CN106299347A - Nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method - Google Patents

Nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method Download PDF

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CN106299347A
CN106299347A CN201610650420.3A CN201610650420A CN106299347A CN 106299347 A CN106299347 A CN 106299347A CN 201610650420 A CN201610650420 A CN 201610650420A CN 106299347 A CN106299347 A CN 106299347A
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solution
ammonia
nickel cobalt
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solion
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CN106299347B (en
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陈勃涛
唐淼
李征玉
徐宁
吴孟涛
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Tianjin B&M Science and Technology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention discloses a kind of nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode of preparation and method, by Ni, the soluble-salt of Co is dissolved in ammonia, form Ni, the ammonia of Co coordinates solion as enveloping agent solution, in aluminum salt solution, add chelating agent form the cooperation solion of Al as aluminum source solution, by Ni, Co soluble salt solutions, precipitant solution and enveloping agent solution and aluminum source solution also flow in addition reactor, control pH value in reaction and reaction temperature, response time at least more than 10h, the slurry obtaining reaction carries out solid-liquid separation, the solids obtained is through washing, drying obtains nickel cobalt aluminium hydroxide presoma.Presoma obtains nickel cobalt aluminum tertiary cathode material through high-temperature heat treatment with the mixture of lithium salts under air or oxygen atmosphere.The mixing homogeneity of tri-kinds of elements of Ni, Co and Al can be effectively improved, improve tap density and the sphericity of granule of persursor material.

Description

Nickel cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method
Technical field
The present invention relates to the preparing technical field of anode material for lithium-ion batteries and persursor material thereof, especially a kind of nickel Cobalt aluminum ternary precursor and preparation method thereof and the positive electrode prepared and method.
Background technology
Owing to having the advantage of high power capacity and high-energy-density, nickel cobalt aluminum lithium ternary material (NCA material) becomes high-energy The preferable positive electrode of density lithium ion positive electrode.Tesla of U.S. electric automobile have employed 8000 more pieces and thinks NCA material For 18650 battery composition set of cells of positive pole, battery pack power density can reach 170wh/kg, it is ensured that charging electric vehicle continues Boat mileage reaches more than 350 kilometers；The 18650 battery nominal capacitys that MAT uses NCA material to be positive pole can reach More than 3.0Ah, this other positive electrode being the most practical is incomparable.
Every physical chemistry of positive electrode and chemical property not only with the Macroscopic physical chemical characteristic of persursor material Relevant, also have with form with the crystal structure of its microcosmic and directly contact.Therefore, the orderly of persursor material crystal structure is improved Property, optimize a grain form and second particle pattern for improving every physically and electrically chemical of nickel cobalt aluminum lithium anode material Vital impact can be had as rolled density, multiplying power discharging property, cyclical stability etc..
Ni(OH)2With Co (OH)2Ksp value be respectively 2.0 × 10-15With 1.5 × 10-15, Ni under alkaline environment2+And Co2 +There is precipitation in moment, produces flocculent deposit, and the degree of crystallinity of resulting materials is very poor, and physical and chemical performance is severe, it is impossible to uses.? Controlling in crystallization preparation method, employing ammonia is chelating agent, nickel, cobalt, the soluble salt solutions of aluminum, precipitant NaOH solution and ammonia Water three pumps in the reactor with stirring simultaneously.In the solution, ammonia first with Ni2+And Co2+Form nickel ammonia and coordinate ion [Ni(NH3)6]2+Ion [Co (NH is coordinated with cobalt ammonia3)6]2+, the ammonia of nickel cobalt coordinates ion to dissociate Ni again2+And Co2+With OH-Send out Raw precipitation generates Ni1-x-yCox(OH)2, Al the most not with NH3Being formed and coordinate ion, therefore settling velocity is quickly, affects NCA The crystal structure order of presoma, its course of reaction is:
Ni2++6NH3·H2O=[Ni (NH3)6]2++6H2O (1)
Co2++6NH3·H2O=[Co (NH3)6]2++6H2O (2)
(1-x-y)[Ni(NH3)6]2++x[Co(NH3)6]2++yAl3++2OH-→Ni1-x-yCoxAly(OH)2+12NH3 (3)
Owing to coordinating being formed of ion relatively slow relative to the settling velocity of metal ion with speed of dissociating, therefore reduce total The speed of precursor reactant process, makes response speed be controlled, and the crystal structure of nickel cobalt co-precipitation hydroxide has the sufficient time Growth, thus it is high to form degree of crystallinity, the hydroxide materials that lattice order is strong, under the effect of stirring, can form density High, the persursor material of good sphericity, this is to ensure that the premise obtaining high-quality NCA material.
