CN109786731A - Electrode material, lithium ion battery and preparation method thereof, application - Google Patents
Electrode material, lithium ion battery and preparation method thereof, application Download PDFInfo
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Abstract
The present invention discloses a kind of electrode material, lithium ion battery and preparation method thereof, application.The preparation method includes the following steps: to calcine the mixture of ternary precursor material, crystal seed and the fused salt containing lithium ion in oxygen-containing atmosphere；Wherein, the molar ratio of ternary precursor material and crystal seed is 2:10-10:1；Ternary precursor material is nickel cobalt manganese hydroxide or nickel cobalt aluminium hydroxide.The average diameter of the electrode obtained material can be controlled in suitable range, therefore reduce its interface side reaction during circulating battery, and then improve the capacity retention ratio of battery by the preparation method, obtain preferable high rate performance and cyclical stability.
Description
Technical field
The present invention relates to a kind of electrode materials, lithium ion battery and preparation method thereof, application.
Background technique
Cobalt acid lithium is most widely used lithium battery material at present, but cobalt resource is increasingly deficient and expensive, serious shadow
It rings to its utilization.Nickel-cobalt lithium manganate material with relatively inexpensive nickel and manganese instead of in cobalt acid lithium 2/3rds or more cobalt, from
And effectively reduce the cost of material and expand raw material sources, it becomes by people's extensive concern and the lithium of research electricity
One of pond material.
Currently, the preparation method of existing nickel-cobalt lithium manganate material have raw material is directly mixed or is mixed after the solid phase that roasts
Method, by coprecipitation dry after dissolution of raw material mixed precipitation, using solvent dispersion and mixed raw material suspension method, use mould
Plate arranges the template being oriented to etc. a variety of methods to limit raw material, but nickel-cobalt lithium manganate material is prepared in above-mentioned method
Certain defect is all had, if uniform particle diameter is poor, poor circulation etc. is not able to satisfy the demand used.
Chinese patent literature CN 104868122A discloses a kind of preparation method of monocrystalline nickel-cobalt lithium manganate material, uses
Solwution method preparation, the diameter of nickel-cobalt lithium manganate material obtained is about 0.5 μm, and gained lithium ion battery is recycled at 0.2C
Capacity retention ratio after 100 times is only 86.4-93.1%.
Also there is the relevant report that nickel cobalt manganese (aluminium) sour lithium material is prepared in fused salt in the prior art, preparation method is such as
Under: the hydroxide and fused salt of nickel cobalt manganese (aluminium) are obtained through calcining.However above-mentioned preparation method makes its material obtained itself
Average diameter (less than 2 μm) it is smaller so that battery capacity conservation rate, high rate performance and cyclical stability obtained compared with
Difference.
Summary of the invention
The technical problem to be solved by the present invention is to the preparation methods in order to overcome the sour lithium material of existing nickel cobalt manganese (aluminium)
So that the average diameter of its material itself is smaller, so that battery capacity conservation rate, high rate performance and stable circulation obtained
Property poor defect, and provide a kind of novel electrode material, lithium ion battery and preparation method thereof, application.System of the invention
The average diameter of the electrode obtained material can be controlled in suitable range by introducing crystal seed, therefore reduce it by Preparation Method
Interface side reaction during circulating battery, and then the capacity retention ratio of battery is improved, obtain preferable high rate performance
And cyclical stability.
The present invention solves above-mentioned technical problem by the following technical programs:
The present invention provides a kind of electrode material, and the average diameter of the electrode material is 3-10 microns；
Wherein, when the electrode material is nickel-cobalt lithium manganate material, the chemical formula of the nickel-cobalt lithium manganate material is
LiaNix1Cox2Mnx3O2, and 0 < x1 <, 1,0 < x2 < 1,0 < x3 < 1, x1+x2+x3=1, a 1-1.2；
Wherein, when the electrode material is nickel cobalt aluminic acid lithium material, the chemical formula of the nickel cobalt aluminic acid lithium material is
LibNiy1Coy2Aly3O2, and 0 < y1 <, 1,0 < y2 < 1,0 < y3 < 1, y1+y2+y3=1, b 1-1.2.
