent and the nickel, the cobalt and three metal ion species of the aluminum always rub The ratio of your amount is 10-15:1.
First aspect present invention prepares the preparation method of nickel cobalt aluminum complex hydroxide, method technique using one step hydro thermal method Simply, controllability is high, and can control aluminium ion can realize equably being co-precipitated in the range of same pH with nickel and cobalt ions, be conducive to Form uniform particle sizes, morphology controllable, metallic element composition and be distributed stable nickel cobalt aluminum complex hydroxide.Solve existing common In sedimentation, aluminium salt is difficult to uniformly be co-precipitated with nickel cobalt metal ion, causes three kinds of element ratios of nickel cobalt aluminum to be difficult to stability contorting Problem.
Second aspect present invention provide a kind of nickel cobalt aluminum complex hydroxide, the nickel cobalt aluminum complex hydroxide be by It is obtained according to the method described in first aspect, the molecular formula of the nickel cobalt aluminum complex hydroxide is NixCoyAl1-x-y(OH)3-x-y, Wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1.
The nickel cobalt aluminum complex hydroxide that second aspect present invention is provided, three element ratio of nickel cobalt aluminum are stable, and product is consistent Property preferably, better crystallinity degree, narrow particle size distribution.
Third aspect present invention provides a kind of preparation method of nickel cobalt aluminium composite oxide, including:
(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt, nickel, cobalt and aluminum metal in the mixing salt solution are prepared The mol ratio of ion is x:y:(1-x-y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;
(2) precipitation and complexation agent is added in the mixing salt solution, be mixing uniformly to form mixed solution, by the mixing Solution is transferred in hydrothermal reaction kettle, and 12-48 hours are reacted at 100 DEG C -180 DEG C;Wherein, the precipitation and complexation agent is urine At least one in element, acetamide, acrylamide, ammonium carbonate and ammonium hydrogen carbonate;
(3), after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain nickel cobalt aluminum multiple Close hydroxide;
(4) the nickel cobalt aluminum complex hydroxide is calcined into 2-8 hours at 300 DEG C -650 DEG C, obtains nickel cobalt aluminum and be combined Oxide.
Wherein, 300 DEG C -650 DEG C are warming up to the heating rate of 5-25 DEG C/min in the calcination process.
The preparation method of the nickel cobalt aluminium composite oxide that third aspect present invention is provided, preparation method are simple, obtained nickel Cobalt aluminum composite oxide homogeneity of product is preferable.
Fourth aspect present invention provides a kind of nickel cobalt aluminium composite oxide, and the nickel cobalt aluminium composite oxide is according to the In terms of three, described method is obtained, and the molecular formula of the nickel cobalt aluminium composite oxide is NixCoyAl1-x-yO1.5-0.5x-0.5y, wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1.
Wherein, the mean diameter of the nickel cobalt aluminium composite oxide is 2.5 μm -4.5 μm, and tap density is 1.1g/cm3- 1.8g/cm3, apparent density is 0.6g/cm3-1.0g/cm3
In the nickel cobalt aluminium composite oxide that fourth aspect present invention is provided, three kinds of element ratios of nickel cobalt aluminum are stable, product one Cause property is preferable, better crystallinity degree, narrow particle size distribution.
To sum up, beneficial effect of the present invention includes the following aspects:
1st, the present invention prepares the preparation method of nickel cobalt aluminum ternary precursor using one step hydro thermal method, and method process is simple can Control property is high, and can control aluminium ion can realize equably being co-precipitated in the range of same pH with nickel and cobalt ions, advantageously form particle diameter Uniformly, morphology controllable, the metallic element composition nickel cobalt aluminum presoma stable with distribution;
2nd, in the nickel cobalt aluminum complex hydroxide and nickel cobalt aluminium composite oxide that the present invention is provided, three kinds of element ratios of nickel cobalt aluminum Example is stable, and homogeneity of product is preferable, better crystallinity degree, narrow particle size distribution.
