CN107445214A - A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof - Google Patents
A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof Download PDFInfo
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Abstract
A kind of lithium ion battery nickel-cobalt-manganternary ternary anode material and preparation method thereof, the tertiary cathode material is made up of following methods：（1）Nickel source, cobalt source, manganese source and soft template are dissolved in polyalcohol, obtain mixed solution；（2）Back flow reaction is carried out, is cooled down, is centrifuged, is washed, dries, obtains metal alkoxide；（3）Calcined in air or oxygen, cool down, obtain presoma；（4）It is scattered in lithium source in lower alcohol, heating stirring obtains black powder to being evaporated；（5）Calcine, cool down in air or oxygen atmosphere,.Material precursor and tertiary cathode material particle of the present invention is uniform, in hollow ball-shape structure；Gained tertiary cathode material is assembled into battery, and under 3.00~4.40V, 15mA/g, the gram volume that discharges first may be up to 196mAh/g, and head effects up to 81.5%, the circle of circulation 20, conservation rate may be up to 95%；The inventive method is simple, and cost is low, suitable for industrialized production.
Description
Technical field
The present invention relates to a kind of anode material for lithium-ion batteries and preparation method thereof, and in particular to a kind of lithium ion battery is used
Nickel-cobalt-manganternary ternary anode material and preparation method thereof.
Background technology
With the development of science and technology, the popularization of various electronic products and electric automobile, the battery as its energy is carried
Higher requirement is gone out.Lithium ion battery is widely applied by its energy density height, advantages of environment protection.At present,
Anode material for lithium-ion batteries mainly has cobalt acid lithium, LiFePO4, ternary material etc., wherein, ternary material by its cost compared with
Low, the features such as specific capacity is high, cycle performance is excellent, shows one's talent.
The A of CN 103280572 disclose a kind of preparation method of nickel-cobalt-manganese ternary material, be by soluble lithium, nickel, cobalt,
Manganese and lutetium salt wiring solution-forming, reaction kettle body is pumped into certain density sodium hydroxide and ammoniacal liquor；By controlling temperature and pH value
The presoma of ternary material is obtained, then forms the presoma and lithium source mixed calcining.But this method is used to prepare ternary
Material precursor, higher is required to the control of the reaction conditions such as the temperature in preparation process, pH, ammonia concn, preparation process is more
It is cumbersome.
The A of CN 104393278 disclose a kind of method that hydroxide nickel cobalt manganese precipitation is made by coprecipitation, are by hydrogen
Cobalt nickel oxide manganses precipitation wash solution, that is, be passed through the deionized water washing of carbon dioxide, and the pH value for controlling wash solution is
6.50~6.70；After the completion of washing, filter, dry, obtain presoma nickel hydroxide cobalt-manganese ternary material；Then enter with lithium carbonate
Row mixing, is placed in multi-steps sintering in high temperature furnace；After the completion of sintering, material is taken out, nickle cobalt lithium manganate is obtained with crusher in crushing
Ternary material.But the control of this method condition is more strict, and presoma, due to preparing in the basic conditions, alkalescence is too high, needs
Washed, process is complicated.
CN103117380 A disclose a kind of preparation method of cobalt nickel lithium manganate ternary material, are by nickel salt, cobalt salt, manganese
Salt, alkali lye, ammoniacal liquor add reactor by Co deposited synthesis nickel-cobalt-manganese ternary presoma, after special wash liquid, use
Batch mixer mixes lithium, while it is modified by the way of ion doping, cladding.But this method prepares ternary material institute
The reaction condition control of the coprecipitation method used is complicated, and pattern is uneven, it is necessary to be doped and coat, cost is higher.
CN103296249A discloses a kind of preparation method of doping vario-property lithium nickel cobalt manganese, is using nickel salt, cobalt salt, manganese
Salt, precipitating reagent, pattern controlling agent, nano-metal-oxide dispersion liquid add reactor, pass through Co deposited synthesis nickel cobalt manganese three
First presoma, then cobalt nickel lithium manganate ternary material is made after overmulling lithium, calcining.But this method use co-precipitation and
The technique that nano-metal-oxide is doped, not only reaction condition control is complicated, and preparation flow is longer.
