CN108682807A - Precursor of lithium ionic cell positive material and preparation method thereof, positive electrode active materials, lithium ion battery, flow reactor - Google Patents
Precursor of lithium ionic cell positive material and preparation method thereof, positive electrode active materials, lithium ion battery, flow reactor Download PDFInfo
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Abstract
The present invention relates to a kind of precursor of lithium ionic cell positive material and preparation method thereof, anode active material of lithium ion battery, lithium ion battery, flow reactors, belong to novel energy resource material technology field.The preparation method of the precursor of lithium ionic cell positive material of the present invention includes the following steps：Nickel salt, cobalt salt, manganese salt, doped metal salt D salt, precipitating reagent, complexing agent are mixed; obtain reaction system; it is reacted while stirring in 30~80 DEG C under the conditions of inert gas shielding, pH are 10.0~13.0; reaction is synthesized using continuous feed, continuous overflow discharge method; the material that overflows be aged 1~5h to get；Reaction system is ultrasonically treated to overflow material granularity when the granularity of the material overflowed reaches setting value and is less than setting value.Precursor of lithium ionic cell positive material obtained by the method for the present invention, granularity and pattern are uniform, and tap density is big, are conducive to the follow-up anode material for lithium-ion batteries for preparing electrochemical performance.
Description
Technical field
The present invention relates to a kind of precursor of lithium ionic cell positive material and preparation method thereof, lithium ion cell positive activity
Material, lithium ion battery, flow reactor belong to novel energy resource material technology field.
Background technology
Commercial lithium-ion batteries positive electrode mainly selects LiCoO at present2、LiMn2O4、LiFePO4、Li
(NixCoyMnz)O2[x+y+z=1.0, abbreviation NCM], Li (Ni0.8Co0.15Al0.05)O2[abbreviation NCA] etc., but cobalt element is opposite
It is poor to lead to LiCoO2Cost is higher, and LiMn2O4、LiFePO4Specific capacity is relatively low.In contrast, NCM/NCA due to having simultaneously
There is many advantages, such as at low cost, capacity is high, safety is good and is widely used.Core former material of the precursor as positive electrode
Material, physicochemical property directly determine that the physics and chemistry of positive electrode and chemical property play.Precursor preparation method include interval and
Two class of continuous synthesis industrially mostly uses continuous synthesis mode batch production, mainly uses co-precipitation side in industry at present
Formula prepares hydroxide nickel cobalt manganese precursor, is then mixed according to a certain ratio with lithium salts, by high temperature solid-phase sintering formed lithium from
Sub- cell positive material.
Traditional continuous synthesis synthesis presoma is the granularity by pH come controlled material, i.e. precursor granularity is in
When ascent stage, slowly increasing pH value makes precursor synthesis tend to be nucleated, when granularity is begun to decline, before slowly reduction pH value makes
Body is driven to tend to grow.This synthetic method can cause precursor synthesis process periodic granularity fluctuation occur, while periodically
PH value fluctuation can also influence the unstable of particle growth rate and nucleation rate, the random growth of particle is caused, under orientation
Drop, the final chemical property for influencing material.
It is before the Chinese invention patent of CN 103943846B discloses a kind of anode material for lithium-ion batteries to authorize publication No.
The preparation method for driving body, has obtained a kind of coated by titanium dioxide NixCoyMnzA1-x-y-z(OH)2Positive electrode material precursor, at it
The granularity of material is not regulated and controled in preparation process, granularity fluctuation is too big, and then influences the chemical property of material.
Invention content
The purpose of the present invention is to provide a kind of preparation method of above-mentioned precursor of lithium ionic cell positive material, this method
Obtained positive electrode material precursor epigranular, particle ordering growth.
Second object of the present invention is to provide a kind of precursor of lithium ionic cell positive material obtained by the above method.
Third object of the present invention is to provide a kind of anode active material of lithium ion battery.
Fourth object of the present invention is to provide a kind of lithium ion battery.
The 5th of the present invention is designed to provide a kind of flow reactor.
To achieve the above object, the technical scheme is that：
A kind of preparation method of precursor of lithium ionic cell positive material, includes the following steps：By nickel salt, cobalt salt, manganese salt,
Doped metal salt D salt, precipitating reagent, complexing agent mixing, obtain reaction system, are 10.0~13.0 conditions in inert gas shielding, pH
Under reacted while stirring in 30~80 DEG C, reaction using continuous feed, continuous overflow discharge by the way of synthesize, by what is overflowed
Material be aged 1~5h to get；The granularity of the material overflowed is ultrasonically treated when reaching setting value to overflowing
Material granularity be less than setting value.