In above-mentioned electrode material, the average diameter of the electrode material is preferably 3-6 microns, more preferably micro- for 3-5
Rice.
In above-mentioned electrode material, the test method of the average diameter is as follows: the ratio in product obtained by random screening
If 100 particles measure the distance between the farthest two o'clock on each particle with flying-spot microscope, average value, as institute are obtained
State average diameter.
In above-mentioned electrode material, x1 is preferably 0.6-0.85, is more preferably 0.6-0.8.
In above-mentioned electrode material, x2 is preferably 0.1-0.2.
In above-mentioned electrode material, x3 is preferably 0.05-0.2, is more preferably 0.1-0.2.
In above-mentioned electrode material, a is preferably 1-1.1.
In above-mentioned electrode material, y1 is preferably 0.6-0.85, is more preferably 0.85.
In above-mentioned electrode material, y2 is preferably 0.1-0.2, is more preferably 0.1.
In above-mentioned electrode material, y3 is preferably 0.05-0.2, is more preferably 0.05.
In above-mentioned electrode material, b is preferably 1-1.1.
In above-mentioned electrode material, the chemical formula of the electrode material is preferably LiNi0.6Co0.2Mn0.2O2。
In above-mentioned electrode material, the chemical formula of the electrode material is preferably LiNi0.8Co0.1Mn0.1O2。
In above-mentioned electrode material, the chemical formula of the electrode material is preferably LiNi0.85Co0.1Al0.05O2。
The present invention also provides a kind of preparation method of electrode material, the preparation method includes the following steps: will be before ternary
The mixture for driving body material, crystal seed and the fused salt containing lithium ion is calcined in oxygen-containing atmosphere；Wherein, the ternary forerunner
The molar ratio of body material and the crystal seed is 2:10-10:1；The ternary precursor material is nickel cobalt manganese hydroxide or nickel cobalt
Aluminium hydroxide；
When the ternary precursor material is nickel cobalt manganese hydroxide, the chemical formula of the nickel cobalt manganese hydroxide is
Nix1Cox2Mnx3(OH)2, the chemical formula of the crystal seed is Lia1Nix1Cox2Mnx3O2, and 0 < x1 <, 1,0 < x2 <, 1,0 < x3 <
1, x1+x2+x3=1, a1 1-1.2；
When the ternary precursor material is nickel cobalt aluminium hydroxide, the chemical formula of the nickel cobalt aluminium hydroxide is
Niy1Coy2Aly3(OH)2, the chemical formula of the crystal seed is Lib1Niy1Coy2Aly3O2, and 0 < y1 <, 1,0 < y2 <, 1,0 < y3 <
1, y1+y2+y3=1, b1 1-1.2.
In above-mentioned preparation method, x1 is preferably 0.6-0.85, is more preferably 0.6-0.8.
In above-mentioned preparation method, x2 is preferably 0.1-0.2.
In above-mentioned preparation method, x3 is preferably 0.05-0.2, is more preferably 0.1-0.2.
In above-mentioned preparation method, a1 is preferably 1.
In above-mentioned preparation method, the chemical formula of the nickel cobalt manganese hydroxide may be, for example, Ni0.6Co0.2Mn0.2(OH)2, right
The chemical formula for the crystal seed answered is LiNi0.6Co0.2Mn0.2O2。
In above-mentioned preparation method, the chemical formula of the nickel cobalt manganese hydroxide may be, for example, Ni0.8Co0.1Mn0.1(OH)2, right
The chemical formula for the crystal seed answered is LiNi0.8Co0.1Mn0.1O2。
In above-mentioned preparation method, y1 is preferably 0.6-0.85, is more preferably 0.85.
In above-mentioned preparation method, y2 is preferably 0.1-0.2, is more preferably 0.1.
In above-mentioned preparation method, y3 is preferably 0.05-0.2, is more preferably 0.05.
In above-mentioned preparation method, b1 is preferably 1.