The content of the invention
The technical problems to be solved by the invention are to overcome drawbacks described above existing for prior art, there is provided a kind of electric conductivity
Good, electric discharge gram volume height, good cycle, preparation flow is simple, and cost is low, is used suitable for the lithium ion battery of industrialized production
Nickel-cobalt-manganternary ternary anode material and preparation method thereof.
The technical solution adopted for the present invention to solve the technical problems is as follows：A kind of lithium ion battery with nickel-cobalt-manganese ternary just
Pole material, is made up of following methods：
（1）Nickel source, cobalt source, manganese source and soft template are dissolved in polyol solvent, obtain mixed solution；
（2）By step（1）Gained mixed solution carries out back flow reaction, naturally cools to room temperature, centrifuges, and washs, and dries, obtains metal
Alkoxide；
（3）By step（2）Gained metal alkoxide is calcined in air or oxygen atmosphere, cools to room temperature with the furnace, obtains presoma；
（4）By step（3）Gained presoma is scattered in lower alcohol with lithium source, and heating stirring obtains black powder to being evaporated；
（5）By step（4）Gained black powder is calcined in air or oxygen atmosphere, cools to room temperature with the furnace, obtains lithium-ion electric
Pond nickel-cobalt-manganternary ternary anode material.
Preferably, step（1）In, nickel, cobalt, the mol ratio of manganese element are any ratio in the nickel source, cobalt source, manganese source（More
It is preferred that 1:0.1~1.0:0.1~1.0, still more preferably 1:1:1、5:2:3、6:2:2 or 8:1:1）.Representational lithium ion
Battery nickel-cobalt-manganternary ternary anode material has LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、
LiNi0.8Co0.1Mn0.1O2Deng.
Preferably, step（1）In, the dosage of the polyol solvent is so that nickel, cobalt, manganese is first in nickel source, cobalt source, manganese source
Total concentration of the amount summation of plain material in polyol solvent is 0.01~0.05mol/L（More preferably 0.02~0.04mol/L）.
Preferably, step（1）In, mass concentration of the soft template in polyol solvent is 1~3g/L.
By controlling the concentration of metal salt and soft template in polyol solvent, the size of product grain can be controlled, i.e.,
When the concentration of metal salt or soft template raises, then product grain increases, when the concentration of metal salt or soft template reduces, then product
Grain reduces, and still, if product grain is excessive, chemical property can be deteriorated, if product grain is too small, not only influence electrochemistry
Can, it can also reduce yield.
Preferably, step（1）In, the nickel source is the one or more in nickel formate, nickel acetate or dicyclopentadienyl nickel etc..It is more excellent
Select nickel acetate.
Preferably, step（1）In, the cobalt source is cobalt acetate or acetylacetone cobalt etc..More preferably cobalt acetate.
Preferably, step（1）In, the manganese source is the one or more in manganese acetate, manganese acetylacetonate or manganese acetate etc..
More preferably manganese acetate.
Preferably, step（1）In, the soft template is polyvinylpyrrolidone or cetyl trimethylammonium bromide.It is soft
Template can exist in polyol solvent with the particle shape of macromolecular aggregation, and metal ion and polyalcohol are in back flow reaction
In, as a spherical template, in the nano particle of its Surface Creation metal alkoxide, finally realize to soft template particle
Parcel, form the metal alkoxide spheric granules of shell kernel of uniform size.
Preferably, step（1）In, the polyol solvent is ethylene glycol or glycerine.
Preferably, step（2）In, the temperature of the back flow reaction is 150~200 DEG C（More preferably 160~190 DEG C）, return
The time of stream reaction is 2~8h.The back flow reaction is mainly the polymerization process of metal alkoxide, generates metal alcohol of uniform size
Salt nano particle, nickel, cobalt, manganese element are settled out from polynary mixed alkoxide solution, if temperature is too low, reaction is difficult to, if
Temperature is too high, then has side reaction.
Preferably, step（2）In, the rotating speed of the centrifugation is 5000~10000 r/min（More preferably 6000~8000
r/min）, the time of centrifugation is 5~10min（More preferably 6~8min）.
