CN106299347B - Nickel cobalt aluminium ternary precursor and preparation method thereof and the positive electrode prepared and method - Google Patents
Nickel cobalt aluminium ternary precursor and preparation method thereof and the positive electrode prepared and method Download PDFInfo
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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
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- 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
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Abstract
The invention discloses a kind of nickel cobalt aluminium ternary precursor and preparation method thereof and the positive electrode prepared and methods, by Ni, the soluble-salt of Co is dissolved in ammonium hydroxide, form Ni, the ammonia of Co coordinates solion as enveloping agent solution, complexing agent is added in aluminum salt solution and forms the cooperation solion of Al as silicon source solution, by Ni, Co soluble salt solutions, precipitant solution and enveloping agent solution and silicon source solution cocurrent are added in reaction kettle, control pH value in reaction and reaction temperature, reaction time at least 10h or more, slurry obtained by the reaction is separated by solid-liquid separation, obtained solids is by washing, drying obtains nickel cobalt aluminium hydroxide precursor.The mixture of presoma and lithium salts obtains nickel cobalt aluminium tertiary cathode material under air or oxygen atmosphere by high-temperature heat treatment.The mixture homogeneity that tri- kinds of elements of Ni, Co and Al can be effectively improved improves the tap density of persursor material and the sphericity of particle.
Description
Technical field
The present invention relates to anode material for lithium-ion batteries and its preparing technical field of persursor material, especially a kind of nickel
Cobalt aluminium ternary precursor and preparation method thereof and the positive electrode prepared and method.
Background technology
Due to having the advantages that high power capacity and high-energy density, nickel cobalt aluminium lithium ternary material (NCA materials) become high-energy
The ideal positive electrode of density lithium ion positive electrode.Tesla of U.S. electric vehicle uses 8000 more pieces with for NCA materials
For 18650 battery composition battery packs of anode, battery pack power density can reach 170wh/kg, it is ensured that electric vehicle charging is continuous
Boat mileage reaches 350 kilometers or more；Matsushita Corporation of Japan uses NCA materials to can reach for 18650 battery nominal capacitys of anode
3.0Ah or more, this is that other positive electrodes practical at present are incomparable.
The every physical chemistry and chemical property of positive electrode not only with the Macroscopic physical chemical characteristic of persursor material
Related, crystal structure also microcosmic with it has with form directly to be contacted.Therefore, the orderly of persursor material crystal structure is improved
Property, grain form of optimization and second particle pattern for improve nickel cobalt aluminium lithium anode material it is every physically and electrically chemically
Density, multiplying power discharging property, cyclical stability, which can such as be rolled, vital influence.
Ni(OH)2With Co (OH)2Ksp values be respectively 2.0 × 10-15With 1.5 × 10-15, the Ni under alkaline environment2+And Co2 +Precipitation reaction occurs for moment, generates flocculent deposit, the crystallinity of resulting materials is very poor, and physical and chemical performance is severe, can not use.
It controls in crystallization preparation method, uses ammonium hydroxide for complexing agent, nickel, cobalt, the soluble salt solutions of aluminium, precipitating reagent NaOH solution and ammonia
Water three is pumped into simultaneously in the reaction kettle with stirring.In the solution, ammonia first with Ni2+And Co2+It forms nickel ammonia and coordinates ion
[Ni(NH3)6]2+With cobalt ammonia cooperation ion [Co (NH3)6]2+, nickel cobalt ammonia cooperation ion dissociate Ni again2+And Co2+With OH-Hair
Raw precipitation reaction generates Ni1-x-yCox(OH)2, Al substantially not with NH3Cooperation ion is formed, therefore settling velocity is quickly, influences NCA
The crystal structure order of presoma, reaction process are：
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)
Formation and dissociation speed due to cooperation ion is slower relative to the settling velocity of metal ion, reduces total
The speed of precursor reactant process, makes reaction speed be controlled, and the crystal structure of nickel cobalt co-precipitation hydroxide has the sufficient time
Growth, to form crystallinity height, the strong hydroxide materials of lattice order can form density under the action of stirring
High, good sphericity persursor material, this is the premise for ensureing to obtain high-quality NCA materials.