In above-mentioned preparation method, the chemical formula of the nickel cobalt aluminium hydroxide may be, for example, Ni0.85Co0.1Al0.05(OH)2,
The chemical formula of the corresponding crystal seed is LiNi0.85Co0.1Al0.05O2。
In above-mentioned preparation method, the ternary precursor material for example can be used coprecipitation and be made.
In above-mentioned preparation method, the molar ratio of the ternary precursor material and the crystal seed is preferably 1:1-10:1.
In above-mentioned preparation method, the fused salt containing lithium ion can for can by the ternary precursor material dissolve and
The inorganic salts containing lithium ion of liquid are able to maintain under the calcining.The fused salt containing lithium ion may be, for example, Li2SO4、LiF、
One of LiCl and LiOH or a variety of.It can also further include Na in the fused salt containing lithium ion2SO4、K2SO4、
Rb2SO4、Cs2SO4、NaCl、KCl、RbCl、CsCl、BaCl2, one of CaCl, NaOH and KOH or a variety of.It is described containing lithium from
The fused salt of son is more preferably LiOH and NaCl.Wherein, the molar ratio of LiOH and NaCl is preferably 1:10-10:1, more preferably for
1:1-1.1:1。
In above-mentioned preparation method, when the fused salt containing lithium ion is LiOH and NaCl, the ternary precursor material
0.25:1-0.44:1 is preferably with the molar ratio of the fused salt containing lithium ion.
In above-mentioned preparation method, before the calcining, the calcining is preferably risen to the heating rate of 5-30 DEG C/min
Temperature, the temperature of the calcining is more preferably risen to the heating rate of 10 DEG C/min.
In above-mentioned preparation method, the oxygen-containing atmosphere can be air atmosphere or oxygen atmosphere.
In above-mentioned preparation method, the calcining can be realized the anti-of the ternary precursor material and oxygen and lithium ion
It answers, and generates the electrode material, and the molar ratio of the ternary precursor material, oxygen and lithium ion in the seed surface
Meet the stoichiometric relationship of above-mentioned reaction.
In above-mentioned preparation method, the temperature of the calcining can be the calcination temperature of this field routine, may be, for example, 600-
1000 DEG C, preferably 900 DEG C.
In above-mentioned preparation method, the time of the calcining can be the calcination time of this field routine, may be, for example, 2-48h,
Preferably 10h.
In above-mentioned preparation method, after the calcining preferably after water washing, then it is dried.
Wherein, the washing is carried out after being preferably first cooled to room temperature after the calcining again, the room temperature is 20-30
DEG C, preferably 25 DEG C.
Wherein, the washing refers to that will have neither part nor lot in fused salt described in reaction containing lithium ion with water removes.
Wherein, preferably, the drying process carries out under vacuum.The temperature of the drying process is preferably 60-200
DEG C, it is more preferably 120 DEG C.The time of the drying process is preferably 1-12, is more preferably 3h.
Wherein, it is preferably calcined again after the drying process.The atmosphere calcined again can be air
Atmosphere or oxygen atmosphere.The temperature calcined again is preferably 400-900 DEG C, is more preferably 750 DEG C.It is described to calcine again
Time be preferably 1-24h, may be, for example, 6h or 20h, be more preferably 10h.It is preferably cooled to after the calcining again
Room temperature, the room temperature are 20-30 DEG C, preferably 25 DEG C.
Wherein, the temperature calcined again is preferably risen to the heating rate of 5-20 DEG C/min after the drying process
Degree more preferably rises to the temperature calcined again after the drying process with the heating rate of 10 DEG C/min.
The present invention also provides one kind electrode material as made from preparation method above-mentioned, the average diameters of the electrode material
It is 3-10 microns, preferably 3-6 microns, be more preferably 3-5 microns.
Compared with the sour lithium material of existing nickel cobalt manganese (aluminium), the average diameter of electrode material of the invention is bigger, specific surface
Product is smaller, and has particular crystal plane pattern.