Above-mentioned reaction carries out in the reaction vessel.Above-mentioned continuous feed is that material is added to the bottom of reaction vessel.It is described
Overflow discharging is to carry out overflow discharging from the overflow port being arranged at the top of reaction vessel.
Above-mentioned nickel salt, cobalt salt, manganese salt, doped metal salt D salt are sulfate, nitrate, acetate, oxalates or chlorination
Salt.
Above-mentioned D is any one or a few in Al, Ti, Zr, Mg, Zn, Cr.
The precipitating reagent is sodium hydroxide solution.The mass concentration of the sodium hydroxide solution is 30~48%.
The complexing agent is ammonium hydroxide.The mass concentration of the ammonium hydroxide is 15~18%.NH3Molecule can be with Ni2+/Co2+/Mn2+
Soluble complexes are formed, to control the settling rate of Ni/Co/Mn.
Nickel salt, cobalt salt, manganese salt, D salt are first dissolved in water and matched by the preparation method of above-mentioned precursor of lithium ionic cell positive material
Be made the mixing salt solution that total concentration of metal ions is the nickel salt of 0.5~3.5mol/L, cobalt salt, manganese salt, D salt, then with precipitating reagent,
Complexing agent mixes.
Nickel salt, cobalt salt, manganese salt, the molar ratio of D salt are (0.3~1.0) in the mixing salt solution：(0~0.5)：(0~
0.4)：(0~0.1).
Above-mentioned mixing salt solution and precipitating reagent, complexing agent are mixed into：Mixing salt solution, precipitating reagent, complexing agent are passed through
Metering pump is pumped into reactor simultaneously, mixes in the reactor.The reactor is continuous tank reactor.
The speed that is pumped into of the mixing salt solution is 60~100mL/min.
The speed that is pumped into of the precipitating reagent is 10-20mL/min.
The speed that is pumped into of the complexing agent is 15-30mL/min.
Above-mentioned inert gas is nitrogen.
The rate of above-mentioned stirring is 400~1000rpm.
The setting value is 1.5~16.0 μm.The setting value is any one granularity in 1.5~16.0 μm.
The frequency of the supersound process is 20~100kHz.
The power density of the supersound process is 4~40W/L.Ultrasonic power is selected according to the volume of reaction kettle.
The supersound process carries out auxiliary synthesis using intermittently or serially supersound process.
The balance of nucleus generation and growth rate is controlled in precursor synthesis, saline and alkaline contact causes part supersaturation heavy
It forms sediment, generates nucleus.The parameters such as control ph, ammonia density and rotating speed, nucleus are grown according to certain crystal face orderly accumulation, to
Reach the pattern of uniform and ordered.The cavitation of ultrasonic wave has an impact the generation of the supersaturated nucleus in saline and alkaline part, avoids two
Secondary dissolving reaches particle size stable balance to balance generation and growth rate.Suffered by nucleus difference crystal face simultaneously for precipitation
To cavitation influence differ, then cause the rate of different crystal face accumulated growths to differ greatly, to reach by radially outwardly
The orderly accumulation appearance of transmitting.
The granularity of the material overflowed is ultrasonically treated when reaching setting value to the grain of the material overflowed
Degree refers to proceeding by ultrasound when material size is more than setting value less than setting value.And when overflow material granularity is less than setting
When value, stop ultrasound.Preferably, it is 10.0-13.0 pH to be controlled in above-mentioned preparation method, within the scope of the pH, the granularity of material
Always it is in the rise stage, is monitored by laser particle analyzer.When granularity exceeds setting value, ultrasonator is opened, reaction is made
System fast nucleation.Ultrasonator is closed after granularity is decreased below setting value, material is realized by this control method
The control of material granularity.
The rotating speed of above-mentioned ageing is 200rpm.The purpose of ageing is to stir the secondary dissolving and again of lower control nucleus slowly in low speed
It is precipitated, keeps particle surface more smooth and fine and close, be conducive to the subsequent processing performance of material.
It is filtered, washed, dried after above-mentioned ageing, obtain precursor of lithium ionic cell positive material.
The temperature of above-mentioned drying is 100~140 DEG C.
A kind of precursor of lithium ionic cell positive material is made using above-mentioned preparation method.