NCA material precursor material Ni at present1-x-yCoxAly(OH)2(0 < x≤0.2,0 < y≤0.05) generally uses control Prepared by crystallization process.It is aluminum source that Chinese patent CN103094546 describes a kind of employing sodium metaaluminate, and ammonia is chelating agent, hydrogen-oxygen Change the preparation method of nickel cobalt aluminium hydroxide that sodium is precipitant, the mixing salt solution of nickel cobalt, precipitant solution, aluminum source solution with Chelating agent ammonia is added simultaneously in reactor carry out coprecipitation reaction, obtains nickel cobalt aluminium hydroxide.Chinese patent CN 105206827A discloses one and aluminium salt is mixed with chelating agent in advance, forms the cooperation solion of Al, mixes with nickel cobalt molten Liquid, carries out coprecipitation reaction under the effect of precipitant and chelating agent, obtains spherical nickel cobalt aluminium hydroxide presoma.At this In a little preparation methoies, sodium metaaluminate utilizes its hydrolysis to control Al (OH)3Generation, but reaction without Al3+Produce, Ni, Co, Al Element all can not be pre-formed stable cooperation ion before precipitation.With the acid-soluble salt of Al for aluminum source, can be with The chelating agent such as EDTA are pre-formed stable cooperation ion, but Ni, Co element cannot be pre-formed stable cooperation ion, impact The speed of coprecipitation reaction.
Summary of the invention
The technical problem to be solved is to provide a kind of nickel cobalt aluminum ternary precursor and preparation method thereof and preparation Positive electrode and method, the mixing homogeneity of tri-kinds of elements of Ni, Co and Al can be effectively improved.
In order to solve above-mentioned technical problem, the technical solution used in the present invention is: the system of a kind of nickel cobalt aluminum ternary precursor Preparation Method, comprises the following steps:
1) being proportionally added in ammonia by the soluble-salt of nickel, cobalt, the ammonia of preparation Ni, Co coordinates solion I；To partially Sodium aluminate solution adds chelating agent so that it is be combined formation Al with Al element and coordinate solion II；By nickel, the soluble-salt of cobalt It is configured to the mixing salt solution III of Ni, Co metal cation in proportion；Preparation NaOH solution IV；
2) in advance equipped with a certain amount of deionized water in reactor, ammonia regulation pH to 10.0～12.0 is added, will preparation Good solution III, solution IV, solution I and solution II pump in reactor simultaneously, fixed solution III, solution I and solution II Speed, in the range of in regulation solution IV speed controlling reactor, the pH value of solution is maintained at 10.0～12.5, in reactor Speed of agitator is 100～500 revs/min, and in reaction, solution temperature is maintained at 30～80 DEG C, and the response time is not less than 10h, stops After adding solution I, II, III, IV, slurry reaction obtained carries out solid-liquid separation, the solids deionization obtained after separation Water washs, the solid after dehydration dries at 100～150 DEG C, sieve after obtain nickel cobalt aluminum ternary precursor；The molecule of presoma Formula is Ni1-x-yCoxAly(OH)2, wherein 0 < x≤0.2,0 < y≤0.05.
Step 1) described in ammonia molar concentration CNH3Being 5～15mol/L, the ammonia of formation coordinates Ni and Co in solion I Molar ratio be (1-x-y)/y, wherein ammoniacal substance amount coordinates total thing mass ratio of Ni+Co element in solion to be with ammonia 6～10；Mixing salt solution III concentration CMe-IIIIt is 0.5～the ratio of 2.3mol/L, Ni and Co element is Ni:Co=(1-x-y): y；NaOH solution IV concentration is 2～10mol/L.