Wherein, when the electrode material is nickel-cobalt lithium manganate material, the chemical formula of the nickel-cobalt lithium manganate material is
LiaNix1Cox2Mnx3O2, and 0 < x1 <, 1,0 < x2 < 1,0 < x3 < 1, x1+x2+x3=1, a 1-1.2.Wherein, a can also be
1-1.1。
Wherein, when the electrode material is nickel cobalt aluminic acid lithium material, the chemical formula of the nickel cobalt aluminic acid lithium material is
LibNiy1Coy2Aly3O2, and 0 < y1 <, 1,0 < y2 < 1,0 < y3 < 1, y1+y2+y3=1, b 1-1.2.Wherein, b can also be
1-1.1。
Wherein, the test method of the average diameter is as follows: such as 100 in product obtained by random screening
Grain measures the distance between the farthest two o'clock on each particle with flying-spot microscope, obtains average value, as described average straight
Diameter.
A kind of application the present invention also provides electrode material above-mentioned as the positive electrode in lithium ion battery.
The present invention also provides one kind lithium ion batteries as made from electrode material above-mentioned.The preparation of the lithium ion battery
Method can be as described below: by electrode material described in 0.9g, 0.05g acetylene black, 0.05g PVDF is dissolved in nmp solvent and mixing
It is even, be coated in aluminium foil on, 80 DEG C drying 2 hours, 120 DEG C drying 6 hours, be made diameter for 1cm round pole piece, use lithium metal
As to electrode, electrolyte is made of the LiPF6 of EC and EMC and 1M that volume ratio is 3:7, is assembled into 2032 button cells i.e.
Can, 2032 button cell is the lithium ion battery.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: the present invention provides a kind of electrode material, lithium ion battery and its preparation side
Method, application.Preparation method of the invention can be controlled the average diameter of the electrode obtained material suitable by introducing crystal seed
In the range of, therefore its interface side reaction during circulating battery is reduced, and then improve the capacity retention ratio of battery, it obtains
Obtained preferable high rate performance and cyclical stability.
Detailed description of the invention
Fig. 1 is the normalization specific capacity of 2 gained battery of embodiment 5, embodiment 6 and comparative example with the variation of cycle-index
Figure；
Fig. 2 is the scanning electron microscope (SEM) photograph of 1 products therefrom of embodiment；
Fig. 3 is the scanning electron microscope (SEM) photograph of 1 products therefrom of comparative example；
Fig. 4 is the scanning electron microscope (SEM) photograph of 3 products therefrom of comparative example.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
In following embodiments, the room temperature refers to 25 DEG C.
In following embodiments and comparative example, persursor material is made using coprecipitation.
The test method of average diameter in following embodiments and comparative example is as follows: in product obtained by random screening
For example 100 particles measure the distance between the farthest two o'clock on each particle with flying-spot microscope, obtain average value, as
Average diameter.
In following embodiments and comparative example, the heating, heating and holding carry out in air atmosphere, and described
The process of holding is the process calcined.
Embodiment 1
By (9.2g, 0.1mol) presoma Ni0.6Co0.2Mn0.2(OH)2, (9.7g, 0.1mol) crystal seed
LiNi0.6Co0.2Mn0.2O2, (4.72g, 0.2mol) LiOH, (11.69g, 0.2mol) NaCl are uniformly mixed, are put into corundum crucible
In, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, cooled to room temperature, mixture deionization
Water washing removes fused salt three times, is dried in vacuo 3 hours, is then placed in crucible in 120 DEG C, with the heating rate of 10 DEG C/min,
750 DEG C are heated to, is kept for 6 hours, cooled to room temperature obtains product 1, chemical formula LiNi0.6Co0.2Mn0.2O2。
Wherein, the elemental analysis of the presoma and product 1 of embodiment 1 is as follows.