Preferably, step（2）In, the mode of washing is to be washed >=4 times with ethanol.
Preferably, step（2）In, the temperature of the drying is 80~120 DEG C, and the dry time is 8~12h.
Preferably, step（3）In, the mode of the calcining is：With 1~5 DEG C/min（More preferably 3~4 DEG C/min）Speed
Rate, from room temperature to 450~650 DEG C（More preferably 500~600 DEG C）, calcine 3~6 h（More preferably 4~5 h）.Pass through calcining
Decompose the soft template of kernel portion in the metal alkoxide spheric granules with shell inner core, kernel is heated produce shrink and
Shrinkage degree is larger up to decomposing, and skin sections decompose the metal oxide of generation, and shrinkage degree is smaller, so as to form sky
Shell structure.
Preferably, step（4）In, elemental lithium and nickel element, cobalt element, manganese member in nickel source, cobalt source, manganese source in the lithium source
The mol ratio of the amount summation of plain material is 1.04~1.06:1.Under the ratio, during subsequent calcination being prevented, lithium salts
Volatilization and cause the missing of product lithium.
Preferably, step（4）In, the dosage of the lower alcohol is 40~100mL/1mol elemental lithiums（More preferably 50~
70mL/1mol elemental lithiums）.
Preferably, step（4）In, the lithium source is the one or more in lithium carbonate, lithium acetate or lithium hydroxide etc..
Preferably, step（4）In, the lower alcohol is the one or more in methanol, ethanol, propyl alcohol or butanol etc..
Preferably, step（4）In, the temperature of the heating is 70~90 DEG C.
Preferably, step（5）In, the mode of the calcining is：With 3~5 DEG C of speed, first from room temperature to 450~
500 DEG C, 4~6h is calcined, then with 3~5 DEG C of speed, be continuously heating to 750~950 DEG C, calcine 8~12h.First section calcining can
Lithium salts is melted, preferably can be sufficiently mixed with metal oxide, the second section calcining can make lithium salts and reactive metal oxide, most
Throughout one's life into ternary material.
The present invention principle be：Soft template with nickel, cobalt, manganese in polyhydric alcohol solutions, generates particle as spherical soft template
The uniform nanoparticle metal alkoxide with shell inner core, by calcining, the kernel of metal alkoxide shrinks, the gold of generation
Belong to oxide and form hollow shell structure, then lithium, calcine by steps generation ternary material are mixed by wet method.The hollow shell structure of resulting materials,
It is uniform to be advantageous to mixed lithium, can fully be contacted with electrolyte, shorten the diffusion admittance of lithium ion and electronics, there is good electrification
Learn performance.
Beneficial effects of the present invention are as follows：
（1）Lithium ion battery of the present invention is uniform with nickel-cobalt-manganternary ternary anode material granular precursor, and particle diameter is about 500nm~1 μm,
In hollow ball-shape structure；Lithium ion battery of the present invention is also in hollow ball-shape structure with nickel-cobalt-manganternary ternary anode material, and particle diameter is about
500~600nm, thickness of the shell are about 50~100nm；
（2）Lithium ion battery of the present invention is assembled into battery with nickel-cobalt-manganternary ternary anode material, in 3.00~4.40V voltage ranges
Interior, under 15mA/g current densities, the gram volume that discharges first may be up to 196mAh/g, head effects（Battery initial charge and the appearance of electric discharge
Measure ratio）Up to 81.5%, the circle of circulation 20, conservation rate may be up to 95%, illustrate tertiary cathode material electron conduction of the present invention
Good, ionic conductivity height, electric discharge gram volume are high, good cycle, and electrochemical ion diffusion admittance is short；
（3）The inventive method preparation flow is simple, and cost is low, suitable for industrialized production.
Brief description of the drawings
Fig. 1 is the SEM figures of the gained presoma of the embodiment of the present invention 1；
Fig. 2 is the TEM figures of the gained tertiary cathode material of the embodiment of the present invention 1；
Fig. 3 is the XRD of the gained tertiary cathode material of the embodiment of the present invention 1；
Fig. 4 is the first charge-discharge curve map of the battery of the gained tertiary cathode material of the embodiment of the present invention 1 assembling；
Fig. 5 is the charge and discharge cycles curve map of the battery of the gained tertiary cathode material of the embodiment of the present invention 1 assembling.
