CN108428885A - A kind of method that continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate - Google Patents
A kind of method that continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate Download PDFInfo
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- H—ELECTRICITY
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract
The present invention relates to a kind of methods that continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, belong to technical field of lithium ion.The technical problem to be solved by the present invention is to provide a kind of methods that continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate.This method is coated by two steps type screw extruder, obtains the nickelic ternary forerunner particle that aluminium oxide continuously coats dispersion.It is not only evenly coated, and is coated in continuous high shear process, the controllable cladding of thickness is realized by the metering of aluminium isopropoxide and screw speed, solves current cladding process defect rambunctious.Realize continuous-stable, the nickelic nickel cobalt aluminium ternary material of controllable preparation.This method is continuously controllable, and the pellumina that surface is evenly distributed is connected firmly with active material, effectively inhibits the side reaction with electrolyte, so that the battery being made of the ternary material that this method is prepared, reversible specific capacity is high for the first time, good cycle.
Description
Technical field
The present invention relates to a kind of method that continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, belong to lithium from
Sub- battery technology field.
Background technology
Lithium ion battery is a kind of secondary cell（That is rechargeable battery）, it relies primarily on lithium ion（Li+）Positive and negative
Movement carrys out work between pole.In charge and discharge process, Li+Round-trip insertion and deintercalation between two electrodes：When charging, Li+From just
Pole deintercalation is embedded in cathode by electrolyte, and cathode is in rich lithium state；It is then opposite when electric discharge.
With traditional accumulator comparatively, lithium ion battery not only energy higher, discharge capability is stronger, and cycle life is more
Long, therefore, lithium ion battery has broad prospects in the application of electric vehicle.In lithium ion battery, positive electrode is it
Most important component part, and determine the key of performance of lithium ion battery.Under the premise of same capacity plays, to improve
The volume energy density of battery is it is necessary to improving the loading of cell active materials unit volume.And stratiform ternary material NCA nickel cobalts
Lithium aluminate（Ni nickel, Co cobalts, Al aluminium）It is the tertiary cathode material of current better performances.But NCA capacity attenuations are serious, especially
When nickelic, cyclical stability is poor.Structure is mainly manifested in be easily varied, generate the influences such as interfacial film use with electrolyte.
Surface coating modification is the current improvement common technological means of NCA nickel cobalt lithium aluminate stability.By coating modification,
To inhibit the side reaction on surface, improve the stability of surface texture, to reduce the capacity attenuation in cyclic process, it is steady to improve heat
It is qualitative.
Chinese patent CN106910881A discloses the preparation method of metatitanic acid lithium cladding nickel cobalt lithium aluminate cathode material.It should
Metatitanic acid lithium cladding nickel cobalt lithium aluminate cathode material preparation method be：Titanium dioxide and nickel cobalt aluminic acid powder for lithium are added simultaneously
In coating unit, process is fully dispersed, adsorbs and recombinates, and obtains solid powder；Solid powder is put into Muffle furnace heating, in sky
It is roasted under gas atmosphere, is then naturally cooling to room temperature, obtain the nickel cobalt lithium aluminate of metatitanic acid lithium cladding.The invention uses metatitanic acid
Lithium coats surface, and the insertion and abjection of Li+ can be better achieved in conductor material of the metatitanic acid lithium as Li+, improves
The cycle performance and high rate performance of material；It is coated simultaneously using metatitanic acid lithium, to reduce NCA to moisture sensitivity, reduces electrode
Material and organic electrolyte are in direct contact, and are further improved the structural stability of NCA, are improved the safety of material.
Chinese patent CN106711444A discloses a kind of preparation for the nickel cobalt lithium aluminate cathode material that in-stiu coating is modified
Method.This method includes：Step 1, titanium source is dissolved in absolute ethyl alcohol, prepares titanium covering liquid；Step 2, will
Ni0.80Co0.15Al0.05(OH)2Presoma, lithium source and complexing agent are added in above-mentioned titanium covering liquid, and heat and stir at 60~80 DEG C
It mixes to obtain colloidal sol；Step 3, above-mentioned colloidal sol is placed in through drying, grinding and sieving gained powder mixing material in resistance furnace successively
It is sintered 10~20h at 800~900 DEG C, sintering feed is obtained after cooling；Step 4, above-mentioned sintering feed is broken, sieving, obtains table
Bread covers Li4Ti5O12Nickel cobalt lithium aluminate cathode material.Covering material prepared by the invention is lithium-containing compound, with Li4Ti5O12
As clad, its cycle performance can be increased substantially under the premise of not significantly affecting nickel cobalt lithium aluminate cathode material capacity.