NCA material precursors material Ni at present1-x-yCoxAly(OH)2(0<x≤0.2,0<Y≤0.05) generally use control
It is prepared by crystallisation.Chinese patent CN103094546 describe it is a kind of use sodium metaaluminate for silicon source, ammonium hydroxide is complexing agent, hydrogen-oxygen
Change the preparation method for the nickel cobalt aluminium hydroxide that sodium is precipitating reagent, the mixing salt solution of nickel cobalt, precipitant solution, silicon source solution with
Complexing agent ammonium hydroxide is added in reaction kettle carries out coprecipitation reaction simultaneously, obtains nickel cobalt aluminium hydroxide.Chinese patent CN
105206827A disclose it is a kind of aluminium salt is mixed with complexing agent in advance, form the cooperation solion of Al, mixed with nickel cobalt molten
Liquid carries out coprecipitation reaction under the action of precipitating reagent and complexing agent, obtains spherical nickel cobalt aluminium hydroxide precursor.At this
In a little preparation methods, sodium metaaluminate utilizes its hydrolysis control Al (OH)3Generation, but react without Al3+It generates, Ni, Co, Al
Element cannot be pre-formed stable cooperation ion before precipitation reaction.It, can be with using the acid-soluble salt of Al as silicon source
The complexing agents such as EDTA are pre-formed stable cooperation ion, but Ni, Co element can not be pre-formed stable cooperation ion, influence
The speed of coprecipitation reaction.
Invention content
The technical problem to be solved by the invention is to provide a kind of nickel cobalt aluminium ternary precursor and preparation method thereof and prepare
Positive electrode and method, the mixture homogeneity of tri- kinds of elements of Ni, Co and Al can be effectively improved.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of system of nickel cobalt aluminium ternary precursor
Preparation Method includes the following steps：
1) soluble-salt of nickel, cobalt is proportionally added into ammonium hydroxide, prepares the ammonia cooperation solion I of Ni, Co；To inclined
Complexing agent is added in sodium aluminate solution, it is made to be combined to form Al cooperation solions II with Al elements；By nickel, the soluble-salt of cobalt
It is configured to the mixing salt solution III of Ni, Co metal cation in proportion；Prepare NaOH solution IV；
2) a certain amount of deionized water is housed in advance in reaction kettle, ammonium hydroxide is added and adjusts pH to 10.0~12.0, will prepare
Good solution III, solution IV, solution I and solution II is pumped into reaction kettle simultaneously, fixed solution III, solution I and solution II
Speed, the pH value by adjusting solution in solution IV speed control reaction kettle is maintained in 10.0~12.5 ranges, in reaction kettle
Speed of agitator is 100~500 revs/min, reacts interior solution temperature and is maintained at 30~80 DEG C, the reaction time is not less than 10h, stops
After solution I, II, III, IV is added, slurry obtained by the reaction is separated by solid-liquid separation, the solids deionization obtained after separation
Water washing, dewatered solid dries at 100~150 DEG C, be sieved after obtain nickel cobalt aluminium ternary precursor；The molecule of presoma
Formula is Ni1-x-yCoxAly(OH)2, wherein 0<x≤0.2,0<y≤0.05.
The C of ammonium hydroxide molar concentration described in step 1)NH3Ammonia for 5~15mol/L, formation coordinates Ni and Co in solion I
Molar ratio be (1-x-y)/y, wherein ammoniacal substance amount and ammonia coordinates the total material amount ratio of Ni+Co elements in solion to be
6~10；Mixing salt solution III concentration CsMe-IIIRatio for 0.5~2.3mol/L, Ni and Co elements is Ni:Co=(1-x-y):
y；A concentration of 2~10mol/L of NaOH solution IV.
The nickel, cobalt soluble-salt be sulfate, nitrate, acetate and chloride in it is one or more.
Complexing agent described in step 1) be in disodium ethylene diamine tetraacetate, sodium citrate, sodium lactate, hydrazine hydrate at least
One kind, the addition of the complexing agent are 0.5~2.0 with the molar ratio of Al elements:1.
The Ni obtained after the drying sieving1-x-yCoxAly(OH)2Presoma meso-position radius granularity D50It is 5~20 μm.