Description of the drawings
Fig. 1 is the preparation method flow chart of nickel cobalt aluminum complex hydroxide in an embodiment of the present invention;
Fig. 2 is the preparation method flow chart of nickel cobalt aluminium composite oxide in an embodiment of the present invention;
Fig. 3 is the scanning electron microscope (SEM) photograph of obtained nickel cobalt aluminum complex hydroxide in the embodiment of the present invention 1.
Fig. 4 is X-ray energy spectrum (EDXA) figure of obtained nickel cobalt aluminium composite oxide 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.
With reference to Fig. 1, Fig. 1 is the preparation method flow chart of nickel cobalt aluminum complex hydroxide in an embodiment of the present invention;The On the one hand, the invention provides a kind of preparation method of nickel cobalt aluminum complex hydroxide, including:
(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt, nickel, cobalt and aluminum metal ion in mixing salt solution are prepared Mol ratio be x:y:(1-x-y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;
(2) precipitation and complexation agent is added in mixing salt solution, be mixing uniformly to form mixed solution, mixed solution is shifted Into hydrothermal reaction kettle, 12-48 hours are reacted at 100-180 DEG C;Wherein, precipitation and complexation agent is carbamide, acetamide, acryloyl At least one in amine, ammonium carbonate and ammonium hydrogen carbonate;
(3), after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain nickel cobalt aluminium lamination Shape complex hydroxide.
In the present invention, in step (1), nickel salt includes at least one in Nickel dichloride., nickel sulfate and nickel nitrate.
In the present invention, in step (1), cobalt salt includes at least one in cobaltous chloride, cobaltous sulfate and cobalt nitrate.
In the present invention, in step (1), aluminium salt includes at least one in aluminum chloride, aluminum sulfate and aluminum nitrate.
In the present invention, in step (1), in mixing salt solution, nickel, the total mol concentration of three metal ion species of cobalt and aluminum are 0.5mol/L-3mol/L。
In the present invention, in step (1), in mixing salt solution, nickel, the total mol concentration of three metal ion species of cobalt and aluminum are 0.5mol/L-1.5mol/L。
In the present invention, in step (1), in mixing salt solution, the mol ratio of nickel, cobalt and aluminum metal ion is n (Ni2+):n (Co2+):n(Al3+)=x:y:(1-x-y), the scope of x is 0.7≤x < 1, and the scope of y is 0 < y < 0.3.
In the present invention, in step (1), in mixing salt solution, the mol ratio of nickel, cobalt and aluminum metal ion is n (Ni2+):n (Co2+):n(Al3+)=0.7:0.2:0.1.
In the present invention, in step (1), in mixing salt solution, the mol ratio of nickel, cobalt and aluminum metal ion is n (Ni2+):n (Co2+):n(Al3+)=0.8:0.15:0.05.
In the present invention, in step (1), in mixing salt solution, the mol ratio of nickel, cobalt and aluminum metal ion is n (Ni2+):n (Co2+):n(Al3+)=0.85:0.1:0.05.
In the present invention, in step (2), compactedness of the mixed solution in hydrothermal reaction kettle is 70%-85%.
In the present invention, in step (2), in course of reaction, the pressure of hydrothermal reaction kettle is 2MPa-4.5MPa.
In the present invention, in step (2), hydrothermal reaction kettle temperature is made to rise to 100 DEG C -180 DEG C using the method for microwave heating. Using the method for microwave heating, homogeneous heating, can effectively accelerate reaction rate.
In the present invention, in step (2), mole and nickel, the total moles of three metal ion species of cobalt and aluminum of precipitation and complexation agent The ratio of amount is 5-20:1.
In the present invention, in step (2), mole and nickel, the total moles of three metal ion species of cobalt and aluminum of precipitation and complexation agent The ratio of amount is 10-15:1.
In the present invention, precipitation and complexation agent had both possessed the effect of complexation, but also with precipitation.