Embodiment
With reference to embodiment and accompanying drawing, the invention will be further described.
Chemical reagent used in the embodiment of the present invention, unless otherwise specified, obtained by routine business approach.
Embodiment 1
（1）0.5mmol nickel acetates, 0.5mmol cobalt acetates, 0.5mmol manganese acetates and 0.1g polyvinylpyrrolidones are dissolved in
In 50mL ethylene glycol solvents, mixed solution is obtained；
（2）By step（1）Gained mixed solution, at 170 DEG C, back flow reaction 6h is carried out, room temperature is naturally cooled to, in rotating speed
Under 6000r/min, 6min is centrifuged, is washed 4 times with ethanol, at 80 DEG C, dried 12h, obtain metal alkoxide；
（3）By step（2）Gained metal alkoxide is in air atmosphere, with 3 DEG C/min of speed, from room temperature to 500 DEG C, calcining
4h, cool to room temperature with the furnace, obtain presoma；
（4）By step（3）Gained presoma is scattered in 100mL ethanol solutions with 1.575mmol lithium hydroxides, at 80 DEG C,
Heating stirring obtains black powder to being evaporated；
（5）By step（4）Gained black powder is in air atmosphere, first from room temperature to 500 DEG C with 5 DEG C/min speed,
4h, then the speed with 5 DEG C/min are calcined, is continuously heating to 950 DEG C, 10h is calcined, obtains lithium ion battery nickel-cobalt-manganese ternary positive pole
Material LiNi1/3Co1/3Mn1/3O2。
As shown in figure 1, presoma uniform particle sizes obtained by the embodiment of the present invention, particle diameter is about 500nm~1 μm.
As shown in Fig. 2 tertiary cathode material obtained by the embodiment of the present invention is hollow ball-shape structure, particle diameter is about 500~
600nm, thickness of the shell are about 50~80nm.
From the figure 3, it may be seen that ternary material obtained by the embodiment of the present invention is pure phase, the peak ＞ 2,006/102,108/ of 003 peak/104
The division of 110 peaks is obvious, and layer structure is good.
The assembling of battery：Lithium ion battery nickel-cobalt-manganternary ternary anode material obtained by the 0.016 g embodiment of the present invention is weighed,
Add that 0.002g acetylene blacks make conductive agent and 0.002g Kynoar makees binding agent, 1-METHYLPYRROLIDONE as dispersant,
It is applied to after well mixed on aluminium foil and positive plate is made, using metal lithium sheet as negative pole in vacuum glove box, with pe, pp composite membrane
For barrier film, 1mol/L lithium hexafluoro phosphates/DMC:EC（Volume ratio is 1:1）For electrolyte, CR2025 button cell is assembled into.
As shown in figure 4, after testing, the battery assembled is in 3.00~4.40V voltage ranges, 15mA/g current densities
Under, the gram volume that discharges first is 158.9mAh/g, and head effects are 81.5%.
As shown in figure 5, after testing, the battery assembled is in 3.00~4.40V voltage ranges, 15mA/g current densities
Under, the circle of circulation 20, capability retention 95%.
Embodiment 2
（1）By 0.9mmol nickel acetates, 0.3mmol cobalt acetates, 0.3mmol manganese acetates and 0.1g cetyl trimethylammonium bromides
It is dissolved in 40mL ethylene glycol solvents, obtains mixed solution；
（2）By step（1）Gained mixed solution, at 180 DEG C, back flow reaction 2h is carried out, room temperature is naturally cooled to, in rotating speed
Under 8000r/min, 7min is centrifuged, is washed 5 times with ethanol, at 100 DEG C, dried 8h, obtain metal alkoxide；
（3）By step（2）Gained metal alkoxide is in oxygen atmosphere, with 4 DEG C/min of speed, from room temperature to 600 DEG C, calcining
5h, cool to room temperature with the furnace, obtain presoma；
（4）By step（3）Gained presoma is scattered in 80mL methanol solutions with 1.575mol lithium acetates, at 70 DEG C, heating
Stirring obtains black powder to being evaporated；
（5）By step（4）Gained black powder is in oxygen atmosphere, first from room temperature to 460 DEG C with 3 DEG C/min speed,
6h, then the speed with 3 DEG C/min are calcined, is continuously heating to 850 DEG C, 12h is calcined, obtains lithium ion battery nickel-cobalt-manganese ternary positive pole
Material LiNi0.6Co0.2Mn0.2O2。
After testing, presoma uniform particle sizes obtained by the embodiment of the present invention, particle diameter is about 600nm~1 μm.