Elemental analysis (ICP) result
| Embodiment 1 | Li | Ni | Co | Mn |
| Presoma | 0 | 0.5949 | 0.2002 | 0.2050 |
| Product 1 | 1.03 | 0.5950 | 0.2000 | 0.2046 |
Embodiment 2
By (9.2g, 0.1mol) presoma Ni0.6Co0.2Mn0.2(OH)2, (0.97g, 0.01mol) crystal seed
LiNi0.6Co0.2Mn0.2O2, (2.9g, 0.121mol) LiOH, (6.43g, 0.11mol) NaCl are uniformly mixed, are put into corundum crucible
In, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, cooled to room temperature, mixture deionization
Water washing removes fused salt three times, is dried in vacuo 3 hours, is then placed in crucible in 120 DEG C, with the heating rate of 10 DEG C/min,
750 DEG C are heated to, is kept for 6 hours, cooled to room temperature obtains product 2, chemical formula LiNi0.6Co0.2Mn0.2O2。
Embodiment 3
By (9.2g, 0.1mol) presoma Ni0.8Co0.1Mn0.1(OH)2, (9.7g, 0.1mol) crystal seed
LiNi0.8Co0.1Mn0.1O2, (4.72g, 0.2mol) LiOH, (11.69g, 0.2mol) NaCl are uniformly mixed, are put into corundum crucible
In, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, cooled to room temperature, mixture deionization
Water washing removes fused salt three times, is dried in vacuo 3 hours, is then placed in crucible in 120 DEG C, with the heating rate of 10 DEG C/min,
750 DEG C are heated to, is kept for 6 hours, cooled to room temperature obtains product 3, chemical formula LiNi0.8Co0.1Mn0.1O2。
Embodiment 4
By (9.1g, 0.1mol) presoma Ni0.85Co0.1Al0.05(OH)2, (9.6g, 0.1mol) crystal seed
LiNi0.85Co0.1Al0.05O2, (4.72g, 0.2mol) LiOH, (11.69g, 0.2mol) NaCl are uniformly mixed, are put into corundum crucible
In, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, cooled to room temperature, mixture deionization
Water washing removes fused salt three times, is dried in vacuo 3 hours, is then placed in crucible in 120 DEG C, with the heating rate of 10 DEG C/min,
750 DEG C are heated to, is kept for 6 hours, cooled to room temperature obtains product 4, chemical formula LiNi0.85Co0.1Al0.05O2。
Embodiment 5
By 0.9g product 1,0.05g acetylene black, 0.05g PVDF is dissolved in nmp solvent and being uniformly mixed, and is coated in aluminium foil
On, 80 DEG C drying 2 hours, 120 DEG C drying 6 hours.The round pole piece that diameter is 1cm is made, uses lithium metal as to electrode, electricity
Solution liquid is that (EC/EMC=3/7 volume ratio, 1MLiPF6) is assembled into 2032 button cells.
Embodiment 6
By 0.9g product 2,0.05g acetylene black, 0.05g PVDF is dissolved in nmp solvent and being uniformly mixed, and is coated in aluminium foil
On, 80 DEG C drying 2 hours, 120 DEG C drying 6 hours.The round pole piece that diameter is 1cm is made, uses lithium metal as to electrode, electricity
Solution liquid is that (EC/EMC=3/7 volume ratio, 1MLiPF6) is assembled into 2032 button cells.
Comparative example 1
By (18.4g, 0.2mol) presoma Ni0.6Co0.2Mn0.2(OH)2, (4.79g, 0.2mol) LiOH, (11.69g,
0.2mol) NaCl is uniformly mixed, and is put into corundum crucible, with the heating rate of 10 DEG C/min, is heated to 900 DEG C, holding 10 is small
When, cooled to room temperature, mixture is washed with deionized three times, is dried in vacuo 3 hours in 120 DEG C, is then placed in crucible
In, with the heating rate of 10 DEG C/min, 750 DEG C are heated to, is kept for 6 hours, cooled to room temperature obtains product 5.
Comparative example 2
By 0.9g product 5,0.05g acetylene black, 0.05g PVDF is dissolved in nmp solvent and being uniformly mixed, and is coated in aluminium foil
On, 80 DEG C drying 2 hours, 120 DEG C drying 6 hours.The round pole piece that diameter is 1cm is made, uses lithium metal as to electrode, electricity
Solution liquid is that (EC/EMC=3/7 volume ratio, 1MLiPF6) is assembled into 2032 button cells.