Prior art when the ternary precursor of nickel and cobalt containing aluminum is prepared using coprecipitation, due to Al3+Property is special, not with Other CO3 2-、C2O4 2-Deng precipitation is formed, Al (OH) is can be only generated3Precipitation, in precipitation generating process needs strictly to control alkali 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 has larger difference, it is impossible to co-precipitation is realized in the range of same pH, and aluminium hydroxide is amphoteric hydroxide, when alkali mistake During amount, aluminium hydroxide dissolving generates meta-aluminate.This be all unfavorable for aluminium element ternary co-precipitation in formed stable composition with Distribution.
In the present invention, using at least one in carbamide, acetamide, acrylamide, ammonium hydrogen carbonate, ammonium carbonate as precipitation Chelating agent, in sealed reactor, carries out hydro-thermal reaction with the mixed solution of nickel, cobalt, aluminum, during reacting by heating, sealing Reactor provides sealing, High Temperature High Pressure reaction environment with the reaction of metal ion for complex precipitant, contributes to each anti- Answer raw material fully dissolve and react, reduce chemical reaction potential energy, under this kind of environment, precipitation and complexation agent is gradually decomposed release Go out ammonia;A small amount of ammonia forms coordination compound with complexing of metal ion;With the carrying out of reaction, excessive ammonia hydrolysis generates NH4 +With Hydroxide ion;Hydroxide ion generates precipitate metal hydroxides with metal ion reaction.As ammonia is weak base, hydroxide Aluminum is to be slightly soluble in ammonia, and the aluminum hydroxide precipitation of generation can not be converted into meta-aluminate.Overcome aluminum in existing coprecipitation technology Content is difficult a difficult problem for stability contorting.The nickel cobalt aluminum complex hydroxide of gained, the concordance of nickel cobalt aluminium composite oxide are higher (elementary composition and distributional difference is little).
In the present invention, precipitation and complexation agent is carbamide.
Urea liquid can form uniform solution with metal ion at room temperature in neutrality.The temperature liter of question response system After up to 60 DEG C, carbamide starts hydrolysis generation carbon dioxide and ammonia, and reaction equation is (NH2)2CO+H2O→ CO2↑+2NH3↑.A small amount of NH3Complexation can occur with metal ion.Question response continues, and discharges a large amount of ammonias, hydrothermal system Reaction solution is in alkaline (pH is 10.0-12.0), NH3With water generating ammonia, NH3·H2O→NH4 ++OH-.The hydroxyl for being generated OH-React to form co-precipitation with the metal ion such as nickel, cobalt, aluminum.
In the present invention, in step (2), reaction temperature is 120 DEG C -150 DEG C.
In the present invention, in step (3), to resulting material solid-liquid separation after reaction after, obtain solid product, to solid product Washed, until filtrate pH is neutrality.
In the present invention, in step (3), the concrete operations of solid-liquid separation are filtration.
Additionally, when prior art adopts coprecipitation, due to Al3+Introducing, easily form colloid or wadded a quilt with cotton by superfine nano Grain is reunited and forms flocculent deposit, and this has had a strong impact on the degree of crystallinity of material, so as to reduce the physical and chemical performance of material.Meanwhile, altogether The sedimentation method can also produce the shortcoming of broad particle distribution.This is because in coprecipitation process, metal ion is reacted with alkaline solution, Reaction condition easily produces little particle when fluctuating, while the size particles time of staying in a kettle. is inconsistent, little particle is stopped Stay the time shorter, and the bulky grain time of staying is longer, causes little particle to increase, bulky grain continues to grow up, the nickel cobalt for finally giving Aluminum complex hydroxide broad particle distribution.
In the present invention, hydro-thermal method provides relatively-high temperature, a reaction environment for high pressure so that reactant is fully molten Solve, react, the nucleation and crystallization under conditions of stable, so as to reach the effect for improving substance crystallization degree.Under hydrothermal conditions, One special physicochemical environment that cannot be obtained in atmospheric conditions can be provided, reactant is sufficiently dissolved in kettle, And certain degree of supersaturation is reached, so as to form atom or molecular growth primitive, carry out nucleation and crystallization growth.Nucleation and crystallization process In, crystal grain ordering growth, size tunable, hydro-thermal method obtain narrower particle size distribution than coprecipitation.