Described nickel, the soluble-salt of cobalt are one or more in sulfate, nitrate, acetate and chloride.
Step 1) described in chelating agent be in disodiumedetate, sodium citrate, sodium lactate, hydrazine hydrate at least One, the addition of described chelating agent is 0.5～2.0:1 with the mol ratio of Al element.
The Ni that described drying obtains after sieving1-x-yCoxAly(OH)2Presoma meso-position radius granularity D50It is 5～20 μm.
Step 2) described in fix Ni, Co mixing salt solution III flow velocity be V3, then the ammonia of Ni, Co coordinates solion I stream Speed V1Draw according to the following formula:
V1=V3×CMe-III/(CNH3×(R2-1/R1)； (1)
In formula:
R1Ammonia coordinates NH in solion3Thing mass values with Ni+Co；
R2—NH3Material amount coordinates the ratio of total material amount of Ni+Co in solion with saline solution neutralization of ammonia；
CNH3NH in ammonia3Concentration, mol/L；
CMe-IIIThe concentration of Ni+Co, mol/L in Ni, Co mixing salt solution.
V3Ni, Co mixing salt solution flow velocity.
Step 2) in aluminum salt solution II flow velocity V2Draw according to the following formula:
V 2 = y ( C M e - I I I &times; V 3 + ( C N H 3 / R 1 ) &times; V 1 ) ( 1 - y ) &times; C A l - - - ( 2 )
In formula:
CMe-IIIThe concentration of Ni+Co, mol/L in Ni, Co mixing salt solution；
CNH3NH in ammonia3Concentration, mol/L；
V3Ni, Co mixing salt solution flow velocity, L/min；
V1The ammonia of Ni, Co coordinates solion flow velocity, L/min；
R1Ammonia coordinates NH in solion3Thing mass values with Ni+Co.
The nickel cobalt aluminum ternary precursor that above-mentioned preparation method prepares.
Use the method that above-mentioned nickel cobalt aluminum ternary precursor prepares positive electrode, use high-speed mixer, by obtain Nickel cobalt aluminum ternary precursor and Lithium hydrate mix homogeneously by a certain percentage, in bell-type roaster, with the speed of 2～10 DEG C/min Rate is warming up to 600～800 DEG C, is incubated 5～20h, is passed through oxygen, it is ensured that in stove, oxygen content is more than in bell-type roaster 70%, insulation is naturally cooling to room temperature after terminating, and the blank that roasting obtains obtains nickel cobalt aluminum tertiary cathode after pulverizing, sieving Material, in Lithium hydrate, Li element is 0.9～1.2 with thing mass ratio Li/ (Ni+Co+Al) of Ni, Co, Al element in presoma: 1。
The nickel cobalt aluminum tertiary cathode material that above-mentioned preparation method prepares.
The invention has the beneficial effects as follows: the mixing homogeneity of tri-kinds of elements of Ni, Co and Al can be effectively improved, at utmost Avoid the generation of Al element Local enrichment phenomenon, improve tap density and the sphericity of granule of persursor material.
Accompanying drawing explanation
Fig. 1 is the flow chart of the present invention.
Detailed description of the invention
With detailed description of the invention, the present invention is described in further detail below in conjunction with the accompanying drawings:
The present invention, first joins in ammonia by the soluble-salt of Ni, Co, in Ni, Co element ratio and target molecule formula Ni, Co element ratio is identical, and the ammonia that the addition of control soluble-salt forms it into close to saturated Ni, Co coordinates ion molten Liquid, pumps in reactor using this solution as chelating agent.By taking the method, by reaction equation (1) and (2) outside reactor pre- First complete, form stable nickel cobalt coordination compound ion, part Ni can be effectively prevented from2+、Co2+Before not forming cooperation ion just With OH—There is precipitation, the order of material microstructure can be effectively improved, improve the vibration density of persursor material Degree.