The molecular formula of the presoma is NixCoyMnzD1-x-y-z(OH)2, wherein 0.85<X+y+z≤1.0,0.3<x<1,0<
y<0.5,0≤z<0.4；D is any one or a few in Al, Ti, Zr, Mg, Zn, Cr.
The granularity D50 of the presoma is 2.5-15.0 μm.
The tap density of the presoma>1.5g/cm3。
The precursor of lithium ionic cell positive material of the present invention, granularity and pattern are uniform, and tap density is larger, are conducive to follow-up
Prepare the anode material for lithium-ion batteries of electrochemical performance.
A kind of anode active material of lithium ion battery, using above-mentioned precursor of lithium ionic cell positive material.
A kind of lithium ion battery, including anode, cathode, the anode include above-mentioned anode active material of lithium ion battery.
The anode includes plus plate current-collecting body and the positive electrode material layer coated in collection liquid surface, and the positive electrode material layer includes that anode is living
Property substance, the positive active material be the anode active material of lithium ion battery.
A kind of flow reactor, including reaction vessel, the reaction vessel upper end are provided with overflow port, the successive reaction
Device further includes the feed pipe for feeding into reaction vessel, and the discharge port of the feed pipe is arranged in the bottom of reaction vessel.
The flow reactor further includes the blender for being stirred to the material in reaction vessel.The reaction is held
The thermometer for the temperature measurement to the material in reaction vessel is provided on device.It is provided with for right on the reaction vessel
The pH meter that the pH of material in reaction vessel is detected.It is provided on the reaction vessel for the material in reaction vessel
The supersonic generator being ultrasonically treated.Water-bath chuck is provided on the reaction vessel.
The feed pipe can be one or two or more.Preferably, feed pipe is three.
The precursor of lithium ionic cell positive material of the present invention, pattern is uniform, and tap density is big, for subsequently obtained electrochemistry
The lithium ion battery haveing excellent performance lays the foundation.
The preparation method of the precursor of lithium ionic cell positive material of the present invention, technique is relatively easy, controllable, reaction system
Each technological parameter can be with stable for extended periods of time, and large-scale production easy to implement, which is steady in pH value of reaction system
It carries out preparing the synthesis of positive electrode material precursor, presoma primary particle aligned orderly under the premise of fixed, and has preferable two
Secondary granule-morphology.
The anode active material of lithium ion battery of the present invention, distribution of particles are concentrated, and lithium ion diffusion is radial orderly, has very
Good processability and electrical property consistency.
The lithium ion battery of the present invention has good processing performance, battery performance hair using above-mentioned positive electrode active materials
Stabilization is waved, cycle life and high temperature high rate performance are excellent.
Description of the drawings
Fig. 1 is the schematic diagram of reaction kettle structure in embodiment 1；
Fig. 2 is the SEM figures of precursor of lithium ionic cell positive material in embodiment 1；
Fig. 3 is the particle size distribution figure of precursor of lithium ionic cell positive material in embodiment 1；
Fig. 4 is the electric discharge gram volume curve graph of anode material for lithium-ion batteries in embodiment 1.
Specific implementation mode
Embodiments of the present invention are described further below in conjunction with the accompanying drawings.
Embodiment 1
The flow reactor of the present embodiment is reaction kettle, and (1 is motor, and 2 be pH as shown in Figure 1 for the structural representation of reaction kettle
Meter, 3 be thermometer, and 4 be supersonic generator, and 5 be feed pipe, and 6 be circulating water outlet, and 7 be overflow discharge nozzle, and 8 be recirculated water
Import).
Specifically, reaction kettle includes reaction vessel and the head cover that coordinates with reaction vessel.Reaction vessel upper end is provided with
Overflow port is connected with overflow discharge nozzle 7 on overflow port.Reaction kettle further includes the feed pipe 5 for feeding into reaction vessel, into
Expects pipe 5 is fixed on the head cover of reaction kettle, and one end stretches into reaction vessel interior until reaction container bottom, feed pipe go out
Material mouth is arranged in the bottom of reaction vessel.Reaction kettle further includes the blender for being stirred to the material in reaction vessel.
Blender includes the agitating shaft being fixed on reaction kettle head cover.The lower end of agitating shaft is stretched into reaction vessel, and reaction is stretched into
It is provided with stirring blade on one end in container.Motor 1 is connected on the upper end of agitating shaft.