The present invention prepares the preparation method of nickel cobalt aluminum complex hydroxide using one step hydro thermal method, and method process is simple can Control property is high, and can control aluminium ion can realize equably being co-precipitated in the range of same pH with nickel and cobalt ions, advantageously form particle diameter Uniformly, morphology controllable, the metallic element composition nickel cobalt aluminum presoma stable with distribution.Solve aluminium salt in existing chemical coprecipitation technique It is difficult to uniformly be co-precipitated with nickel cobalt metal ion, causes three kinds of element ratios of nickel cobalt aluminum to be difficult to the problem of stability contorting.Meanwhile, this Invention provide one step hydro thermal method coprecipitation can also be overcome to prepare product degree of crystallinity is relatively low, the shortcoming of broad particle distribution.
Second aspect present invention additionally provides a kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminum complex hydroxide be according to Method described in first aspect is obtained, and the molecular formula of nickel cobalt aluminum complex hydroxide is NixCoyAl1-x-y(OH)3-x-y, wherein, 0 1,0 < y < 1 of < x <, and 0 < x+y < 1.
In the present invention, the molecular formula of nickel cobalt aluminum complex hydroxide is NixCoyAl1-x-y(OH)3-x-y, wherein, 0.7≤x < 1,0 < y < 0.3.
In the present invention, the mean diameter of nickel cobalt aluminum complex hydroxide is 2.5-4.5 μm, is characterized using XRD, the nickel cobalt aluminum The highest peak intensity of complex hydroxide>2000, show that the degree of crystallinity of granule is preferable.
In the present invention, nickel cobalt aluminum complex hydroxide is spherical.
The nickel cobalt aluminum complex hydroxide that second aspect present invention is provided, three kinds of element ratios of nickel cobalt aluminum are stable, product one Cause property is preferable, better crystallinity degree, narrow particle size distribution.
With reference to Fig. 2, Fig. 2 is the preparation method flow chart of nickel cobalt aluminium composite oxide in an embodiment of the present invention;3rd Aspect, the invention provides a kind of preparation method of nickel cobalt aluminium composite oxide, including:
(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt, nickel, cobalt and aluminum metal ion in mixing salt solution are prepared Mol ratio be x:y:(1-x-y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;
(2) precipitation and complexation agent is added in mixing salt solution, be mixing uniformly to form mixed solution, mixed solution is shifted Into hydrothermal reaction kettle, 12-48 hours are reacted at 100 DEG C -180 DEG C;Wherein, precipitation and complexation agent is carbamide, acetamide, propylene At least one in amide, ammonium carbonate and ammonium hydrogen carbonate;
(3), after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain nickel cobalt aluminium lamination Shape complex hydroxide;
(4) nickel cobalt aluminum layered double hydroxide is calcined into 2-8 hours at 300 DEG C -650 DEG C, obtains nickel cobalt aluminum and be combined Oxide.
In the present invention, in step (4), in calcination process with the heating rate of 5 DEG C/min-25 DEG C/min be warming up to 300 DEG C- 650℃。
In the present invention, in step (4), nickel cobalt aluminum layered double hydroxide is calcined in air atmosphere.
In the present invention, after calcining terminates, resulting material is sieved, nickel cobalt aluminium composite oxide is obtained.
The preparation method of the nickel cobalt aluminium composite oxide that third aspect present invention is provided, preparation method are simple, obtained nickel Cobalt aluminum composite oxide homogeneity of product is preferable.
Fourth aspect, the invention provides a kind of nickel cobalt aluminium composite oxide, nickel cobalt aluminium composite oxide is according to the 3rd Method described in aspect is obtained, and the molecular formula of nickel cobalt aluminium composite oxide is NixCoyAl1-x-yO1.5-0.5x-0.5y, wherein, 0 < x < 1,0 < y < 1, and 0 < x+y < 1.
In the present invention, the mean diameter of nickel cobalt aluminium composite oxide is 2.5 μm -4.5 μm, and tap density is 1.1g/cm3- 1.8g/cm3, apparent density is 0.6g/cm3-1.0g/cm3
In the nickel cobalt aluminium composite oxide that fourth aspect present invention is provided, three kinds of element ratios of nickel cobalt aluminum are stable, product one Cause property is preferable, better crystallinity degree, narrow particle size distribution.