It is V that Ni, Co mixing salt solution III flow velocitys are fixed described in step 2)3, then the ammonia cooperation solion I stream of Ni, Co
Fast V1It obtains according to the following formula：
V1=V3×CMe-III/(CNH3×(R2-1/R1)； (1)
In formula：
R1- ammonia coordinates NH in solion3With the amount of substance ratio of Ni+Co；
R2—NH3The ratio of amount of substance and the total material amount of Ni+Co in salting liquid neutralization of ammonia cooperation solion；
CNH3NH in-ammonium hydroxide3Concentration, mol/L；
CMe-IIIThe concentration of Ni+Co, mol/L in-Ni, Co mixing salt solutions.
V3- Ni, Co mixing salt solution flow velocitys.
Aluminum salt solution II flow velocitys V in step 2)2It obtains according to the following formula：
In formula：
CMe-IIIThe concentration of Ni+Co, mol/L in-Ni, Co mixing salt solutions；
CNH3NH in-ammonium hydroxide3Concentration, mol/L；
V3- Ni, Co mixing salt solution flow velocitys, L/min；
V1The ammonia of-Ni, Co coordinates solion flow velocity, L/min；
R1- ammonia coordinates NH in solion3With the amount of substance ratio of Ni+Co.
Nickel cobalt aluminium ternary precursor made from above-mentioned preparation method.
The method that positive electrode is prepared using above-mentioned nickel cobalt aluminium ternary precursor, using high-speed mixer, by what is obtained
Nickel cobalt aluminium ternary precursor and lithium hydroxide are mixed in a certain ratio uniformly, in bell-type roaster, with the speed of 2~10 DEG C/min
Rate is warming up to 600~800 DEG C, keeps the temperature 5~20h, and oxygen is passed through into bell-type roaster, ensures that oxygen content is more than in stove
70%, it is naturally cooling to room temperature after heat preservation, the blank roasted obtains nickel cobalt aluminium tertiary cathode after crushing, being sieved
Material, the amount of substance ratio Li/ (Ni+Co+Al) of Li elements and Ni, Co, Al element in presoma is 0.9~1.2 in lithium hydroxide：
1。
Nickel cobalt aluminium tertiary cathode material made from above-mentioned preparation method.
The beneficial effects of the invention are as follows：The mixture homogeneity of tri- kinds of elements of Ni, Co and Al can be effectively improved, utmostly
Ground avoids the generation of Al element Local enrichment phenomenons, improves the tap density of persursor material and the sphericity of particle.
Description of the drawings
Fig. 1 is the flow chart of the present invention.
Specific implementation mode
Invention is further described in detail with reference to the accompanying drawings and detailed description：
The soluble-salt of Ni, Co are added in ammonium hydroxide by the present invention first, in Ni, Co element ratio and target molecule formula
Ni, Co element ratio are identical, and the ammonia cooperation ion for Ni, Co that the addition for controlling soluble-salt forms it into close saturation is molten
Liquid is pumped into using this solution as complexing agent in reaction kettle.It is by taking the method, reaction equation (1) and (2) is pre- outside reaction kettle
It first completes, forms stable nickel cobalt complex ion, part Ni can be effectively prevented from2+、Co2+Before not forming cooperation ion just
With OH—Precipitation reaction occurs, 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 reaction-33, with Ni (OH)2With Co (OH)2Ksp values difference compared with
Greatly, thus settling velocity faster, increase the randomness of crystal structure.Therefore it needs to take measures to reduce Al (OH)3Precipitation is anti-
The speed answered is so that itself and Ni (OH)2With Co (OH)2Settling velocity is mutually coordinated.Use sodium metaaluminate for aluminium salt, in H+Effect
Under, following reaction occurs for meta-aluminic acid radical ion：
H++AlO2 -+H2O→Al(OH)3↓ (4)
Under the reaction system of alkalinity, 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, keep it consistent with the settling velocity of Ni, Co hydroxide, improve nickel cobalt aluminium hydroxide forerunner
The crystal order of body material improves the density of crystal structure intensity and second particle.