The thermometer 3 for the temperature measurement to the material in reaction vessel is provided on reaction vessel.Thermometer 3 it is upper
End is fixed on the head cover of reaction kettle.The pH being detected for the pH to the material in reaction vessel is provided on reaction vessel
Meter 2.The upper end of pH meter 2 is also fixed on the head cover of reaction kettle.It is provided on reaction vessel in reaction vessel
The supersonic generator 4 that material is ultrasonically treated.The upper end of supersonic generator 4 is fixed on the head cover of reaction kettle,
Lower end is stretched into reaction vessel.Water-bath chuck is provided on reaction vessel.Water-bath chuck includes that setting is held on the reaction vessel
Water outlet 6 and the water inlet 8 in reaction vessel lower end is set.
The preparation method of the precursor of lithium ionic cell positive material of the present embodiment, includes the following steps：
1) by nickel sulfate, cobaltous sulfate, manganese sulfate Ni in molar ratio:Co:Mn=6:2:2 ratio dissolving is configured to nickel cobalt manganese
Mixing salt solution, a concentration of 2.0mol/L of total metal ion in mixing salt solution；Prepare the hydrogen-oxygen that mass concentration is 32%
Change sodium solution；Prepare the ammonium hydroxide that mass concentration is 17%；
2) nickel cobalt manganese mixing salt solution, sodium hydroxide solution, ammonium hydroxide are pumped into 50L reaction kettles simultaneously respectively with metering pump
In.It is reacted while stirring while being pumped into material, the speed that is pumped into of wherein mixing salt solution is 60mL/min, the pump of sodium hydroxide solution
It is 10mL/min to enter speed, and the speed that is pumped into of ammonium hydroxide is 15mL/min；15L ultra-pure waters are previously added in aforesaid reaction vessel；It is above-mentioned
The actual conditions reacted while stirring are：Under the conditions of nitrogen protection, pH value are 11.9 ± 0.05, controlling reaction temperature is stablized
50 ± 1 DEG C, the rotating speed of motor stirring is 800r/min；The pH value of reaction system is tested by pH meter；It can also be taken in overflow port
Sample is tested in reaction kettle external application pH meter；The granularity of reaction system is monitored using laser particle analyzer；It is (big when granularity is more than 10 μm
In equal to 10 μm), opening ultrasonator makes reaction system fast nucleation, when reaction system granularity is less than 10 μm, stops super
Sound, controls in reaction process particle D50 granularities at 10.0 ± 1 μm, and the frequency of ultrasonic vibration is 40kHz, power 800W；Work as grain
Degree control starts to collect overflow material, and stir overflow material progress 200rpm slowly and be aged 1h after 10.0 ± 1 μ ms, complete
Press filtration is carried out to feed liquid after finishing, obtains filter cake；
3) filter cake in step 2) is washed with deionized until filtrate pH value is less than 8.0, then in vacuum drying chamber
In at 120 DEG C be dried in vacuo 6h to get positive electrode material precursor.
The precursor of lithium ionic cell positive material of the present invention is made using above-mentioned preparation method, and molecular formula is
Ni0.6Co0.2Mn0.2(OH)2。
SEM tests are carried out to the positive electrode material precursor of the present embodiment, Fig. 2 (a) is as a result seen, can be obtained by Fig. 2 (a), this reality
It is spherical in shape to apply positive electrode material precursor pattern obtained by example；Fig. 2 (b) is the cross-section structure of the positive electrode material precursor of the present embodiment
SEM schemes, and by Fig. 2 (b) it is found that particle is primary particle, primary particle is evenly distributed, internal radially orderly transmitting arrangement,
Be conducive to lithium ion diffusive migration.
Testing graininess is carried out to the positive electrode material precursor of the present embodiment, as a result sees Fig. 3, from size distribution, particle
Distribution is concentrated, and is illustrated that particle growth rate and nucleation rate control are stablized, is conducive to the processing performance and electric performance stablity of material
Property.
The tap density of the positive electrode material precursor of the present embodiment is 2.25g/cm3。
The anode active material of lithium ion battery of the present embodiment is made, specially using above-mentioned positive electrode material precursor：It will
The anode material precursor of the present embodiment is mixed with the lithium carbonate of stoichiometric ratio, is sintered 15h at a high temperature of 890 DEG C, is obtained
The positive electrode active materials of the present embodiment.