Chinese patent 106328936A discloses the preparation method of the spherical nickel cobalt aluminium presoma of cladding, nickel cobalt aluminic acid pole piece
The preparation method of material.The preparation method of the spherical nickel cobalt aluminium presoma of cladding, includes the following steps：It is molten metal cation salt will to be coated
Liquid, complexing agent aqueous solution and precipitating reagent aqueous solution are continuously injected into nickel cobalt aluminium hydroxide co-precipitation presoma slurries, and control is anti-
The system pH of answering is 8.5~12.5, the content of free ammonia is 9.0~15.0g/L in reaction system, must coat spherical nickel cobalt aluminium forerunner
Body；The complexing agent is ammonium hydroxide.The preparation method of the spherical nickel cobalt aluminium presoma of cladding of the present invention, it is total in nickel cobalt aluminium hydroxide
The hydroxide of presoma surface metal ions is precipitated, the spherical nickel cobalt aluminium presoma of cladding obtained is spherical in shape, and wraps
It covers evenly, the impedance of pole piece can be reduced, while improving the cycle performance of pole piece.
To sum up, the surface covering material of nickel cobalt lithium aluminate has much at present, and the method coated is mainly by directly mixed
Closing, precipitating or stirring makes covering material and active material bond, and such method, common problem is that covering material is difficult to
It is effectively connect with active material, to cause the adhesion property of covering material and matrix bad, in addition, there is also cladding thickness
Not easy to control, cladding is uneven, in long-term cyclic process coating film easily split failure the defects of.
Invention content
For existing nickelic nickel cobalt aluminium ternary material coating modification be difficult to control cladding thickness, coating is uneven, film with
Active material connects unstable defect, and the present invention proposes that a kind of continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate
The method of material.
First technical problem that the present invention solves is to provide a kind of continuous coating preparation nickelic ternary lithium of nickel cobalt lithium aluminate
The method of battery material.
The method that the continuous coating of the present invention prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, includes the following steps：
A, the preparation of presoma：In nickel ion, cobalt ions and aluminum ions mixed aqueous solution, sodium hydroxide is added as precipitation
Agent, then it is 9~10 to adjust pH value with ammonium hydroxide, 2~8h of coprecipitation reaction is filtered, washed, and obtains nickelic ternary precursor；Wherein,
In molar ratio, Ni：Co：Al=8:1~2:0.1~1；
B, two steps type Screw Extrusion：Lithium salts is mixed with nickelic ternary precursor, is sent into two steps type screw extruder, control first
Rank screw extruder temperature is 150~200 DEG C；Second-order screw extruder temperature is 250~300 DEG C；And it is tieed up by oxygen pump
The oxygen-enriched environment in two steps type screw rod is held, aluminium isopropoxide is added in the second section screw extruder, passes through two steps type Screw Extrusion
After machine squeezes out, the nickelic ternary forerunner particle that aluminium oxide continuously coats dispersion is obtained；
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 4~8h in 850~950 DEG C, obtains nickel
The nickelic ternary material of cobalt lithium aluminate.
The method of the present invention is sheared using the first rank of two steps type screw rod and disperses lithium ion in nickelic ternary predecessor, and
Aluminium isopropoxide is added by metering pump in second-order, is continuously scattered in the nickelic ternary that oxidation in predecessor forms alumina-coated
Forerunner's particle.It is not only evenly coated, and is coated in continuous high shear process, pass through the metering pump and spiral shell of aluminium isopropoxide
Bar rotating speed realizes the controllable cladding of thickness, solves current cladding process defect rambunctious.It realizes continuous-stable, can control
Standby nickelic nickel cobalt aluminium ternary material.This method is continuously controllable, and the pellumina that surface is evenly distributed is connected firmly with active material,
Effectively inhibit the side reaction with electrolyte.