If shown in specific preparation flow Fig. 1, comprise the following steps：
1) will be (Ni+Co)/NH according to molar ratio3=1/6~1/10, add into the ammonium hydroxide of a concentration of 5~15mol/L
Enter the soluble-salt of Ni, Co, be configured to nickel ammonia and cobalt ammonia cooperation solion (I) after dissolving, the ratio of wherein Ni and Co are (1-
x-y)/x；
2) compound concentration is the sodium aluminate solution (II) of 0.5~5mol/L, complexing agent is added into solution, complexing agent is
NaF、NH3F, at least one of disodium ethylene diamine tetraacetate (EDTA), sodium citrate, sodium lactate, the addition of the complexing agent
Amount and the molar ratio of Al elements are 0.5~2.0:1；Ratio compound concentration according to Ni/Co=(1-x-y)/y is 1~2.3mol/
The nickel cobalt mixing salt solution (III) of L, salt can be nitrate, sulfate and chloride；
3) sodium hydroxide solution (IV) that compound concentration is 2~10mol/L is used as precipitating reagent；
4) solution (I), solution (II), solution (III) and solution (IV) cocurrent are pumped into reaction kettle, respectively fixed solution (I),
The speed of solution (II) and solution (III) is enabled by adjusting solution ph in solution (IV) speed control reaction kettle 10.0~12.5
Solution (III) flow velocity is V3, then V1=(0.5~2.0) × (CMe/CNH3)×V3,
5) reaction temperature is 30~80 DEG C, and 100~500 revs/min of speed of agitator, reaction kettle top is equipped with overflow port, kettle
Solution is overflowed from the overflow pipe on reaction kettle top after full, spillage solution is collected, after separation of solid and liquid, washing, drying, sieving
Obtain nickel cobalt aluminium ternary precursor.
6) high-speed mixer is used, by the nickel cobalt aluminium ternary precursor obtained in step 5) and lithium hydroxide according to Li/ (Ni
+ Co+Al)=0.9~1.20 ratio is uniformly mixed, in bell-type roaster, 600 are warming up to the rate of 2~10 DEG C/min
~800 DEG C, 5~20h is kept the temperature, oxygen is passed through in roasting process, ensures that oxygen content is not less than 70% in bell-type roaster, heat preservation
After be naturally cooling to room temperature, the blank roasted obtains nickel cobalt aluminium tertiary cathode material after crushing, being sieved.
Embodiment 1
The ratio of nickel sulfate 368.9g and cobaltous sulfate 74.0g are added according to every liter of ammonium hydroxide for the ammonium hydroxide for taking a concentration of 10mol/L
Nickel sulfate and cobaltous sulfate is added, stirring makes nickel sulfate be dissolved with cobaltous sulfate, makes the ammonia cooperation solion (solution of Ni, Co
I), by every liter of 81.9gNaAlO2Ratio prepare inclined sodium chlorate solution's (solution II), it is (molten to prepare 6mol/L sodium hydroxide solutions
Liquid IV), the mixing salt solution of nickel sulfate and cobaltous sulfate, salting liquid total concentration are prepared according to the ratio of Ni/Co=0.842/0.158
For 2.5mol/L (solution III).Four kinds of solution cocurrents are added in reaction kettle, wherein the stream of nickel cobalt salting liquid (solution III)
Speed be 100ml/min, from formula (1) obtain nickel, cobalt cooperation solion flow velocity be 30ml/min, inclined aluminium is obtained by formula (2)
Acid sodium solution flow velocity is 15.8ml/min, adjusts sodium hydroxide solution (solution IV) flow velocity, and pH value control in reaction kettle is made to exist
Between 11.0 ± 0.1, after reacting 20h, stops charging, obtained slurry is separated by solid-liquid separation, obtained solids is spent
Ion water washing, dewatered solids dry 8~10h at 120~130 DEG C, obtain nickel cobalt aluminium hydroxide precursor
Ni0.8Co0.15Al0.05(OH)2。
Using high-speed mixer by the obtained nickel cobalt aluminium presoma of previous step and lithium hydroxide according to Li/Me=1.10's
Ratio is uniformly mixed, and 750 DEG C are warming up to the speed of 10 DEG C/min in van-type stove, keeps the temperature 10h, oxygen is passed through in roasting process
Gas, flow 0.6m3/ h, oxygen content is more than 90% in stove, is naturally cooling to room temperature after heat preservation, the blank roasted
Nickel cobalt aluminium tertiary cathode material is obtained after crushing, being sieved.After tested, nickel cobalt aluminium tertiary cathode material D50It is 10.2 μm, shakes
Real density reaches 2.62g/cm3, chemical property is tested using 2032 button cells, 0.1C is put in 3.0~4.3V voltage ranges
Capacitance reaches 198mAh/g.