The lithium ion battery of the present embodiment, including anode and cathode are lived wherein anode includes above-mentioned lithium ion cell positive
Property material, specially by above-mentioned positive electrode active materials and SP, PVDF according to 9:0.5:0.5 mass ratio be added in solvent NMP into
Then row mixed ingredients slurrying, coating, dry obtained positive plate prepare 2032 model button electricity with negative plate metal lithium sheet
Pond carries out electrochemical property test.
Embodiment 2
The preparation method of the precursor of lithium ionic cell positive material of the present embodiment, includes the following steps：
1) by nickel sulfate, cobaltous sulfate, manganese sulfate Ni in molar ratio:Co:Mn=8:1:1 ratio dissolving is configured to nickel cobalt manganese
Mixing salt solution, a concentration of 2.6mol/L of total metal ion in mixing salt solution；Prepare the hydroxide that mass fraction is 32%
Sodium solution；The ammonium hydroxide that mass fraction is 17% is prepared, it is spare；
2) nickel cobalt manganese mixing salt solution, sodium hydroxide solution, ammonium hydroxide are pumped into 50L reaction kettles simultaneously respectively with metering pump
In, synthetic reaction is stirred when being pumped into material, the speed that is pumped into of wherein mixing salt solution is 100mL/min, sodium hydroxide solution
Be pumped into speed be 20mL/min, ammonium hydroxide be pumped into speed be 30mL/min；15L ultra-pure waters are previously added in aforesaid reaction vessel；
The actual conditions of above-mentioned synthetic reaction while stirring are：Under the conditions of nitrogen protection, pH value are 12.3 ± 0.05, control reaction temperature
Degree is stablized at 55 ± 1 DEG C, speed of agitator 900r/min, and the pH value of reaction system is sampled in overflow port, is tested with pH meter；Reaction
The granularity of system is monitored using laser particle analyzer, (is more than or equal to 10 μm) when granularity is more than 10 μm, is opened ultrasonator
Make reaction system fast nucleation；When reaction system granularity is less than 10 μm, stop ultrasound, controls particle D50 in reaction process
Degree is at 10.0 ± 1 μm；Ultrasonic vibration frequency is 80kHz, power 600W；After granularity is controlled in 10.0 ± 1 μ m, start
Collect overflow material, and to overflow material carry out 200rpm slowly stir ageing 5h, after to feed liquid carry out press filtration, obtain filter cake；
3) filter cake in step 2) is washed with deionized until filtrate pH value is less than 8.0, then in vacuum drying chamber
In at 120 DEG C be dried in vacuo 6h to get positive electrode material precursor.
The precursor of lithium ionic cell positive material of the present invention is made using above-mentioned preparation method, and molecular formula is
Ni0.8Co0.1Mn0.1(OH)2, the present embodiment gained positive electrode material precursor pattern is spherical in shape, and narrow particle size distribution D50 is 10.43
μm, tap density 2.28g/cm3。
The anode active material of lithium ion battery of the present embodiment is made using above-mentioned positive electrode material precursor, specially will
The anode material precursor of the present embodiment is mixed with the lithium hydroxide of stoichiometric ratio, is sintered 15h at a high temperature of 850 DEG C, is obtained
To positive electrode active materials.
The lithium ion battery of the present embodiment, including anode and cathode, wherein anode includes lithium ion cell positive activity material
Material, specially by above-mentioned positive electrode active materials and SP, PVDF according to 9:0.5:0.5 mass ratio is added in solvent NMP and is mixed
Dispensing slurrying, coating are closed, then it is electrical to prepare the progress of 2032 model button cells with metal lithium sheet for dry obtained positive plate
It can test.