Form Al (OH)3Ksp=1.33 × 10 of precipitation-33, with Ni (OH)2With Co (OH)2Ksp value differ relatively Greatly, therefore settling velocity is faster, increases the randomness of crystal structure.Al (OH) is reduced it is thus desirable to take measures3Precipitation is anti- The speed answered is so that itself and Ni (OH)2With Co (OH)2Settling velocity is coordinated mutually.Employing sodium metaaluminate is aluminium salt, at H+Effect Under, meta-aluminic acid radical ion occurs to react as follows:
H++AlO2 -+H2O→Al(OH)3↓ (4)
Under the reaction system of alkalescence, H+Content is relatively low, and the speed that reaction equation occurs to the right is suppressed, and can effectively control Al(OH)3Generation speed so that it is consistent with the settling velocity of Ni, Co hydroxide, improve nickel cobalt aluminium hydroxide forerunner The crystal order of body material, improves crystal structure intensity and the density of second particle.
If shown in concrete preparation flow Fig. 1, comprised the steps of:
1) will be (Ni+Co)/NH according to molar ratio3=1/6～1/10, add in the ammonia that concentration is 5～15mol/L Entering the soluble-salt of Ni, Co, be configured to nickel ammonia and coordinate solion (I) with cobalt ammonia after dissolving, wherein the ratio of Ni Yu Co is (1- x-y)/x；
2) compound concentration is the sodium aluminate solution (II) of 0.5～5mol/L, adds chelating agent in solution, and chelating agent is NaF、NH3At least one in F, disodiumedetate (EDTA), sodium citrate, sodium lactate, the addition of described chelating agent Amount is 0.5～2.0:1 with the mol ratio of Al element；It is 1～2.3mol/ according to the proportions concentration of Ni/Co=(1-x-y)/y The nickel cobalt mixing salt solution (III) of L, salt can be nitrate, sulfate and chloride；
3) compound concentration is that the sodium hydroxide solution (IV) of 2～10mol/L is as precipitant；
4) solution (I), solution (II), solution (III) and solution (IV) stream are pumped into reactor, respectively fixed solution (I), solution (II) and the speed of solution (III), by solution ph in regulation solution (IV) speed controlling reactor 10.0 ～12.5, making solution (III) flow velocity is V3, then V1=(0.5～2.0) × (CMe/CNH3)×V3,
5) reaction temperature is 30～80 DEG C, and speed of agitator 100～500 revs/min, reactor top is equipped with overfall, still After full, solution overflows from the overflow pipe on reactor top, collection spillage solution, through solid-liquid separation, wash, dry, sieve after Obtain nickel cobalt aluminum ternary precursor.
6) use high-speed mixer, by step 5) in the nickel cobalt aluminum ternary precursor that obtains and Lithium hydrate according to Li/ (Ni + Co+Al)=ratio the mix homogeneously of 0.9～1.20, in bell-type roaster, with the ramp of 2～10 DEG C/min to 600 ～800 DEG C, it is incubated 5～20h, roasting process is passed through oxygen, it is ensured that in bell-type roaster, oxygen content is not less than 70%, insulation Being naturally cooling to room temperature after end, the blank that roasting obtains obtains nickel cobalt aluminum tertiary cathode material after pulverizing, sieving.