Embodiment 2
The ratio of nickel sulfate 406.5g and cobaltous sulfate 33.80g is added according to every liter of ammonium hydroxide for the ammonium hydroxide for taking a concentration of 10mol/L
Nickel sulfate and cobaltous sulfate is added in example, and stirring makes nickel sulfate be dissolved with cobaltous sulfate, and the ammonia cooperation solion for making Ni, Co is (molten
Liquid I), by every liter of 163.9gNaAlO2Ratio prepare inclined sodium chlorate solution's (solution II), prepare 6mol/L sodium hydroxide solutions
(solution IV), the mixing salt solution of nickel sulfate and cobaltous sulfate is prepared according to the ratio of Ni/Co=0.928/0.072, and salting liquid is total
A concentration of 2.3mol/L (solution III).Four kinds of solution cocurrents are added in reaction kettle, wherein nickel cobalt salting liquid (solution III)
Flow velocity be 200ml/min, nickel is obtained from formula (1), solion flow velocity V with cobalt1For 48ml/min, obtained by formula (2)
To sodium aluminate solution flow velocity V2For 25.3ml/min, sodium hydroxide solution (solution IV) flow velocity is adjusted, pH value in reaction kettle is made
Control is between 10.8 ± 0.1, after reacting 10h, stops charging, is separated by solid-liquid separation to obtained slurry, obtained solid
Object is washed with deionized, and dewatered solids dries 8~10h at 120~130 DEG C, obtains nickel cobalt aluminium hydroxide forerunner
Body Ni0.9Co0.07Al0.03(OH)2。
Using high-speed mixer by the obtained nickel cobalt aluminium presoma of previous step and lithium hydroxide according to Li/Me=1.20's
Ratio is uniformly mixed, and 600 DEG C are warming up to the speed of 10 DEG C/min in van-type stove, keeps the temperature 10h, oxygen is passed through in roasting process
Gas, flow 0.6m3/ h, oxygen content is more than 90% in stove, is naturally cooling to room temperature after heat preservation, the blank roasted
Nickel cobalt aluminium tertiary cathode material is obtained after crushing, being sieved.After tested, nickel cobalt aluminium tertiary cathode material D50It is 9.7 μm, jolt ramming
Density reaches 2.63g/cm3, chemical property is tested using 2032 button cells, 0.1C discharges in 3.0~4.3V voltage ranges
Capacity reaches 205mAh/g.
Embodiment 3
Prepare Ni0.98Co0.01Al0.01(OH)2Presoma:The ammonium hydroxide for taking a concentration of 15mol/L is added according to every liter of ammonium hydroxide
Nickel sulfate and cobaltous sulfate is added in the ratio of nickel sulfate 390.3g and cobaltous sulfate 4.3g, and stirring makes nickel sulfate be dissolved with cobaltous sulfate, matches
The ammonia cooperation solion (solution I) for making Ni, Co, by every liter of 245.9gNaAlO2Ratio to prepare inclined sodium chlorate solution (molten
Liquid II), 10mol/L sodium hydroxide solutions (solution IV) are prepared, nickel sulfate is prepared according to the ratio of Ni/Co=0.928/0.072
With the mixing salt solution of cobaltous sulfate, salting liquid total concentration is 2.3mol/L (solution III).Four kinds of solution cocurrents are added to reaction
In kettle, wherein the flow velocity of nickel cobalt salting liquid (solution III) is 150ml/min, obtains nickel from formula (1), solion with cobalt
Flow velocity V1For 48ml/min, sodium aluminate solution flow velocity V is obtained by formula (2)2For 6.4ml/min, sodium hydroxide solution is adjusted
(solution IV) flow velocity makes pH value control in reaction kettle after reaction 30h, stop charging, to obtained between 11.5 ± 0.1
Slurry is separated by solid-liquid separation, and obtained solids is washed with deionized, and dewatered solids dries 8 at 140~150 DEG C~
10h obtains nickel cobalt aluminium hydroxide precursor Ni0.98Co0.01Al0.01(OH)2。
Using high-speed mixer by the obtained nickel cobalt aluminium presoma of previous step and lithium hydroxide according to Li/Me=1.10's
Ratio is uniformly mixed, and 800 DEG C are warming up to the speed of 2 DEG C/min in van-type stove, keeps the temperature 10h, oxygen is passed through in roasting process,
Flow is 0.6m3/ h, oxygen content is more than 90% in stove, and room temperature is naturally cooling to after heat preservation, the blank warp roasted
Nickel cobalt aluminium tertiary cathode material is obtained after crossing crushing, sieving.After tested, nickel cobalt aluminium tertiary cathode material D50It is 8.5 μm, vibration density
Degree reaches 2.43g/cm3, using 2032 button cells test chemical property, in 3.0~4.3V voltage ranges, 0.1C, which discharges, holds
Amount reaches 209.1mAh/g.