Embodiment 3
The preparation method of the precursor of lithium ionic cell positive material of the present embodiment, includes the following steps：
1) by nickel sulfate, cobaltous sulfate, manganese sulfate, zirconium sulfate Ni in molar ratio:Co:Mn：Zr=0.6:0.15:0.2：0.05
Ratio dissolving be configured to nickel cobalt manganese zirconium mixing salt solution, a concentration of 2.6mol/L of total metal ion in mixing salt solution；Match
The sodium hydroxide solution that mass fraction processed is 32%；The ammonia spirit that mass fraction is 17% is prepared, it is spare；
2) nickel cobalt manganese zirconium mixing salt solution, sodium hydroxide solution, ammonium hydroxide are pumped into 50L reactions simultaneously respectively with metering pump
In kettle, synthetic reaction is stirred when being pumped into material, the speed that is pumped into of wherein mixing salt solution is 80mL/min, sodium hydroxide solution
Be pumped into speed be 15mL/min, ammonium hydroxide be pumped into speed be 20mL/min；15L ultra-pure waters are previously added in aforesaid reaction vessel；
The actual conditions of above-mentioned synthetic reaction while stirring are：Under the conditions of nitrogen protection, pH value are 11.5 ± 0.05, control reaction temperature
Degree is stablized at 60 ± 1 DEG C, and the rotating speed of motor stirring is 800r/min, and the pH value of reaction system is sampled in overflow port, surveyed with pH meter
Examination；The granularity of reaction system is used to be monitored in laser particle analyzer, (is more than or equal to 10 μm) when granularity is more than 10 μm, is opened super
Sound oscillator makes reaction system fast nucleation；When reaction system granularity be less than 10 μm when, stop ultrasound, control reaction process in
Grain D50 granularities are at 10.0 ± 1 μm；Ultrasonic vibration frequency is 30kHz, power 500W；When granularity is controlled in 10.0 ± 1 μ ms
Afterwards, start collect overflow material, and to overflow material carry out 200rpm slowly stir ageing 2h, after to feed liquid carry out press filtration
Filter, obtains filter cake；
3) filter cake in step 2) is washed with deionized until filtrate pH value is less than 8.0, then in vacuum drying chamber
In at 120 DEG C be dried in vacuo 5h to get positive electrode material precursor.
The precursor of lithium ionic cell positive material of the present invention is made using above-mentioned preparation method, and molecular formula is
Ni0.6Co0.15Mn0.2Zr0.05(OH)2, the present embodiment gained positive electrode material precursor pattern is spherical in shape, and narrow particle size distribution D50 is
9.0 μm, tap density 2.05g/cm3。
The anode active material of lithium ion battery of the present embodiment is made using above-mentioned positive electrode material precursor, specially will
The precursor of the present embodiment is mixed with the lithium carbonate of stoichiometric ratio, is sintered 15h at a high temperature of 890 DEG C, is obtained positive-active
Material.
The lithium ion battery of the present embodiment, including anode and cathode are lived wherein anode includes above-mentioned lithium ion cell positive
Property material, specially by above-mentioned positive electrode active materials and SP, PVDF according to 9:0.5:0.5 mass ratio is added solvent NMP and carries out
Then mixed ingredients slurrying, coating, dry obtained positive plate prepare 2032 model button cells with metal lithium sheet and carry out electricity
Performance test.
Embodiment 4
The preparation method of the precursor of lithium ionic cell positive material of the present embodiment, includes the following steps：
1) by nickel sulfate, cobaltous sulfate, manganese sulfate, magnesium sulfate Ni in molar ratio:Co:Mn：Mg=0.5:0.15:0.3：0.05
Ratio dissolving be configured to nickel cobalt manganese magnesium mixing salt solution, a concentration of 2.5mol/L of total metal ion in mixing salt solution；Match
The sodium hydroxide solution that mass fraction processed is 32%；Prepare the ammonium hydroxide that mass fraction is 17%；
2) nickel cobalt manganese magnesium mixing salt solution, sodium hydroxide solution, ammonium hydroxide are pumped into 50L reactions simultaneously respectively with metering pump
In kettle, synthetic reaction is stirred when being pumped into material, the speed that is pumped into of wherein mixing salt solution is 90mL/min, sodium hydroxide solution
Be pumped into speed be 18mL/min, ammonium hydroxide be pumped into speed be 22mL/min；15L ultra-pure waters are previously added in aforesaid reaction vessel；
The actual conditions of above-mentioned synthetic reaction while stirring are：Under the conditions of nitrogen protection, pH value are 11.3 ± 0.05, control reaction temperature
Degree is stablized at 60 ± 1 DEG C, speed of agitator 850r/min, and the pH value of reaction system is sampled in overflow port, is tested with pH meter；Reaction
The granularity of system is monitored using laser particle analyzer, (is more than or equal to 10 μm) when granularity is more than 10 μm, is opened ultrasonator
Make reaction system fast nucleation；When reaction system granularity is less than 10 μm, stop ultrasound, controls particle D50 in reaction process
Degree is at 10.0 ± 1 μm；Ultrasonic vibration frequency is 60kHz, power 400W；After granularity is controlled in 10.0 ± 1 μ m, start
Collect overflow material, and to overflow material carry out 200rpm slowly stir ageing 2h, after to feed liquid carry out press filtration filtering, must filter
Cake；
3) filter cake in step 2) is washed with deionized until filtrate pH value is less than 8.0, then in vacuum drying chamber
In at 120 DEG C be dried in vacuo 4h to get positive electrode material precursor.