A steps are the step of preparing nickelic ternary precursor.By nickel cobalt aluminium metallic compound be configured to containing nickel ion, cobalt from
Sub and aluminum ions mixed aqueous solution makees precipitating reagent using sodium hydroxide, and ammonium hydroxide adjusts pH value, before co-precipitation obtains nickelic ternary
Drive body Ni0.8Co0.15Al0.05(OH)2。
In nickel ion, cobalt ions and aluminum ions mixed aqueous solution, in molar ratio, Ni：Co：Al=8:1~2:0.1~1,
It is preferred that in molar ratio, Ni：Co：Al=8:1.5:0.5.
Conventional method may be used in nickel ion, cobalt ions and aluminum ions mixed aqueous solution to be configured.For example, by sulphur
Sour nickel, cobaltous sulfate and aluminum sulfate difference are soluble in water, then each solution is mixed to get mixed aqueous solution.The gold of mixed aqueous solution
Coprecipitation reaction will be influenced by belonging to ion concentration.Preferably, the concentration of metal ions in mixed aqueous solution is 0.5~2mol/L, more
Preferably, the concentration of metal ions in mixed aqueous solution is 1.0mol/L.Wherein, the concentration of metal ions is that mixing is water-soluble
The concentration of all metal ions in liquid, i.e., nickel ion, cobalt ions and aluminium ion concentration the sum of.
Sodium hydroxide is preferably added mode and is added for solution, i.e., sodium hydroxide is configured to aqueous solution as precipitating reagent,
It is added in nickel ion, cobalt ions and aluminum ions mixed aqueous solution.Wherein, the concentration and addition of sodium hydroxide solution can
Influence the formation of nickelic ternary precursor.Preferably, a concentration of 3~5mol/L of sodium hydroxide solution；It is furthermore preferred that hydroxide
A concentration of 4mol/L of sodium solution.
Preferably, the volume ratio of mixed aqueous solution and sodium hydroxide solution is 1:0.5~2；It is further preferred that mixing water
The volume ratio of solution and sodium hydroxide solution is 1:1.
B step uses two steps type screw extruder, and lithium salts is mixed with nickelic ternary precursor, and coats oxygen on its surface layer
Change aluminium, obtains the nickelic ternary forerunner particle that aluminium oxide continuously coats dispersion.
Lithium salts commonly used in the art is suitable for the present invention.Preferably, the lithium salts is lithium sulfate.The molecular formula of lithium sulfate
For Li2SO4, molecular weight 109.94 is colourless monoclinic crystal or white crystals sprills, is dissolved in water, does not dissolve in acetone and nothing
Water-ethanol.Lithium sulfate used in the present invention may be used commercially available.
Preferably, lithium salts and nickelic ternary precursor in mass ratio 0.3~1:1 mixing；It is further preferred that lithium salts and height
Nickel ternary precursor in mass ratio 0.6:1 mixing.
B step of the present invention is carried out using two steps type screw extruder.Two steps type screw extruder is to solve one
Mutual restrain of multi-functional-area on root screw rod and the concept proposed, i.e., come each function distinguishing of an extruder, respectively
It is put on two extruders and completes, two extruders are cascaded, complete entire extrusion together.First extruder
Referred to as the first rank, second extruder are known as second-order, are exhausted in two extruders joint.Dual inoculation can be in
Right-angle array can also be in aligned arrangement.The two functionality of two steps type screw extruder series detaches, and operator is allowed to carry out
More flexible predictable mixing process and temperature control.
In the methods of the invention, the first rank screw extruder is primarily to lithium salts and nickelic ternary precursor are mixed equal
It is even, disperse lithium ion in nickelic ternary predecessor using shearing.Therefore, it is necessary to control the first rank screw extruder temperature to be
150~200 DEG C；And the oxygen-enriched environment in the first rank screw rod is maintained by oxygen pump, to form the nickelic ternary of nickel cobalt lithium aluminate
Material.First rank extruder can be the continuous mixer of double screw extruder, single screw extrusion machine or other forms.Due to
Under identical extrusion capacity, residence time of the material in double screw extruder is short, and the good mixing effect of twin-screw, has good
Self-cleaning function, it is therefore preferable that the first rank screw extruder is double screw extruder.