Embodiment 1
Take the ammonia that concentration is 10mol/L, add nickel sulfate 368.9g and the ratio of cobaltous sulfate 74.0g according to every liter of ammonia Adding nickel sulfate and cobaltous sulfate, stirring makes nickel sulfate dissolve with cobaltous sulfate, and the ammonia making Ni, Co coordinates solion (solution I), by every liter of 81.9gNaAlO2The inclined sodium chlorate solution of proportions (solution II), preparation 6mol/L sodium hydroxide solution (molten Liquid IV), according to proportions nickel sulfate and the mixing salt solution of cobaltous sulfate of Ni/Co=0.842/0.158, saline solution total concentration For 2.5mol/L (solution III).Four kinds of solution stream are joined in reactor, wherein the stream of nickel cobalt saline solution (solution III) Speed is 100ml/min, formula (1) obtaining solion flow velocity with nickel, cobalt is 30ml/min, formula (2) obtain inclined aluminum Acid sodium solution flow velocity is 15.8ml/min, regulates sodium hydroxide solution (solution IV) flow velocity, and in making reactor, pH value controls Between 11.0 ± 0.1, after reaction 20h, stopping charging, obtained slurry is carried out solid-liquid separation, the solids obtained spends Ionized water washs, and the solids after dehydration dries 8～10h at 120～130 DEG C, obtains nickel cobalt aluminium hydroxide presoma Ni0.8Co0.15Al0.05(OH)2。
Use high-speed mixer by the nickel cobalt aluminum presoma obtained by previous step and Lithium hydrate according to Li/Me=1.10's Ratio mix homogeneously, is warming up to 750 DEG C with the speed of 10 DEG C/min in van-type stove, is incubated 10h, is passed through oxygen in roasting process Gas, flow is 0.6m3/ h, in stove, oxygen content is more than 90%, and insulation is naturally cooling to room temperature after terminating, the blank that roasting obtains Nickel cobalt aluminum tertiary cathode material is obtained after pulverizing, sieving.After tested, nickel cobalt aluminum tertiary cathode material D50It is 10.2 μm, shakes Real density reaches 2.62g/cm3, using 2032 button cell test chemical properties, in 3.0～4.3V voltage ranges, 0.1C is put Capacitance reaches 198mAh/g.
Embodiment 2
Take the ammonia that concentration is 10mol/L, add the ratio of nickel sulfate 406.5g and cobaltous sulfate 33.80g according to every liter of ammonia Example adds nickel sulfate and cobaltous sulfate, and stirring makes nickel sulfate dissolve with cobaltous sulfate, and the ammonia making Ni, Co coordinates solion (molten Liquid I), by every liter of 163.9gNaAlO2The inclined sodium chlorate solution of proportions (solution II), prepare 6mol/L sodium hydroxide solution (solution IV), according to proportions nickel sulfate and the mixing salt solution of cobaltous sulfate of Ni/Co=0.928/0.072, saline solution is total Concentration is 2.3mol/L (solution III).Four kinds of solution stream are joined in reactor, wherein nickel cobalt saline solution (solution III) Flow velocity be 200ml/min, formula (1) obtain solion flow velocity V with nickel, cobalt1For 48ml/min, formula (2) obtain To sodium aluminate solution flow velocity V2For 25.3ml/min, regulate sodium hydroxide solution (solution IV) flow velocity, make pH value in reactor Control between 10.8 ± 0.1, after reaction 10h, stop charging, obtained slurry is carried out solid-liquid separation, the solid obtained Thing is washed with deionized, and the solids after dehydration dries 8～10h at 120～130 DEG C, obtains nickel cobalt aluminium hydroxide forerunner Body Ni0.9Co0.07Al0.03(OH)2。
Use high-speed mixer by the nickel cobalt aluminum presoma obtained by previous step and Lithium hydrate according to Li/Me=1.20's Ratio mix homogeneously, is warming up to 600 DEG C with the speed of 10 DEG C/min in van-type stove, is incubated 10h, is passed through oxygen in roasting process Gas, flow is 0.6m3/ h, in stove, oxygen content is more than 90%, and insulation is naturally cooling to room temperature after terminating, the blank that roasting obtains Nickel cobalt aluminum tertiary cathode material is obtained after pulverizing, sieving.After tested, nickel cobalt aluminum tertiary cathode material D50It is 9.7 μm, jolt ramming Density reaches 2.63g/cm3, use 2032 button cell test chemical properties, 0.1C electric discharge in 3.0～4.3V voltage ranges Capacity reaches 205mAh/g.