The precursor of lithium ionic cell positive material of the present invention, is obtained, molecular formula is using above-mentioned preparation method
Ni0.5Co0.15Mn0.3Mg0.05(OH)2.Positive electrode material precursor pattern is spherical in shape obtained by the present embodiment, narrow particle size distribution D50
It is 9 μm, tap density 1.91g/cm3。
The anode active material of lithium ion battery of the present embodiment is made using above-mentioned positive electrode material precursor, specially will
The precursor of the present embodiment is mixed with the lithium carbonate of stoichiometric ratio, is sintered 15h at a high temperature of 930 DEG C, is obtained positive-active
Material.
The lithium ion battery of the present embodiment, including anode and cathode are lived wherein anode includes above-mentioned lithium ion cell positive
Property material, specially will be by above-mentioned positive electrode active materials and SP, PVDF according to 9:0.5:0.5 mass ratio is added in solvent and carries out
Then mixed ingredients slurrying, coating, dry obtained positive plate prepare 2032 model button cells with metal lithium sheet and carry out electricity
Performance test.
Experimental example
Electrochemical Properties are carried out to the button cell obtained by embodiment 1-4, the results are shown in Table 1.Wherein embodiment 1
In button cell electric discharge gram volume figure as shown in Figure 4, wherein curve a be 1C discharge gram volume curve；B is 0.5C electric discharges gram
Capacity curve；C is 0.2C electric discharge gram volume curves.
The chemical property of button cell in 1 embodiment 1-4 of table
| Project (button electricity 3.0-4.3V) | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| 0.2C electric discharge gram volumes mAh/g | 173.2 | 198.7 | 175.1 | 168.9 |
| 1C electric discharge gram volumes mAh/g | 159.7 | 185.4 | 161.0 | 154.1 |
| 1C recycles 50 weeks conservation rate % | 98.4% | 97.1% | 98.8% | 99.3% |
Claims (10)
1. a kind of preparation method of precursor of lithium ionic cell positive material, which is characterized in that include the following steps：By nickel salt,
Cobalt salt, manganese salt, doped metal salt D salt, precipitating reagent, complexing agent mixing, obtain reaction system；In inert gas shielding, pH 10.0
It is reacted while stirring in 30~80 DEG C under the conditions of~13.0, reaction is synthesized by the way of continuous feed, continuous overflow discharging；It will
The material that overflows be aged 1~5h to get；When the granularity of the material overflowed reaches setting value to reaction system into
Row, which is ultrasonically treated to the granularity of the material overflowed, is less than setting value.
2. the preparation method of precursor of lithium ionic cell positive material according to claim 1, which is characterized in that described to set
Definite value is 1.5~16.0 μm.
3. the preparation method of precursor of lithium ionic cell positive material according to claim 1, which is characterized in that described super
The frequency of sonication is 20~100kHz.
4. the preparation method of precursor of lithium ionic cell positive material according to claim 1, which is characterized in that described super
The power density of sonication is 4~40W/L.
5. a kind of precursor of lithium ionic cell positive material, which is characterized in that use preparation method system described in claim 1
.
6. precursor of lithium ionic cell positive material according to claim 5, which is characterized in that the molecule of the presoma
Formula is NixCoyMnzD1-x-y-z(OH)2, wherein 0.85<X+y+z≤1.0,0.3<x<1,0<y<0.5,0≤z<0.4；D be Al, Ti,
Any one or a few in Zr, Mg, Zn, Cr.
7. precursor of lithium ionic cell positive material according to claim 5, which is characterized in that the granularity of the presoma
D50 is 1.5-16.0 μm.
8. a kind of anode active material of lithium ion battery, which is characterized in that using the lithium ion cell positive described in claim 5
Material precursor is made.
9. a kind of lithium ion battery, including anode, cathode, which is characterized in that the anode include lithium according to any one of claims 8 from
Sub- battery anode active material.
10. a kind of flow reactor, including reaction vessel, which is characterized in that the reaction vessel upper end is provided with overflow port, institute
It further includes the feed pipe for feeding into reaction vessel to state flow reactor, and the discharge port setting of the feed pipe is held in reaction
The bottom of device.
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