Second-order screw extruder also needs aluminium isopropoxide being added by metering pump other than further disperseing material, even
The continuous nickelic ternary forerunner particle for being scattered in oxidation in predecessor and forming alumina-coated.In the step, second-order spiral shell need to be controlled
Bar extruder temperature is 250~300 DEG C；And the oxygen-enriched environment in second-order screw rod is maintained by oxygen pump.Preferably, second
Screw extruder uses the single screw extrusion machine of larger diameter energy low-speed running.
After being squeezed out under oxygen-enriched environment by two steps type screw extruder, aluminium oxide continuously coats dispersion nickelic three are obtained
First forerunner's particle.Not only be evenly coated, and coated in continuous high shear process, by the metering pump of aluminium isopropoxide and
Screw speed realizes the controllable cladding of thickness, and the addition of aluminium isopropoxide is big, screw speed is slow, then the thickness of clad is larger,
Vice versa, thus solves current cladding process defect rambunctious.
Oxygen-enriched environment of the present invention refers to that the percentage by volume of oxygen is greater than or equal to 21% environment, that is, compares air
In the high environment of oxygen concentration.Oxygen-enriched environment can be realized by conventional oxygen pump.
In b step, the thickness of clad can be adjusted by adjusting the addition of aluminium isopropoxide, after improving cladding
The performance of material, it is preferred that the addition of aluminium isopropoxide is the 20~60% of nickelic ternary precursor weight.It is further preferred that
The addition of aluminium isopropoxide is the 40% of nickelic ternary precursor weight.
The calcining of step c can further obtain the nickelic ternary material of nickel cobalt lithium aluminate.Preferably, the burning in step c
Junction temperature is 900 DEG C.The time of sintering is the normal sintering time of this field, it is preferred that sintering time is 4~8h.Further
Preferably, sintering time 6h.Sintering can carry out in conventional agglomerating plant, for example, in continuous tunnel furnace in be sintered.
Compared with prior art, the present invention has the advantages that：
The present invention is coated by two steps type screw extruder, obtains the nickelic ternary forerunner that aluminium oxide continuously coats dispersion
Particle.It is not only evenly coated, and is coated in continuous high shear process, the metering by aluminium isopropoxide and screw speed
It realizes the controllable cladding of thickness, solves current cladding process defect rambunctious.It is nickelic to realize continuous-stable, controllable preparation
Nickel cobalt aluminium ternary material.This method is continuously controllable, and the pellumina that surface is evenly distributed is connected firmly with active material, effectively presses down
System and the side reaction of electrolyte, so that the battery being made of the ternary material that this method is prepared, reversible specific volume for the first time
Amount is high, good cycle.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
The nickelic ternary material of nickel cobalt lithium aluminate is prepared using following continuous membrane wrapping modified method：
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:1:0.1, and nickel from
The sum of son, cobalt ions and aluminium ion concentration are 0.5mol/L.Then in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Sodium hydroxide solution is added as precipitating reagent, a concentration of 3mol/L of sodium hydroxide solution controls mixed aqueous solution and hydroxide
The volume ratio of sodium solution is 1:0.5, then it is 9 to adjust pH value with ammonium hydroxide, coprecipitation reaction 2h is filtered, washed, and obtains nickelic ternary
Presoma.