Comparative example 3
By (9.2g, 0.1mol) presoma Ni0.6Co0.2Mn0.2(OH)2, (0.49g, 0.005mol) crystal seed
LiNi0.6Co0.2Mn0.2O2, (4.79g, 0.2mol) LiOH, (11.69g, 0.2mol) NaCl are uniformly mixed, are put into corundum crucible
In, with the heating rate of 10 DEG C/min, 900 DEG C are heated to, is kept for 10 hours, cooled to room temperature, mixture deionization
Water washing removes fused salt three times, is dried in vacuo 3 hours, is then placed in crucible in 120 DEG C, with the heating rate of 10 DEG C/min,
750 DEG C are heated to, is kept for 6 hours, cooled to room temperature obtains product 5, chemical formula LiNi0.6Co0.2Mn0.2O2。
1 loop test of effect example
1, test condition: voltage range 2.8-4.3V, after current cycle 3 times of first 0.1C multiplying power, the electric current of 1C multiplying power is followed
Ring 300 times.
As a result: from figure 1 it appears that after 300 circulations, the appearance of 6 gained battery of comparative example 2, embodiment 5 and embodiment
Measuring conservation rate is respectively 74.6%, 87.5%, 82.93%.It can be seen that with the addition of crystal seed, the finished product nickel cobalt manganese that is generated by it
The cyclical stability of battery made from sour lithium significantly improves.
2, test condition: current cycle 100 times of voltage range 2.8-4.3V, 0.2C multiplying power.
As a result: the capacity retention ratio of 6 gained battery of embodiment 5 and embodiment is respectively 96.3%, 92.8%.
3, test condition: current cycle 100 times of voltage range 2.8-4.3V, 1C multiplying power.
As a result: the capacity retention ratio of 6 gained battery of embodiment 5 and embodiment is respectively 94.7%, 89.5%.
The test of 2 multiplying power of effect example
Test condition is voltage range 2.8-4.3V, and charging current is 0.2C multiplying power, and discharge current 0.2C is recycled 5 times；
Then, discharge current 1C is recycled 5 times；Discharge current is 3C, is recycled 5 times；Discharge current is 5C, is recycled 5 times；Discharge current
For 10C, recycle 5 times；Discharge current is 20C, is recycled 5 times；Wherein, 5 specific capacities are taken respectively, and 5 specific capacities of gained are averaged
Value is the Average specific capacities in following table.
The Average specific capacities (unit (mAh/g)) of gained battery in the test of 1 multiplying power of table
| 0.2C | 1C | 3C | 5C | 10C | 20C | |
| Comparative example 2 | 173 | 166 | 156 | 145 | 136 | 128 |
| Embodiment 5 | 178 | 170 | 163 | 151 | 144 | 132 |
| Embodiment 6 | 175 | 168 | 160 | 149 | 141 | 130 |
Seen from table 1, the high rate performance of 5 gained battery of embodiment is optimal, and embodiment 6 is taken second place, and comparative example 2 is better than.
3 scanning electron microscopic observation of effect example
From Fig. 2 and Fig. 3 it is found that the average diameter of 1 products therefrom of embodiment is 3-5 microns, 1 products therefrom of comparative example is put down
Equal diameter is 1-2 microns.It can be seen that the average diameter of 1 products therefrom of embodiment is significantly greater than comparative example 1, and inventor exists
It is found in R&D process, the specific surface area of 1 products therefrom of embodiment is smaller, and interface side reaction is less, and then it is made
Battery show better capacity retention ratio, high rate performance and cyclical stability.That is, the performance of 5 gained battery of embodiment
Better than the performance of 2 gained battery of comparative example.
From fig. 4, it can be seen that the average diameter of 3 products therefrom of comparative example is 0.4 micron, specific surface area is greater than embodiment
1 and embodiment 2, interface side reaction increases, so that the capacity retention ratio of its battery obtained, high rate performance and stable circulation
Property is worse than battery made from 2 products therefrom of embodiment 1 and embodiment.That is, the performance of battery made from 3 products therefrom of comparative example
It is worse than the performance of battery obtained by embodiment 5 and embodiment 6.