Embodiment 1:
A kind of preparation method of nickel cobalt aluminium composite oxide, including:
(1) according to nickel, cobalt, aluminum metal ion molar concentration rate be n (Ni2+):n(Co2+):n(Al3+)=0.7:0.2: Nickel salt, cobalt salt, aluminium salt are configured to mixing salt solution by 0.1 ratio, nickel in mixing salt solution, cobalt, three metal ion species of aluminum Total mol concentration is in 1mol/L;
(2) add carbamide in mixing salt solution, the mole of carbamide it is total with nickel, cobalt and three metal ion species of aluminum mole Amount ratio is 10:1, mixed solution is mixing uniformly to form, mixed solution is put in politef hydrothermal reaction kettle, anti- The filling rate for answering kettle is 80%, is reacted 24 hours at 120 DEG C, and the pressure of reactor is 3MPa;
(3) after reaction terminates, room temperature is cooled to, resulting material is filtered, is washed, until filtrate pH is neutrality, after drying, Obtain nickel cobalt aluminum complex hydroxide;
(4) nickel cobalt aluminum complex hydroxide is warming up to into 500 DEG C with the heating rate of 20 DEG C/min, 3 are calcined at 500 DEG C Hour.Nickel cobalt aluminium composite oxide is obtained.
Repeat the method in the present embodiment 1, prepare the nickel cobalt aluminum complex hydroxide product of tri- batches of A, B, C, respectively ICP component analyses are carried out to which.According to analysis result, it is known that the corresponding nickel cobalt aluminum metal elemental mole ratios of A batch products are 0.695:0.203:0.102;The corresponding nickel cobalt aluminum metal elemental mole ratios of B batch products are 0.698:0.201:0.101;C batch The corresponding nickel cobalt aluminum metal elemental mole ratios of secondary product are 0.703:0.206:0.091.The metallic element of three batch products contains Amount is more or less the same, it was demonstrated that hydro-thermal method can obtain the good nickel cobalt aluminum complex hydroxide of elementary composition concordance really.
Meanwhile, to same batch A nickel cobalt aluminum complex hydroxide product, zones of different is taken (such as upper strata, lower floor, left side, the right side Side etc.) three samples E, F, G, ICP component analyses are carried out to which respectively, obtain the distinguished corresponding nickel cobalt aluminum of E, F, G be combined Nickel cobalt aluminum metal elemental mole ratios in hydroxide product are respectively 0.701:0.200:0.099、0.698:0.199: 0.103、0.697:0.202:0.101.It follows that elementary composition being more or less the same of same batch zones of different sample (removes Personal error, instrumental error in weighing sample and test process).
Ultramicroscope (SEM) sign is scanned to gained nickel cobalt aluminum complex hydroxide, Fig. 3 is the embodiment of the present invention The scanning electron microscope (SEM) photograph of obtained nickel cobalt aluminum complex hydroxide in 1.As can be seen from Figure 3 the shape of nickel cobalt aluminum complex hydroxide Shape is spherical, and sphericity is higher, and particle diameter is more uniform, about 3.0 μm of mean diameter.
Meanwhile, equipped with Energy Dispersive X-ray spectrogrph (EDX) on SEM equipment, to occurring in scanning electron microscope picture Different spherical compounds, 4 different locis 1,2,3,4 of same spherical compound carry out energy spectrum analysiss, gained Ni, Co, The element proportion of Al is more or less the same.1st, 2,3,4 four Ni corresponding to point:Co:Al is respectively 0.699:0.200: 0.101;0.698:0.201:0.101;0.699:0.200:0.101;0.703:0.201:0.096.This has been proved further The method of bright offer can obtain the good nickel cobalt aluminum complex hydroxide of elementary composition concordance really.