Embodiment 4
Prepare Ni0.7Co0.25Al0.05(OH)2Presoma:Sulphur is added according to every liter of ammonium hydroxide in the ammonium hydroxide for taking a concentration of 5mol/L
Nickel sulfate and cobaltous sulfate is added in the ratio of sour nickel 121.0g and cobaltous sulfate 46.2g, and stirring makes nickel sulfate be dissolved with cobaltous sulfate, prepares
The ammonia cooperation solion (solution I) for going out Ni, Co, by every liter of 278.7gNaAlO2Ratio prepare inclined sodium chlorate solution's (solution
II), 2mol/L sodium hydroxide solutions (solution IV) are prepared, nickel sulfate and sulphur are prepared according to the ratio of Ni/Co=0.737/0.263
The mixing salt solution of sour cobalt, salting liquid total concentration are 1.0mol/L (solution III).Four kinds of solution cocurrents are added to reaction kettle
In, wherein the flow velocity of nickel cobalt salting liquid (solution III) is 200ml/min, obtains nickel from formula (1), solion stream with cobalt
Fast V1For 48ml/min, sodium aluminate solution flow velocity V is obtained by formula (2)2For 6.4ml/min, it is (molten to adjust sodium hydroxide solution
Liquid IV) flow velocity, so that pH value control in reaction kettle after reaction 30h, is stopped charging, to obtained slurry between 12.0 ± 0.1
It being separated by solid-liquid separation, obtained solids is washed with deionized, and dewatered solids dries 8~10h at 140~150 DEG C,
Obtain nickel cobalt aluminium hydroxide precursor Ni0.7Co0.25Al0.05(OH)2。
Using high-speed mixer by the obtained nickel cobalt aluminium presoma of previous step and lithium hydroxide according to Li/Me=1.20's
Ratio is uniformly mixed, and 800 DEG C are warming up to the speed of 2 DEG C/min in van-type stove, keeps the temperature 10h, oxygen is passed through in roasting process,
Flow is 0.6m3/ h, oxygen content is more than 70% in stove, and room temperature is naturally cooling to after heat preservation, the blank warp roasted
Nickel cobalt aluminium tertiary cathode material is obtained after crossing crushing, sieving.After tested, nickel cobalt aluminium tertiary cathode material D50It is 6.5 μm, vibration density
Degree reaches 2.41g/cm3, using 2032 button cells test chemical property, in 3.0~4.3V voltage ranges, 0.1C, which discharges, holds
Amount reaches 190.7mAh/g.