B, two steps type Screw Extrusion：By lithium sulfate and nickelic ternary precursor in mass ratio 0.3:1 mixing, is sent into two steps type
Screw extruder, the first rank screw extruder temperature of control are 150 DEG C；Second-order screw extruder temperature is 250 DEG C；And pass through
Oxygen pump maintains the oxygen-enriched environment in two steps type screw rod, and aluminium isopropoxide is added in the second section screw extruder, aluminium isopropoxide
Addition is the 20% of nickelic ternary precursor weight；After being squeezed out by two steps type screw extruder, obtains aluminium oxide and continuously coat
The nickelic ternary forerunner particle of dispersion.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 4h in 850 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Embodiment 2
The nickelic ternary material of nickel cobalt lithium aluminate is prepared using following continuous membrane wrapping modified method：
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:2:1, and nickel ion,
The sum of cobalt ions and aluminium ion concentration are 2mol/L.Then it is added in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Sodium hydroxide solution is as precipitating reagent, and a concentration of 5mol/L of sodium hydroxide solution, controls mixed aqueous solution and sodium hydroxide is molten
The volume ratio of liquid is 1:2, then it is 10 to adjust pH value with ammonium hydroxide, coprecipitation reaction 8h is filtered, washed, and obtains nickelic ternary forerunner
Body.
B, two steps type Screw Extrusion：By lithium sulfate and nickelic ternary precursor in mass ratio 1:1 mixing, is sent into two steps type spiral shell
Bar extruder, the first rank screw extruder temperature of control are 200 DEG C；Second-order screw extruder temperature is 300 DEG C；And by adding
Oxygen pump maintains the oxygen-enriched environment in two steps type screw rod, and aluminium isopropoxide is added in the second section screw extruder, and aluminium isopropoxide adds
Enter 60% that amount is nickelic ternary precursor weight；After being squeezed out by two steps type screw extruder, aluminium oxide continuously cladding point is obtained
Scattered nickelic ternary forerunner particle.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 8h in 950 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Embodiment 3
The nickelic ternary material of nickel cobalt lithium aluminate is prepared using following continuous membrane wrapping modified method：
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:1.5:0.5, and nickel from
The sum of son, cobalt ions and aluminium ion concentration are 0.8mol/L.Then in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Sodium hydroxide solution is added as precipitating reagent, a concentration of 4.5mol/L of sodium hydroxide solution controls mixed aqueous solution and hydrogen-oxygen
The volume ratio for changing sodium solution is 1:0.8, then it is 10 to adjust pH value with ammonium hydroxide, coprecipitation reaction 5h is filtered, washed, and is obtained nickelic
Ternary precursor.
B, two steps type Screw Extrusion：By lithium sulfate and nickelic ternary precursor in mass ratio 0.8:1 mixing, is sent into two steps type
Screw extruder, the first rank screw extruder temperature of control are 190 DEG C；Second-order screw extruder temperature is 290 DEG C；And pass through
Oxygen pump maintains the oxygen-enriched environment in two steps type screw rod, and aluminium isopropoxide is added in the second section screw extruder, aluminium isopropoxide
Addition is the 50% of nickelic ternary precursor weight；After being squeezed out by two steps type screw extruder, obtains aluminium oxide and continuously coat
The nickelic ternary forerunner particle of dispersion.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 6h in 920 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Embodiment 4
The nickelic ternary material of nickel cobalt lithium aluminate is prepared using following continuous membrane wrapping modified method：
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:1.5:0.5, and nickel from
The sum of son, cobalt ions and aluminium ion concentration are 1.5mol/L.Then in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Sodium hydroxide solution is added as precipitating reagent, a concentration of 3.5mol/L of sodium hydroxide solution controls mixed aqueous solution and hydrogen-oxygen
The volume ratio for changing sodium solution is 1:1.5, then it is 9 to adjust pH value with ammonium hydroxide, coprecipitation reaction 3h is filtered, washed, and obtains nickelic three
First presoma.
B, two steps type Screw Extrusion：By lithium sulfate and nickelic ternary precursor in mass ratio 0.7:1 mixing, is sent into two steps type
Screw extruder, the first rank screw extruder temperature of control are 160 DEG C；Second-order screw extruder temperature is 260 DEG C；And pass through
Oxygen pump maintains the oxygen-enriched environment in two steps type screw rod, and aluminium isopropoxide is added in the second section screw extruder, aluminium isopropoxide
Addition is the 30% of nickelic ternary precursor weight；After being squeezed out by two steps type screw extruder, obtains aluminium oxide and continuously coat
The nickelic ternary forerunner particle of dispersion.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 5h in 880 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Embodiment 5
The nickelic ternary material of nickel cobalt lithium aluminate is prepared using following continuous membrane wrapping modified method：
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:1.5:0.5, and nickel from
The sum of son, cobalt ions and aluminium ion concentration are 1.2mol/L.Then in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Sodium hydroxide solution is added as precipitating reagent, a concentration of 4.5mol/L of sodium hydroxide solution controls mixed aqueous solution and hydrogen-oxygen
The volume ratio for changing sodium solution is 1:1.2, then it is 10 to adjust pH value with ammonium hydroxide, coprecipitation reaction 6h is filtered, washed, and is obtained nickelic
Ternary precursor.