The nickel cobalt aluminum complex hydroxide that the A batches of the present embodiment 1 are obtained simultaneously is carried out calcining the nickel cobalt aluminum for obtaining multiple Closing oxide A ' carries out ICP component analyses, is as a result that the structural formula of nickel cobalt aluminium composite oxide A ' is Ni0.695Co0.202Al0.103O1.0515
Ultramicroscope (SEM) sign is scanned to obtained nickel cobalt aluminium composite oxide in the embodiment of the present invention 1.Can To find out, being shaped as nickel cobalt aluminium composite oxide A ' is spherical, and sphericity is higher, and particle diameter is more uniform, and mean diameter is about 2.95μm.In addition, apparent density is 0.8g/cm3, tap density is 1.2g/cm3
Fig. 4 is X-ray energy spectrum (EDXA) photo of obtained nickel cobalt aluminium composite oxide in the embodiment of the present invention 1.From Fig. 4 In as can be seen that each metallic element Ni (left figure), Co (middle figure), Al (right figure) are generally evenly distributed in granule.
Embodiment 2:
A kind of preparation method of nickel cobalt aluminium composite oxide, including:
(1) according to nickel, cobalt, aluminum metal ion molar concentration rate be n (Ni2+):n(Co2+):n(Al3+)=0.7:0.2: Nickel salt, cobalt salt, aluminium salt are configured to mixing salt solution by 0.1 ratio, nickel in mixing salt solution, cobalt, three metal ion species of aluminum Total mol concentration is in 0.5mol/L;
(2) add carbamide in mixing salt solution, the mole of carbamide it is total with nickel, cobalt and three metal ion species of aluminum mole Amount ratio is 10:1, mixed solution is mixing uniformly to form, mixed solution is put in politef hydrothermal reaction kettle, reacted The filling rate of kettle is 80%, is reacted 36 hours at 150 DEG C, and the pressure of reactor is 3.5MPa.
(3) after reaction terminates, room temperature is cooled to, resulting material is filtered, is washed, until filtrate pH is neutrality, after drying, Obtain nickel cobalt aluminum complex hydroxide.
(4) nickel cobalt aluminum complex hydroxide is warming up at 500 DEG C with the heating rate of 20 DEG C/min, is forged at 500 DEG C Burn 3 hours.Nickel cobalt aluminium composite oxide is obtained.
In step (3), being shaped as gained nickel cobalt aluminum complex hydroxide is spherical, and sphericity is higher, and particle diameter is more uniform, It is computed, mean diameter is 2.5 μm;Nickel cobalt aluminum complex hydroxide sample is carried out using ICP (inductively coupled plasma) Component analyses, it is known that nickel cobalt aluminum complex hydroxide consists of Ni obtained in the present embodiment0.703Co0.201Al0.096(OH)2.096
Being shaped as nickel cobalt aluminium composite oxide obtained in the present embodiment is spherical, and sphericity is higher, and particle diameter is more uniform, puts down Particle diameter is about 2.46 μm.Nickel cobalt aluminium composite oxide sample is carried out into component analyses using ICP (inductively coupled plasma), Understand nickel cobalt aluminium composite oxide obtained in the present embodiment consists of Ni0.701Co0.202Al0.097O1.0485.In addition, apparent density For 0.6g/cm3, tap density is 1.1g/cm3
Embodiment 3:
A kind of preparation method of nickel cobalt aluminium composite oxide, including:
(1) according to nickel, cobalt, aluminum metal ion molar concentration rate be n (Ni2+):n(Co2+):n(Al3+)=0.8:0.15: Nickel salt, cobalt salt, aluminium salt are configured to mixing salt solution by 0.05 ratio, nickel in mixing salt solution, cobalt, three metal ion species of aluminum Total mol concentration is in 1mol/L;
(2) add carbamide in mixing salt solution, the mole of carbamide it is total with nickel, cobalt and three metal ion species of aluminum mole Amount ratio is 10:1, it is mixing uniformly to form mixed solution.Mixed solution is put in politef hydrothermal reaction kettle, anti- The filling rate for answering kettle is 80%, is reacted 24 hours at 120 DEG C, and the pressure in reactor is 2.5MPa.