Embodiment 3
Preparation Ni0.98Co0.01Al0.01(OH)2Presoma: take the ammonia that concentration is 15mol/L, adds according to every liter of ammonia The ratio of nickel sulfate 390.3g and cobaltous sulfate 4.3g adds nickel sulfate and cobaltous sulfate, and stirring makes nickel sulfate dissolve with cobaltous sulfate, joins The ammonia making Ni, Co coordinates solion (solution I), by every liter of 245.9gNaAlO2The inclined sodium chlorate solution of proportions (molten Liquid II), preparation 10mol/L sodium hydroxide solution (solution IV), according to the proportions nickel sulfate of Ni/Co=0.928/0.072 With the mixing salt solution of cobaltous sulfate, saline solution total concentration is 2.3mol/L (solution III).Four kinds of solution stream are joined reaction In still, wherein the flow velocity of nickel cobalt saline solution (solution III) is 150ml/min, formula (1) obtain solion with nickel, cobalt Flow velocity V1For 48ml/min, formula (2) obtain sodium aluminate solution flow velocity V2For 6.4ml/min, regulate sodium hydroxide solution (solution IV) flow velocity, in making reactor, pH value controls between 11.5 ± 0.1, after reaction 30h, stops charging, to obtained Slurry carries out solid-liquid separation, and the solids obtained is washed with deionized, the solids after dehydration 140～150 DEG C dry 8～ 10h, obtains nickel cobalt aluminium hydroxide presoma Ni0.98Co0.01Al0.01(OH)2。
Use high-speed mixer by the nickel cobalt aluminum presoma obtained by previous step and Lithium hydrate according to Li/Me=1.10's Ratio mix homogeneously, is warming up to 800 DEG C with the speed of 2 DEG C/min in van-type stove, is incubated 10h, is passed through oxygen in roasting process, Flow is 0.6m3/ h, in stove, oxygen content is more than 90%, and insulation is naturally cooling to room temperature after terminating, the blank warp that roasting obtains Cross pulverize, sieve after obtain nickel cobalt aluminum tertiary cathode material.After tested, nickel cobalt aluminum tertiary cathode material D50It is 8.5 μm, vibration density Degree reaches 2.43g/cm3, using 2032 button cell test chemical properties, in 3.0～4.3V voltage ranges, 0.1C electric discharge is held Amount reaches 209.1mAh/g.
Embodiment 4
Preparation Ni0.7Co0.25Al0.05(OH)2Presoma: take the ammonia that concentration is 5mol/L, adds sulfur according to every liter of ammonia The ratio of acid nickel 121.0g and cobaltous sulfate 46.2g adds nickel sulfate and cobaltous sulfate, and stirring makes nickel sulfate dissolve with cobaltous sulfate, preparation The ammonia going out Ni, Co coordinates solion (solution I), by every liter of 278.7gNaAlO2Proportions inclined sodium chlorate solution (solution II), preparation 2mol/L sodium hydroxide solution (solution IV), according to proportions nickel sulfate and the sulfur of Ni/Co=0.737/0.263 The mixing salt solution of acid cobalt, saline solution total concentration is 1.0mol/L (solution III).Four kinds of solution stream are joined reactor In, wherein the flow velocity of nickel cobalt saline solution (solution III) is 200ml/min, formula (1) obtain solion stream with nickel, cobalt Speed V1For 48ml/min, formula (2) obtain sodium aluminate solution flow velocity V2For 6.4ml/min, regulation sodium hydroxide solution is (molten Liquid IV) flow velocity, in making reactor, pH value controls between 12.0 ± 0.1, after reaction 30h, stops charging, to obtained slurry Carrying out solid-liquid separation, the solids obtained is washed with deionized, and the solids after dehydration dries 8～10h at 140～150 DEG C, Obtain nickel cobalt aluminium hydroxide presoma Ni0.7Co0.25Al0.05(OH)2。
Use high-speed mixer by the nickel cobalt aluminum presoma obtained by previous step and Lithium hydrate according to Li/Me=1.20's Ratio mix homogeneously, is warming up to 800 DEG C with the speed of 2 DEG C/min in van-type stove, is incubated 10h, is passed through oxygen in roasting process, Flow is 0.6m3/ h, in stove, oxygen content is more than 70%, and insulation is naturally cooling to room temperature after terminating, the blank warp that roasting obtains Cross pulverize, sieve after obtain nickel cobalt aluminum tertiary cathode material.After tested, nickel cobalt aluminum tertiary cathode material D50It is 6.5 μm, vibration density Degree reaches 2.41g/cm3, using 2032 button cell test chemical properties, in 3.0～4.3V voltage ranges, 0.1C electric discharge is held Amount reaches 190.7mAh/g.