After testing, tertiary cathode material obtained by the embodiment of the present invention is hollow ball-shape structure, and particle diameter is about 500~600nm,
Thickness of the shell is about 60~100nm.
After testing, ternary material obtained by the embodiment of the present invention is pure phase, and layer structure is good.
The assembling of battery：Lithium ion battery nickel-cobalt-manganternary ternary anode material obtained by the 0.016 g embodiment of the present invention is weighed,
Add that 0.002g acetylene blacks make conductive agent and 0.002g Kynoar makees binding agent, 1-METHYLPYRROLIDONE as dispersant,
It is applied to after well mixed on aluminium foil and positive plate is made, using metal lithium sheet as negative pole in vacuum glove box, with pe, pp composite membrane
For barrier film, 1mol/L lithium hexafluoro phosphates/DMC:EC（Volume ratio is 1:1）For electrolyte, CR2025 button cell is assembled into.
After testing, the battery assembled under 15mA/g current densities, discharges first in 3.00~4.40V voltage ranges
Gram volume is 173mAh/g, and head effects are 81.1%.
After testing, the battery assembled is in 3.00~4.40V voltage ranges, under 15mA/g current densities, the circle of circulation 20,
Capability retention is 93%.
Embodiment 3
（1）1.2mmol nickel acetates, 0.15mmol cobalt acetates, 0.15mmol manganese acetates and 0.1g polyvinylpyrrolidones are dissolved
In 60mL glycerine solvents, mixed solution is obtained；
（2）By step（1）Gained mixed solution, at 170 DEG C, back flow reaction 4h is carried out, room temperature is naturally cooled to, in rotating speed
Under 6000r/min, 8min is centrifuged, is washed 4 times with ethanol, at 90 DEG C, dried 10h, obtain metal alkoxide；
（3）By step（2）Gained metal alkoxide is in oxygen atmosphere, with 3 DEG C/min of speed, from room temperature to 500 DEG C, calcining
4h, cool to room temperature with the furnace, obtain presoma；
（4）By step（3）Gained presoma is scattered in 80mL ethanol solutions with 1.56mol lithium hydroxides, at 80 DEG C, heating
Stirring obtains black powder to being evaporated；
（5）By step（4）Gained black powder is in oxygen atmosphere, first from room temperature to 480 DEG C with 4 DEG C/min speed,
5h, then the speed with 4 DEG C/min are calcined, is continuously heating to 750 DEG C, 10h is calcined, obtains lithium ion battery nickel-cobalt-manganese ternary positive pole
Material LiNi0.8Co0.1Mn0.1O2。
After testing, presoma uniform particle sizes obtained by the embodiment of the present invention, particle diameter is about 500nm~1 μm.
After testing, tertiary cathode material obtained by the embodiment of the present invention is hollow ball-shape structure, and particle diameter is about 500~600nm,
Thickness of the shell is about 70~100nm.
After testing, ternary material obtained by the embodiment of the present invention is pure phase, and layer structure is good.
The assembling of battery：Lithium ion battery nickel-cobalt-manganternary ternary anode material obtained by the 0.016 g embodiment of the present invention is weighed,
Add that 0.002g acetylene blacks make conductive agent and 0.002g Kynoar makees binding agent, 1-METHYLPYRROLIDONE as dispersant,
It is applied to after well mixed on aluminium foil and positive plate is made, using metal lithium sheet as negative pole in vacuum glove box, with pe, pp composite membrane
For barrier film, 1mol/L lithium hexafluoro phosphates/DMC:EC（Volume ratio is 1:1）For electrolyte, CR2025 button cell is assembled into.