Embodiment 5
Prepare Ni0.75Co0.23Al0.02(OH)2Presoma:Sulphur is added according to every liter of ammonium hydroxide in the ammonium hydroxide for taking a concentration of 5mol/L
Nickel sulfate and cobaltous sulfate is added in the ratio of sour nickel 295.3g and cobaltous sulfate 59.0g, and stirring makes nickel sulfate be dissolved with cobaltous sulfate, prepares
The ammonia cooperation solion (solution I) for going out Ni, Co, by every liter of 245.9g NaAlO2Ratio prepare inclined sodium chlorate solution's (solution
II), 4mol/L sodium hydroxide solutions (solution IV) are prepared, nickel sulfate and sulphur are prepared according to the ratio of Ni/Co=0.765/0.235
The mixing salt solution of sour cobalt, salting liquid total concentration are 1.5mol/L (solution III).Four kinds of solution cocurrents are added to reaction kettle
In, wherein the flow velocity of nickel cobalt salting liquid (solution III) is 50ml/min, obtains nickel from formula (1), solion flow velocity with cobalt
V1For 7.03ml/min, sodium aluminate solution flow velocity V is obtained by formula (2)2For 1.1ml/min, it is (molten to adjust sodium hydroxide solution
Liquid IV) flow velocity, so that pH value control in reaction kettle after reaction 100h, is stopped charging, to obtained slurry between 12.4~12.5
Material is separated by solid-liquid separation, and obtained solids is washed with deionized, and dewatered solids dries 8 at 140~150 DEG C~
10h obtains nickel cobalt aluminium hydroxide precursor Ni0.75Co0.23Al0.02(OH)2。
Using high-speed mixer by the obtained nickel cobalt aluminium presoma of previous step and lithium hydroxide according to Li/Me=1.15's
Ratio is uniformly mixed, and 800 DEG C are warming up to the speed of 8 DEG C/min in van-type stove, keeps the temperature 10h, oxygen is passed through in roasting process,
Flow is 0.6m3/ h, oxygen content is not less than 80% in stove, is naturally cooling to room temperature after heat preservation, the blank roasted
Nickel cobalt aluminium tertiary cathode material is obtained after crushing, being sieved.After tested, nickel cobalt aluminium tertiary cathode material D50It is 5.2 μm, jolt ramming
Density reaches 2.11g/cm3, chemical property is tested using 2032 button cells, 0.1C discharges in 3.0~4.3V voltage ranges
Capacity reaches 195.2mAh/g.
In conclusion present disclosure is not limited in the above embodiments, the knowledgeable people in same area can
Can propose other embodiments easily within the technological guidance's thought of the present invention, but this embodiment is included in this hair
Within the scope of bright.
Claims (8)
1. a kind of preparation method of nickel cobalt aluminium ternary precursor, which is characterized in that include the following steps：
1) soluble-salt of nickel, cobalt is proportionally added into ammonium hydroxide, prepares the ammonia cooperation solion I of Ni, Co；To meta-aluminic acid
Complexing agent is added in sodium solution, it is made to be combined to form Al cooperation solions II with Al elements；By the soluble-salt of nickel, cobalt press than
Example is configured to the mixing salt solution III of Ni, Co metal cation；Prepare NaOH solution IV；
2) a certain amount of deionized water is housed in advance in reaction kettle, ammonium hydroxide is added and adjusts pH to 10.0~12.0, it will be prepared
Solution III, solution IV, solution I and solution II are pumped into reaction kettle simultaneously, fixed solution III, solution I and solution II speed,
PH value by adjusting solution in solution IV speed control reaction kettle is maintained in 10.0~12.5 ranges, stirring turn in reaction kettle
Speed is 100~500 revs/min, reacts interior solution temperature and is maintained at 30~80 DEG C, and the reaction time is not less than 10h, stops being added molten
After liquid I, II, III, IV, slurry obtained by the reaction is separated by solid-liquid separation, the solids obtained after separation is washed with deionized water
Wash, dewatered solid dries at 100~150 DEG C, be sieved after obtain nickel cobalt aluminium ternary precursor；The molecular formula of presoma is
Ni1-x-yCoxAly(OH)2, wherein 0<x≤0.2,0<y≤0.05；
Wherein,
Fixed Ni, Co mixing salt solution III flow velocitys are V3, then the ammonia cooperation solion I flow velocitys V of Ni, Co1Based on following formula
It obtains：
V1=V3×CMe-III/(CNH3×(R2-1/R1)； (1)
In formula：
R1- ammonia coordinates NH in solion3With the amount of substance ratio of Ni+Co；
R2—NH3The ratio of amount of substance and the total material amount of Ni+Co in salting liquid neutralization of ammonia cooperation solion；
CNH3NH in-ammonium hydroxide3Concentration, mol/L；
CMe-IIIThe concentration of Ni+Co, mol/L in-Ni, Co mixing salt solutions；
V3- Ni, Co mixing salt solution flow velocitys；
Aluminum salt solution II flow velocitys V2It obtains according to the following formula：
In formula：
CMe-IIIThe concentration of Ni+Co, mol/L in-Ni, Co mixing salt solutions；
CNH3NH in-ammonium hydroxide3Concentration, mol/L；
V3- Ni, Co mixing salt solution flow velocitys, L/min；
V1The ammonia of-Ni, Co coordinates solion flow velocity, L/min；
R1- ammonia coordinates NH in solion3With the amount of substance ratio of Ni+Co.