Although specific embodiments of the present invention have been described above, it will be appreciated by those of skill in the art that this is only
For example, protection scope of the present invention is to be defined by the appended claims.Those skilled in the art without departing substantially from
Under the premise of the principle and substance of the present invention, many changes and modifications may be made, but these change and
Modification each falls within protection scope of the present invention.
Claims (10)
1. a kind of electrode material, which is characterized in that the average diameter of the electrode material is 3-10 microns；
Wherein, when the electrode material is nickel-cobalt lithium manganate material, the chemical formula of the nickel-cobalt lithium manganate material is
LiaNix1Cox2Mnx3O2, and 0 < x1 <, 1,0 < x2 < 1,0 < x3 < 1, x1+x2+x3=1, a 1-1.2；
Wherein, when the electrode material is nickel cobalt aluminic acid lithium material, the chemical formula of the nickel cobalt aluminic acid lithium material is
LibNiy1Coy2Aly3O2, and 0 < y1 <, 1,0 < y2 < 1,0 < y3 < 1, y1+y2+y3=1, b 1-1.2.
2. electrode material as described in claim 1, which is characterized in that the average diameter of the electrode material is 3-6 microns, compared with
It goodly is 3-5 microns；
And/or x1 0.6-0.85, preferably 0.6-0.8；
And/or x2 0.1-0.2；
And/or x3 0.05-0.2, preferably 0.1-0.2；
And/or a 1-1.1；
And/or y1 0.6-0.85, preferably 0.85；
And/or y2 0.1-0.2, preferably 0.1；
And/or y3 0.05-0.2, preferably 0.05；
And/or b 1-1.1；
Preferably, the chemical formula of the electrode material is LiNi0.6Co0.2Mn0.2O2；Or, the chemical formula of the electrode material is
LiNi0.8Co0.1Mn0.1O2；Or, the chemical formula of the electrode material is LiNi0.85Co0.1Al0.05O2。
3. a kind of preparation method of electrode material, which is characterized in that the preparation method includes the following steps: ternary precursor
The mixture of material, crystal seed and the fused salt containing lithium ion is calcined in oxygen-containing atmosphere；Wherein, the ternary precursor material
The molar ratio of material and the crystal seed is 2:10-10:1；The ternary precursor material is nickel cobalt manganese hydroxide or nickel cobalt aluminium hydrogen
Oxide；
When the ternary precursor material is nickel cobalt manganese hydroxide, the chemical formula of the nickel cobalt manganese hydroxide is
Nix1Cox2Mnx3(OH)2, the chemical formula of the crystal seed is Lia1Nix1Cox2Mnx3O2, and 0 < x1 <, 1,0 < x2 <, 1,0 < x3 <
1, x1+x2+x3=1, a1 1-1.2；
When the ternary precursor material is nickel cobalt aluminium hydroxide, the chemical formula of the nickel cobalt aluminium hydroxide is
Niy1Coy2Aly3(OH)2, the chemical formula of the crystal seed is Lib1Niy1Coy2Aly3O2, and 0 < y1 <, 1,0 < y2 <, 1,0 < y3 <
1, y1+y2+y3=1, b1 1-1.2.