After testing, the battery assembled under 15mA/g current densities, discharges first in 3.00~4.40V voltage ranges
Gram volume is 196mAh/g, and head effects are 80%.
After testing, the battery assembled is in 3.00~4.40V voltage ranges, under 15mA/g current densities, the circle of circulation 20,
Capability retention is 92.4%.
Claims (9)
1. a kind of lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that be made up of following methods：
（1）Nickel source, cobalt source, manganese source and soft template are dissolved in polyol solvent, obtain mixed solution；
（2）By step（1）Gained mixed solution carries out back flow reaction, naturally cools to room temperature, centrifuges, and washs, and dries, obtains metal
Alkoxide；
（3）By step（2）Gained metal alkoxide is calcined in air or oxygen atmosphere, cools to room temperature with the furnace, obtains presoma；
（4）By step（3）Gained presoma is scattered in lower alcohol with lithium source, and heating stirring obtains black powder to being evaporated；
（5）By step（4）Gained black powder is calcined in air or oxygen atmosphere, cools to room temperature with the furnace, obtains lithium-ion electric
Pond nickel-cobalt-manganternary ternary anode material.
2. lithium ion battery nickel-cobalt-manganternary ternary anode material according to claim 1, it is characterised in that：Step（1）In, institute
It is any ratio to state nickel in nickel source, cobalt source, manganese source, cobalt, the mol ratio of manganese element；The dosage of the polyol solvent is so that nickel
Total concentration of the amount summation of nickel, cobalt, manganese element material in polyol solvent is 0.01~0.05mol/ in source, cobalt source, manganese source
L；Mass concentration of the soft template in polyol solvent is 1~3g/L.
3. lithium ion battery nickel-cobalt-manganternary ternary anode material according to claim 1 or claim 2, it is characterised in that：Step（1）
In, the nickel source is the one or more in nickel formate, nickel acetate or dicyclopentadienyl nickel；The cobalt source is cobalt acetate or acetylacetone,2,4-pentanedione
Cobalt；The manganese source is the one or more in manganese acetate, manganese acetylacetonate or manganese acetate；The soft template is polyvinylpyrrolidine
Ketone or cetyl trimethylammonium bromide；The polyol solvent is ethylene glycol or glycerine.
4. according to one of claims 1 to 3 lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that：Step
（2）In, the temperature of the back flow reaction is 150~200 DEG C, and the time of back flow reaction is 2~8h.
5. according to one of Claims 1 to 4 lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that：Step
（2）In, the rotating speed of the centrifugation is 5000~10000 r/min, and the time of centrifugation is 5~10min；The mode of washing is use
Ethanol washs >=4 times；The temperature of the drying is 80~120 DEG C, and the dry time is 8~12h.
6. according to one of Claims 1 to 5 lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that：Step
（3）In, the mode of the calcining is：With 1~5 DEG C/min speed, from room temperature to 450~650 DEG C, 3~6 h are calcined.
7. according to one of claim 1~6 lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that：Step
（4）In, elemental lithium and nickel element in nickel source, cobalt source, manganese source in the lithium source, cobalt element, the amount summation of manganese element material are rubbed
You are than being 1.04~1.06:1；The dosage of the lower alcohol is 40~100mL/1mol elemental lithiums；The lithium source is lithium carbonate, second
One or more in sour lithium or lithium hydroxide；The lower alcohol is the one or more in methanol, ethanol, propyl alcohol or butanol.
8. according to one of claim 1~7 lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that：Step
（4）In, the temperature of the heating is 70~90 DEG C.
9. according to one of claim 1~8 lithium ion battery nickel-cobalt-manganternary ternary anode material, it is characterised in that：Step
（5）In, the mode of the calcining is：It is first from room temperature to 450~500 DEG C with 3~5 DEG C of speed, 4~6h of calcining, then with
3~5 DEG C of speed, 750~950 DEG C are continuously heating to, calcine 8~12h.
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