2. the preparation method of nickel cobalt aluminium ternary precursor according to claim 1, which is characterized in that ammonia described in step 1)
Water molar concentration CNH3Ammonia for 5~15mol/L, formation coordinates the molar ratio of Ni and Co in solion I to be (1-x-y)/x,
Wherein the total material amount ratio of Ni+Co elements is 6~10 in ammoniacal substance amount and ammonia cooperation solion；Mixing salt solution III is dense
Spend CMe-IIIRatio for 0.5~2.3mol/L, Ni and Co elements is Ni:Co=(1-x-y):x；NaOH solution IV a concentration of 2~
10mol/L。
3. the preparation method of nickel cobalt aluminium ternary precursor according to claim 1, which is characterized in that the nickel, cobalt can
Soluble is one or more in sulfate, nitrate, acetate and chloride.
4. the preparation method of nickel cobalt aluminium ternary precursor according to claim 1, which is characterized in that described in step 1)
Complexing agent is at least one of disodium ethylene diamine tetraacetate, sodium citrate, sodium lactate, hydrazine hydrate, the addition of the complexing agent
Amount and the molar ratio of Al elements are 0.5~2.0:1.
5. the preparation method of nickel cobalt aluminium ternary precursor according to claim 1, which is characterized in that after the drying sieving
Obtained Ni1-x-yCoxAly(OH)2Presoma meso-position radius granularity D50It is 5~20 μm.
6. the nickel cobalt aluminium ternary precursor as made from the preparation method of any one of claim 1-5.
7. the method for preparing positive electrode using the nickel cobalt aluminium ternary precursor of claim 6, which is characterized in that mixed using high speed
Obtained nickel cobalt aluminium ternary precursor and lithium hydroxide are mixed in a certain ratio uniformly, in bell-type roaster, with 2 by conjunction machine
The rate of~10 DEG C/min is warming up to 600~800 DEG C, keeps the temperature 5~20h, and oxygen is passed through into bell-type roaster, ensures oxygen in stove
Gas content is more than 70%, is naturally cooling to room temperature after heat preservation, the blank roasted obtains nickel cobalt after crushing, being sieved
Aluminium tertiary cathode material, the amount of substance ratio Li/ (Ni+Co+Al) of Li elements and Ni, Co, Al element in presoma in lithium hydroxide
It is 0.9~1.2：1.
8. nickel cobalt aluminium tertiary cathode material made from preparation method as claimed in claim 7.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1893151A (en) * | 2005-07-01 | 2007-01-10 | 深圳市比克电池有限公司 | Method for preparing lithium composite metal oxide |
| CN101262061A (en) * | 2008-04-14 | 2008-09-10 | 天津巴莫科技股份有限公司 | Spherical aluminum-doped nickel cobalt lithium for lithium ion battery and its making method |
| CN104425815A (en) * | 2013-08-19 | 2015-03-18 | 日电（中国）有限公司 | High-density spherical Ni-Co lithium aluminate material and preparation of precursor of the material |
| CN105206827A (en) * | 2015-08-31 | 2015-12-30 | 宁波金和锂电材料有限公司 | Nickel, cobalt and aluminum hydroxide and preparation method thereof and cathode material for lithium ion cell |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4586991B2 (en) * | 2006-03-24 | 2010-11-24 | ソニー株式会社 | Positive electrode active material, method for producing the same, and secondary battery |
-
2016
- 2016-08-08 CN CN201610650420.3A patent/CN106299347B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1893151A (en) * | 2005-07-01 | 2007-01-10 | 深圳市比克电池有限公司 | Method for preparing lithium composite metal oxide |
| CN101262061A (en) * | 2008-04-14 | 2008-09-10 | 天津巴莫科技股份有限公司 | Spherical aluminum-doped nickel cobalt lithium for lithium ion battery and its making method |
| CN104425815A (en) * | 2013-08-19 | 2015-03-18 | 日电（中国）有限公司 | High-density spherical Ni-Co lithium aluminate material and preparation of precursor of the material |
| CN105206827A (en) * | 2015-08-31 | 2015-12-30 | 宁波金和锂电材料有限公司 | Nickel, cobalt and aluminum hydroxide and preparation method thereof and cathode material for lithium ion cell |
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