4. the preparation method of electrode material as claimed in claim 3, which is characterized in that
The ternary precursor material is made using coprecipitation；
And/or the molar ratio of the ternary precursor material and the crystal seed is 1:1-10:1；
And/or x1 0.6-0.85, preferably 0.6-0.8；
And/or x2 0.1-0.2；
And/or x3 0.05-0.2, preferably 0.1-0.2；
And/or a1 1；
And/or y1 0.6-0.85, preferably 0.85；
And/or y2 0.1-0.2, preferably 0.1；
And/or y3 0.05-0.2, preferably 0.05；
And/or b1 1；
Preferably, the chemical formula of the nickel cobalt manganese hydroxide is Ni0.6Co0.2Mn0.2(OH)2, the chemistry of the corresponding crystal seed
Formula is LiNi0.6Co0.2Mn0.2O2；Or, the chemical formula of the nickel cobalt manganese hydroxide is Ni0.8Co0.1Mn0.1(OH)2, corresponding institute
The chemical formula for stating crystal seed is LiNi0.8Co0.1Mn0.1O2；Or, the chemical formula of the nickel cobalt aluminium hydroxide is Ni0.85Co0.1Al0.05
(OH)2, the chemical formula of the corresponding crystal seed is LiNi0.85Co0.1Al0.05O2。
5. the preparation method of electrode material as claimed in claim 3, which is characterized in that the fused salt containing lithium ion is
Li2SO4, one of LiF, LiCl and LiOH or a variety of；
It preferably include Na in the fused salt containing lithium ion2SO4、K2SO4、Rb2SO4、Cs2SO4、NaCl、KCl、RbCl、CsCl、
BaCl2, one of CaCl, NaOH and KOH or a variety of；
The fused salt containing lithium ion is more preferably LiOH and NaCl；Wherein, the molar ratio of LiOH and NaCl is preferably 1:10-
10:1 is more preferably 1:1-1.1:1；
When the fused salt containing lithium ion is LiOH and NaCl, the ternary precursor material and the fused salt containing lithium ion
Molar ratio be preferably 0.25:1-0.44:1.
6. the preparation method of electrode material as claimed in claim 3, which is characterized in that before the calcining, with 5-30 DEG C/
The heating rate of min rises to the temperature of the calcining, and the temperature of the calcining is preferably risen to the heating rate of 10 DEG C/min；
And/or the oxygen-containing atmosphere is air atmosphere or oxygen atmosphere；
And/or the temperature of the calcining is 600-1000 DEG C, preferably 900 DEG C；
And/or the time of the calcining is 2-48h, preferably 10h.
7. the preparation method of electrode material as claimed in claim 3, which is characterized in that after the calcining after water washing,
It is dried again；
Wherein, the washing is carried out after being preferably first cooled to room temperature after the calcining again, the room temperature is 20-30 DEG C, compared with
It goodly is 25 DEG C；
Wherein, the drying process preferably carries out under vacuum；The temperature of the drying process is preferably 60-200 DEG C, more
It goodly is 120 DEG C；The time of the drying process is preferably 1-12h, is more preferably 3h；
Wherein, it is preferably calcined again after the drying process；The atmosphere calcined again is preferably air
Atmosphere or oxygen atmosphere；The temperature calcined again is preferably 400-900 DEG C, is more preferably 750 DEG C；It is described to calcine again
Time be preferably 1-24h, be more preferably 10h；It is preferably cooled to room temperature after the calcining again, the room temperature is
20-30 DEG C, preferably 25 DEG C；
Wherein, the temperature calcined again is preferably risen to the heating rate of 5-20 DEG C/min after the drying process,
The temperature calcined again is more preferably risen to the heating rate of 10 DEG C/min after the drying process.
8. a kind of electrode material, which is characterized in that the electrode material is by such as described in any item preparation methods of claim 3-7
It is made, the average diameter of the electrode material is 3-10 microns, and preferably 3-6 microns, be more preferably 3-5 microns；
Wherein, when the electrode material is nickel-cobalt lithium manganate material, the chemical formula of the nickel-cobalt lithium manganate material is
LiaNix1Cox2Mnx3O2, and 0 < x1 <, 1,0 < x2 < 1,0 < x3 < 1, x1+x2+x3=1, a 1-1.2；Wherein, a is preferably
For 1-1.1；
Wherein, when the electrode material is nickel cobalt aluminic acid lithium material, the chemical formula of the nickel cobalt aluminic acid lithium material is
LibNiy1Coy2Aly3O2, and 0 < y1 <, 1,0 < y2 < 1,0 < y3 < 1, y1+y2+y3=1, b 1-1.2；Wherein, b is preferably
For 1-1.1.
9. a kind of application of electrode material as described in claim 1,2 or 8 as the positive electrode in lithium ion battery.
10. a kind of lithium ion battery, which is characterized in that the lithium ion battery is as the electrode material as described in claim 1,2 or 8
Material is made.
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| CN115084506A (en) * | 2022-05-18 | 2022-09-20 | 广东邦普循环科技有限公司 | Large-particle-size single crystal ternary cathode material and preparation method and application thereof |
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