B, two steps type Screw Extrusion：By lithium sulfate and nickelic ternary precursor in mass ratio 0.5:1 mixing, is sent into two steps type
Screw extruder, the first rank screw extruder temperature of control are 170 DEG C；Second-order screw extruder temperature is 270 DEG C；And pass through
Oxygen pump maintains the oxygen-enriched environment in two steps type screw rod, and aluminium isopropoxide is added in the second section screw extruder, aluminium isopropoxide
Addition is the 50% of nickelic ternary precursor weight；After being squeezed out by two steps type screw extruder, obtains aluminium oxide and continuously coat
The nickelic ternary forerunner particle of dispersion.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 7h in 900 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Embodiment 6
The nickelic ternary material of nickel cobalt lithium aluminate is prepared using following continuous membrane wrapping modified method：
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:1.5:0.5, and nickel from
The sum of son, cobalt ions and aluminium ion concentration are 1mol/L.Then add in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Enter sodium hydroxide solution as precipitating reagent, a concentration of 4mol/L of sodium hydroxide solution controls mixed aqueous solution and sodium hydroxide
The volume ratio of solution is 1:1, then it is 9 to adjust pH value with ammonium hydroxide, coprecipitation reaction 5h is filtered, washed, and obtains nickelic ternary forerunner
Body.
B, two steps type Screw Extrusion：By lithium sulfate and nickelic ternary precursor in mass ratio 0.6:1 mixing, is sent into two steps type
Screw extruder, the first rank screw extruder temperature of control are 180 DEG C；Second-order screw extruder temperature is 280 DEG C；And pass through
Oxygen pump maintains the oxygen-enriched environment in two steps type screw rod, and aluminium isopropoxide is added in the second section screw extruder, aluminium isopropoxide
Addition is the 40% of nickelic ternary precursor weight；After being squeezed out by two steps type screw extruder, obtains aluminium oxide and continuously coat
The nickelic ternary forerunner particle of dispersion.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 6h in 900 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Comparative example 1
A, the preparation of presoma：Nickel sulfate, cobaltous sulfate and aluminum sulfate difference is soluble in water, then each solution is mixed, contained
Have in nickel ion, cobalt ions and aluminum ions mixed aqueous solution, wherein in molar ratio, Ni：Co：Al=8:1.5:0.5, and nickel from
The sum of son, cobalt ions and aluminium ion concentration are 1mol/L.Then add in nickel ion, cobalt ions and aluminum ions mixed aqueous solution
Enter sodium hydroxide solution as precipitating reagent, a concentration of 4mol/L of sodium hydroxide solution controls mixed aqueous solution and sodium hydroxide
The volume ratio of solution is 1:1, then it is 9 to adjust pH value with ammonium hydroxide, coprecipitation reaction 5h is filtered, washed, and obtains nickelic ternary forerunner
Body.
B, by lithium sulfate and nickelic ternary precursor in mass ratio 0.6:1 mixing, is added aluminium isopropoxide, and aluminium isopropoxide adds
Enter 40% that amount is nickelic ternary precursor weight；By heated oxide, the nickelic ternary forerunner of alumina-coated dispersion is obtained
Grain.
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 6h in 900 DEG C, obtains nickel cobalt aluminium
The sour nickelic ternary material of lithium.
Battery is tested to prepare and test：The nickelic ternary of nickel cobalt lithium aluminate being prepared with Examples 1 to 6 and comparative example 1
Material is active material, by weight, active material：Carbon black：PVDF=93:3:After 4 mixing, suitable N- methyl pyrrole is added
Slurry is made after pyrrolidone mixing, coated machine coating is made pole piece, is then assembled into diaphragm, graphite cathode and electrolyte
Experimental cell, test battery its charge/discharge capacity, high rate performance and cycle performance, the result is shown in tables 1.