Embodiment 5
Preparation Ni0.75Co0.23Al0.02(OH)2Presoma: take the ammonia that concentration is 5mol/L, adds sulfur according to every liter of ammonia The ratio of acid nickel 295.3g and cobaltous sulfate 59.0g adds nickel sulfate and cobaltous sulfate, and stirring makes nickel sulfate dissolve with cobaltous sulfate, preparation The ammonia going out Ni, Co coordinates solion (solution I), by every liter of 245.9g NaAlO2Proportions inclined sodium chlorate solution (solution II), preparation 4mol/L sodium hydroxide solution (solution IV), according to proportions nickel sulfate and the sulfur of Ni/Co=0.765/0.235 The mixing salt solution of acid cobalt, saline solution total concentration is 1.5mol/L (solution III).Four kinds of solution stream are joined reactor In, wherein the flow velocity of nickel cobalt saline solution (solution III) is 50ml/min, formula (1) obtain solion flow velocity with nickel, cobalt V1For 7.03ml/min, formula (2) obtain sodium aluminate solution flow velocity V2For 1.1ml/min, regulation sodium hydroxide solution is (molten Liquid IV) flow velocity, in making reactor, pH value controls between 12.4～12.5, after reaction 100h, stops charging, to obtained slurry Material carry out solid-liquid separation, the solids obtained is washed with deionized, the solids after dehydration 140～150 DEG C dry 8～ 10h, obtains nickel cobalt aluminium hydroxide presoma Ni0.75Co0.23Al0.02(OH)2。
Use high-speed mixer by the nickel cobalt aluminum presoma obtained by previous step and Lithium hydrate according to Li/Me=1.15's Ratio mix homogeneously, is warming up to 800 DEG C with the speed of 8 DEG C/min in van-type stove, is incubated 10h, is passed through oxygen in roasting process, Flow is 0.6m3/ h, in stove, oxygen content is not less than 80%, and insulation is naturally cooling to room temperature after terminating, the blank that roasting obtains Nickel cobalt aluminum tertiary cathode material is obtained after pulverizing, sieving.After tested, nickel cobalt aluminum tertiary cathode material D50It is 5.2 μm, jolt ramming Density reaches 2.11g/cm3, use 2032 button cell test chemical properties, 0.1C electric discharge in 3.0～4.3V voltage ranges Capacity reaches 195.2mAh/g.
In sum, present disclosure is not limited in the above embodiments, and the knowledgeable people in same area can Can propose other embodiment within technological guidance's thought of the present invention easily, but this embodiment is included in this Within the scope of bright.

Claims (10)

1. the preparation method of a nickel cobalt aluminum ternary precursor, it is characterised in that comprise the following steps:
1) being proportionally added in ammonia by the soluble-salt of nickel, cobalt, the ammonia of preparation Ni, Co coordinates solion I；To meta-aluminic acid Sodium solution adds chelating agent so that it is be combined formation Al with Al element and coordinate solion II；By the soluble-salt of nickel, cobalt by than Example is configured to the mixing salt solution III of Ni, Co metal cation；Preparation NaOH solution IV；
2) in advance equipped with a certain amount of deionized water in reactor, ammonia regulation pH to 10.0～12.0 is added, by prepare Solution III, solution IV, solution I and solution II pump in reactor simultaneously, the speed of fixed solution III, solution I and solution II, In the range of in regulation solution IV speed controlling reactor, the pH value of solution is maintained at 10.0～12.5, in reactor, stirring turns Speed is 100～500 revs/min, and in reaction, solution temperature is maintained at 30～80 DEG C, and the response time is not less than 10h, stops addition molten After liquid I, II, III, IV, slurry reaction obtained carries out solid-liquid separation, and the solids obtained after separation is washed with deionized water Wash, the solid after dehydration dries at 100～150 DEG C, sieve after obtain nickel cobalt aluminum ternary precursor；The molecular formula of presoma is Ni1-x-yCoxAly(OH)2, wherein 0 < x≤0.2,0 < y≤0.05.