(3) after reaction terminates, room temperature is cooled to, resulting material is filtered, is washed, until filtrate pH is neutrality, after drying, Obtain nickel cobalt aluminum complex hydroxide.
(4) nickel cobalt aluminum complex hydroxide is warming up to into 500 DEG C with the heating rate of 20 DEG C/min, 3 are calcined at 500 DEG C Hour.Nickel cobalt aluminium composite oxide is obtained.
In step (3), being shaped as gained nickel cobalt aluminum complex hydroxide is spherical, and sphericity is higher, and particle diameter is more uniform, It is computed, mean diameter is 3.2 μm;Nickel cobalt aluminum complex hydroxide sample is carried out using ICP (inductively coupled plasma) Component analyses, it is known that nickel cobalt aluminum complex hydroxide consists of Ni obtained in the present embodiment0.798Co0.149Al-0.053 (OH)2.053
Nickel cobalt aluminium composite oxide obtained in the present embodiment is shaped as regular spherical, and sphericity is higher, and particle diameter is more uniform, About 3.15 μm of mean diameter.Nickel cobalt aluminium composite oxide sample is carried out into composition point using ICP (inductively coupled plasma) Analysis, it is known that nickel cobalt aluminium composite oxide consists of Ni obtained in the present embodiment0.798Co0.149Al-0.053O1.0265.In addition, pine dress Density is 0.9g/cm3, tap density is 1.3g/cm3
Embodiment 4:
A kind of preparation method of nickel cobalt aluminium composite oxide, including:
(1) according to nickel, cobalt, aluminum metal ion molar concentration rate be n (Ni2+):n(Co2+):n(Al3+)=0.85:0.1: Nickel salt, cobalt salt, aluminium salt are configured to mixing salt solution by 0.05 ratio, nickel in mixing salt solution, cobalt, three metal ion species of aluminum Total mol concentration is in 1.5mol/L;
(2) add carbamide in mixing salt solution, the mole of carbamide it is total with nickel, cobalt and three metal ion species of aluminum mole Amount ratio is 15:1, mixed solution is mixing uniformly to form, mixed solution is put in politef hydrothermal reaction kettle, anti- The filling rate for answering kettle is 85%, is reacted 24 hours at 150 DEG C, and the pressure in reactor is 4MPa.
(3) after reaction terminates, room temperature is cooled to, resulting material is filtered, is washed, until filtrate pH is neutrality, after drying, Obtain nickel cobalt aluminum complex hydroxide.
(4) nickel cobalt aluminum complex hydroxide is warming up to into 600 DEG C with the heating rate of 20 DEG C/min, 2 are calcined at 600 DEG C Hour.Nickel cobalt aluminium composite oxide is obtained.
In step (3), being shaped as gained nickel cobalt aluminum complex hydroxide is spherical, and sphericity is higher, and particle diameter is more uniform, It is computed, mean diameter is 4.1 μm;Nickel cobalt aluminum complex hydroxide sample is carried out using ICP (inductively coupled plasma) Component analyses, it is known that nickel cobalt aluminum complex hydroxide consists of Ni obtained in the present embodiment0.846Co0.103Al0.051(OH)2.051
Being shaped as nickel cobalt aluminium composite oxide obtained in the present embodiment is spherical, and sphericity is higher, and particle diameter is more uniform, puts down Particle diameter is about 4.02 μm.Nickel cobalt aluminium composite oxide sample is carried out into component analyses using ICP (inductively coupled plasma), Understand nickel cobalt aluminium composite oxide obtained in the present embodiment consists of Ni0.847Co0.103Al0.050O1.025.In addition, apparent density For 1.0g/cm3, tap density is 1.6g/cm3
Embodiment described above only expresses the several embodiments of the present invention, and its description is more concrete and detailed, but and Therefore the restriction to the scope of the claims of the present invention can not be interpreted as.It should be pointed out that for one of ordinary skill in the art For, without departing from the inventive concept of the premise, some deformations and improvement can also be made, these belong to the guarantor of the present invention Shield scope.Therefore, the protection domain of patent of the present invention should be defined by claims.