Table 1
| Number | The reversible specific capacity for the first time of 1C charge and discharge in the sections 3~4.2V（mAh/g） | Conservation rate is recycled after 150 times (1C/1C RT) cycle（%） |
| Embodiment 1 | 191 | 89.4 |
| Embodiment 2 | 192 | 88.5 |
| Embodiment 3 | 198 | 81.5 |
| Embodiment 4 | 196 | 82.3 |
| Embodiment 5 | 204 | 83.4 |
| Embodiment 6 | 208 | 84.7 |
| Comparative example 1 | 173 | 65.9 |
Claims (9)
1. a kind of method that continuous coating prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, which is characterized in that including as follows
Step：
A, the preparation of presoma：In nickel ion, cobalt ions and aluminum ions mixed aqueous solution, sodium hydroxide is added as precipitation
Agent, then it is 9~10 to adjust pH value with ammonium hydroxide, 2~8h of coprecipitation reaction is filtered, washed, and obtains nickelic ternary precursor；Wherein,
In molar ratio, Ni：Co：Al=8:1~2:0.1~1；
B, two steps type Screw Extrusion：Lithium salts is mixed with nickelic ternary precursor, is sent into two steps type screw extruder, control first
Rank screw extruder temperature is 150~200 DEG C；Second-order screw extruder temperature is 250~300 DEG C；And it is tieed up by oxygen pump
The oxygen-enriched environment in two steps type screw rod is held, aluminium isopropoxide is added in the second section screw extruder, passes through two steps type Screw Extrusion
After machine squeezes out, the nickelic ternary forerunner particle that aluminium oxide continuously coats dispersion is obtained；
C, it calcines：The nickelic ternary forerunner particle that aluminium oxide is continuously coated to dispersion is sintered 4~8h in 850~950 DEG C, obtains nickel
The nickelic ternary material of cobalt lithium aluminate.
2. the method that continuous coating according to claim 1 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In a steps, in molar ratio, Ni：Co：Al=8:1.5:0.5.
3. the method that continuous coating according to claim 1 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In a steps, the concentration of metal ions in mixed aqueous solution is 0.5~2 mol/L.
4. the method that continuous coating according to claim 1 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In a steps, sodium hydroxide solution is added as precipitating reagent, and a concentration of 3~5mol/L of sodium hydroxide solution.
5. the method that continuous coating according to claim 4 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：The volume ratio of mixed aqueous solution and sodium hydroxide solution is 1:0.5~2.
6. the method that continuous coating according to claim 1 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In b step, the lithium salts is lithium sulfate.
7. the method that continuous coating according to claim 6 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In b step, lithium salts and nickelic ternary precursor in mass ratio 0.3~1:1 mixing.
8. the method that continuous coating according to claim 1 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In b step, the addition of aluminium isopropoxide is the 20~60% of nickelic ternary precursor weight.
9. the method that continuous coating according to claim 1 prepares the nickelic ternary lithium battery material of nickel cobalt lithium aluminate, special
Sign is：In step c, 6h is sintered in 900 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111682196A (en) * | 2020-05-20 | 2020-09-18 | 欣旺达电动汽车电池有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN111916688A (en) * | 2019-05-09 | 2020-11-10 | 天津国安盟固利新材料科技股份有限公司 | Lithium cobaltate composite positive electrode material and preparation method thereof |
-
2018
- 2018-03-08 CN CN201810188840.3A patent/CN108428885A/en not_active Withdrawn
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111916688A (en) * | 2019-05-09 | 2020-11-10 | 天津国安盟固利新材料科技股份有限公司 | Lithium cobaltate composite positive electrode material and preparation method thereof |
| CN111682196A (en) * | 2020-05-20 | 2020-09-18 | 欣旺达电动汽车电池有限公司 | Cathode material, preparation method thereof and lithium ion battery |
| CN111682196B (en) * | 2020-05-20 | 2023-03-10 | 欣旺达电动汽车电池有限公司 | Cathode material, preparation method thereof and lithium ion battery |
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