The preparation method of nickel cobalt aluminum ternary precursor the most according to claim 1, it is characterised in that step 1) described in ammonia Water molar concentration CNH3Being 5～15mol/L, the ammonia of formation coordinates the molar ratio of Ni Yu Co in solion I to be (1-x-y)/y, Wherein ammoniacal substance amount coordinates total thing mass ratio of Ni+Co element in solion to be 6～10 with ammonia；Mixing salt solution III is dense Degree CMe-IIIIt is 0.5～the ratio of 2.3mol/L, Ni and Co element is Ni:Co=(1-x-y): y；NaOH solution IV concentration be 2～ 10mol/L。
The preparation method of nickel cobalt aluminum ternary precursor the most according to claim 1, it is characterised in that described nickel, cobalt can Soluble is one or more in sulfate, nitrate, acetate and chloride.
The preparation method of nickel cobalt aluminum ternary precursor the most according to claim 1, it is characterised in that step 1) described in Chelating agent is at least one in disodiumedetate, sodium citrate, sodium lactate, hydrazine hydrate, the addition of described chelating agent Amount is 0.5～2.0:1 with the mol ratio of Al element.
The preparation method of nickel cobalt aluminum ternary precursor the most according to claim 1, it is characterised in that after described drying is sieved The Ni obtained1-x-yCoxAly(OH)2Presoma meso-position radius granularity D50It is 5～20 μm.
The preparation method of nickel cobalt aluminum ternary precursor the most according to claim 1, it is characterised in that step 2) described in solid Determining Ni, Co mixing salt solution III flow velocity is V3, then the ammonia of Ni, Co coordinates solion I flow velocity V1Draw according to the following formula:
V1=V3×CMe-III/(CNH3×(R2-1/R1)； (1)
In formula:
R1Ammonia coordinates NH in solion3Thing mass values with Ni+Co；
R2—NH3Material amount coordinates the ratio of total material amount of Ni+Co in solion with saline solution neutralization of ammonia；
CNH3NH in ammonia3Concentration, mol/L；
CMe-IIIThe concentration of Ni+Co, mol/L in Ni, Co mixing salt solution.
V3Ni, Co mixing salt solution flow velocity.
The preparation method of nickel cobalt aluminum ternary precursor the most according to claim 1, it is characterised in that step 2) in aluminium salt molten Liquid II flow velocity V2Draw according to the following formula:
V 2 = y ( C M e - I I I &times; V 3 + ( C N H 3 / R 1 ) &times; V 1 ) ( 1 - y ) &times; C A l - - - ( 2 )
In formula:
CMe-IIIThe concentration of Ni+Co, mol/L in Ni, Co mixing salt solution；
CNH3NH in ammonia3Concentration, mol/L；
V3Ni, Co mixing salt solution flow velocity, L/min；
V1The ammonia of Ni, Co coordinates solion flow velocity, L/min；
R1Ammonia coordinates NH in solion3Thing mass values with Ni+Co.
8. the nickel cobalt aluminum ternary precursor prepared such as the preparation method of any one of claim 1-7.
9. use the method that the nickel cobalt aluminum ternary precursor of claim 8 prepares positive electrode, it is characterised in that use the most mixed Conjunction machine, by the nickel cobalt aluminum ternary precursor obtained and Lithium hydrate mix homogeneously by a certain percentage, in bell-type roaster, with 2 ～the ramp of 10 DEG C/min is to 600～800 DEG C, it is incubated 5～20h, in bell-type roaster, is passed through oxygen, it is ensured that oxygen in stove Gas content is more than 70%, and insulation is naturally cooling to room temperature after terminating, and the blank that roasting obtains obtains nickel cobalt after pulverizing, sieving Aluminum tertiary cathode material, Li element and thing mass ratio Li/ (Ni+Co+Al) of Ni, Co, Al element in presoma in Lithium hydrate It is 0.9～1.2:1.
10. the nickel cobalt aluminum tertiary cathode material that preparation method as claimed in claim 9 prepares.
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