Claims (10)

1. a kind of preparation method of nickel cobalt aluminum complex hydroxide, it is characterised in that include:
(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt, nickel, cobalt and aluminum metal ion in the mixing salt solution are prepared Mol ratio be x:y:(1-x-y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;
(2) precipitation and complexation agent is added in the mixing salt solution, be mixing uniformly to form mixed solution, by the mixed solution It is transferred in hydrothermal reaction kettle, 12-48 hours is reacted at 100 DEG C -180 DEG C;Wherein, the precipitation and complexation agent is carbamide, second At least one in amide, acrylamide, ammonium carbonate and ammonium hydrogen carbonate;
(3) after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain the compound hydrogen of nickel cobalt aluminum Oxide.
2. the preparation method of nickel cobalt aluminum complex hydroxide as claimed in claim 1, it is characterised in that the scope of the x is The scope of 0.7≤x < 1, the y is 0 < y < 0.3.
3. the preparation method of nickel cobalt aluminum complex hydroxide as claimed in claim 1, in the mixing salt solution, nickel, cobalt and The total mol concentration of three metal ion species of aluminum is 0.5mol/L-3mol/L.
4. the preparation method of nickel cobalt aluminum complex hydroxide as claimed in claim 1, it is characterised in that the precipitation and complexation agent Mole and the nickel, the integral molar quantity of three metal ion species of the cobalt and the aluminum ratio be 5-20:1.
5. the preparation method of nickel cobalt aluminum complex hydroxide as claimed in claim 4, it is characterised in that the precipitation and complexation agent Mole and the nickel, the integral molar quantity of three metal ion species of the cobalt and the aluminum ratio be 10-15:1.
6. nickel cobalt aluminum complex hydroxide obtained in a kind of method according to described in any one of claim 1-5, the nickel cobalt aluminum The molecular formula of complex hydroxide is NixCoyAl1-x-y(OH)3-x-y, wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1.
7. a kind of preparation method of nickel cobalt aluminium composite oxide, it is characterised in that include:
(1) mixing salt solution containing nickel salt, cobalt salt and aluminium salt, nickel, cobalt and aluminum metal ion in the mixing salt solution are prepared Mol ratio be x:y:(1-x-y), wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1;
(2) precipitation and complexation agent is added in the mixing salt solution, be mixing uniformly to form mixed solution, by the mixed solution It is transferred in hydrothermal reaction kettle, 12-48 hours is reacted at 100 DEG C -180 DEG C;Wherein, the precipitation and complexation agent is carbamide, second At least one in amide, acrylamide, ammonium carbonate and ammonium hydrogen carbonate;
(3) after question response terminates, solid-liquid separation, washing are carried out to resulting material after reaction and is dried, obtain the compound hydrogen of nickel cobalt aluminum Oxide;
(4) the nickel cobalt aluminum complex hydroxide is calcined into 2-8 hours at 300 DEG C -650 DEG C, obtains nickel cobalt aluminum composite oxide Thing.
8. the preparation method of nickel cobalt aluminium composite oxide as claimed in claim 7, it is characterised in that in the calcination process with The heating rate of 5 DEG C/min-25 DEG C/min is warming up to described 300 DEG C -650 DEG C.
9. nickel cobalt aluminium composite oxide obtained in a kind of method according to described in any one of claim 7-8, the nickel cobalt aluminum are multiple The molecular formula for closing oxide is NixCoyAl1-x-yO1.5-0.5x-0.5y, wherein, 0 < x <, 1,0 < y < 1, and 0 < x+y < 1.
10. nickel cobalt aluminium composite oxide as claimed in claim 9, it is characterised in that the nickel cobalt aluminium composite oxide it is flat Particle diameter is 2.5 μm -4.5 μm, and tap density is 1.1g/cm3-1.8g/cm3, apparent density is 0.6g/cm3-1.0g/cm3
CN201610937957.8A 2016-10-25 2016-10-25 A kind of nickel cobalt aluminum complex hydroxide, nickel cobalt aluminium composite oxide and preparation method thereof Pending CN106558695A (en)

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Application publication date: 20170405