CN109037672A - A kind of preparation method of power battery nickel-cobalt lithium manganate material - Google Patents
A kind of preparation method of power battery nickel-cobalt lithium manganate material Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
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- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention discloses a kind of preparation methods of power battery nickel-cobalt lithium manganate material.The preparation method of this power battery nickel-cobalt lithium manganate material, comprising the following steps: 1) precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is put into electric field arrangement, be subsequently placed in sintering furnace, be passed through protection gas；2) furnace temperature is gradually heated to 500 DEG C~650 DEG C from room temperature, keeps constant temperature；3) to electric field arrangement loading current, be powered processing agglomerated material, continues to keep constant temperature after power-off；4) it is first passed through oxygen-protection gas gaseous mixture, then is passed through oxygen, is continuously heating to 700 DEG C~950 DEG C, constant temperature is kept, obtains nickel-cobalt lithium manganate material.The present invention prepares power battery nickel-cobalt lithium manganate material using the method for electric field synergistic sintering, and material sintering is more uniform, fine and close, and resulting ternary material tap density is high, and electrical property is good.
Description
Technical field
The present invention relates to a kind of preparation methods of power battery nickel-cobalt lithium manganate material.
Background technique
Data are issued according to Ministry of Industry and Information, China's new-energy automobile yield is respectively 34.0 ten thousand, 51.7 within 2015 to 2017
Ten thousand, 79.4 ten thousand, sales volume are respectively 33.1 ten thousand, 50.7 ten thousand, 77.7 ten thousand.In recent years, China's new-energy automobile industry
Obtain development continuously and healthily.Key components and parts of the power battery as new-energy automobile, it is desirable that it is good with safety, energy
The features such as density is high, and charge discharge life is long, lithium ion battery is with above-mentioned advantage by industrial application in new-energy automobile.
Nickel-cobalt lithium manganate cathode material meets China's power battery high-energy density technology path and is widely used, according to
Starting point Research statistics, China's nickel-cobalt lithium manganate cathode material yield in 2017 is 8.6 ten thousand tons, accounts for positive electrode total output
41.0%, considerably beyond the yield of LiFePO4, LiMn2O4 and cobalt acid lithium.The performance of positive electrode is to influence the master of battery performance
Factor is wanted, high density positive electrode is the important channel for realizing high-energy density power.
Conventional solid-state method is the common method for preparing battery material, and a certain proportion of ternary precursor is mixed with lithium source,
Ternary material is obtained through high temperature sintering.Ternary precursor is mechanically to mix with lithium source in conventional solid-state method, and the two is difficult to realize
Complete uniformly sintered material is easy to happen the rich lithium in part or scarce lithium, causes defect, influences the performance of material.To understand
The certainly problem of material mixing uniformity has researcher to propose using mixing-pre-sintering-cooling-rerolling-double sintering side
The disadvantages of method is sintered ternary material, but there are long flow path, low efficiency, high energy consumptions.Meanwhile conventional solid-state method produces to obtain
Ternary material sintering after cathode material structure it is loose, density is low, and the service life is short, and capacity is few.Wang Zhenhua etc. proposes a kind of " lithium ion
The preparation method of cell positive material " (CN107611414A), it is suppressed after persursor material is mixed with lithium source, is applying electric field
Under conditions of carry out low-temperature sintering.However suppression process can destroy the original exterior appearance of persursor material, even if using spherical
Persursor material does raw material, is also difficult to obtain spherical anode material after sintering, and obtained aspherical positive electrode vibration density
Spend low, capacity is few, and limitation is obvious.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation methods of power battery nickel-cobalt lithium manganate material.
The technical solution used in the present invention is:
A kind of preparation method of power battery nickel-cobalt lithium manganate material, comprising the following steps:
1) precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is put into electric field arrangement, be subsequently placed in sintering furnace, be passed through protection gas；
2) furnace temperature is gradually heated to 500 DEG C~650 DEG C from room temperature, keeps constant temperature；
3) to electric field arrangement loading current, be powered processing agglomerated material, continues to keep constant temperature after power-off；
4) it is first passed through oxygen-protection gas gaseous mixture, then is passed through oxygen, is continuously heating to 700 DEG C~950 DEG C, keeps constant temperature,
Obtain nickel-cobalt lithium manganate material.
In preparation method, electric field arrangement is the crucible boat that both ends are equipped with platinized platinum, and platinized platinum connects DC plant.
In the step 1) of preparation method, precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material be by nickel cobalt manganese hydroxide and lithium source by
Elemental mole ratios (Ni+Co+Mn): Li is 1:(1.1~1.3) it is mixed；Nickel, cobalt, manganese member in nickel cobalt manganese hydroxide
Plain ratio is x:y:(100-x-y), wherein 20≤x≤80,0≤y≤20.
In the step 2) of preparation method, the process of heating specifically: be first warming up to 120 with 0.5 DEG C/min~4 DEG C/min
DEG C, constant temperature 0.5h~1h；500 DEG C~650 DEG C are warming up to 0.5 DEG C/min~10 DEG C/min again, constant temperature 0.5h~1h.
In the step 3) of preparation method, the voltage of the processing that is powered is 6V~9V, and electric current is 100A~2000A, energization when
Between be 0.5h~1h；The time for continuing to keep constant temperature after power-off is 1h~2h.
In the step 4) of preparation method, specifically: it is first passed through oxygen-protection gas gaseous mixture 0.5h~1h, then is passed through oxygen,
700 DEG C~950 DEG C are continuously heating to 1 DEG C/min~5 DEG C/min, constant temperature 1h~20h.
In the step 4) of preparation method, the concentration of oxygen is 2ppm~20ppm in oxygen-protection gas gaseous mixture.
In the step 1) or step 4) of preparation method, protection gas is at least one of nitrogen, inert gas.
A kind of power battery nickel-cobalt lithium manganate material is made by preparation method above-mentioned.
A kind of power battery, nickel-cobalt lithium manganate material just extremely above-mentioned.
The beneficial effects of the present invention are:
The present invention prepares power battery nickel-cobalt lithium manganate material using the method for electric field synergistic sintering, and material is sintered more
Uniformly, fine and close, resulting ternary material tap density is high, and electrical property is good.
1, the present invention is sintered using electric field synergistic, and part lithium source is reduced into lithium metal in sintering process, and fusing point is lower
It is easier to flow and migrate after lithium metal melting, independently mixed with ternary precursor during the sintering process, avoid material after sintering
The intergranular rich lithium in part or scarce lithium.Meanwhile molten metal lithium is easier to penetrate presoma, after sintering inside material granule
Chemical component consistency is higher, is conducive to the performance of ternary material performance.
2, the present invention using electric field synergistic be sintered, material be sintered under the action of electric field it is more fine and close, be not necessarily to material into
Row chemical modification obtains very high tap density after material can also be made to be sintered.
3, the present invention is sintered under conditions of applying electric field after being mixed using presoma and lithium source, avoids pressing process
Destruction to presoma exterior appearance can also obtain spherical nickel cobalt manganese acid lithium, effectively increase the vibration density of material after sintering
Degree.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph for the nickel-cobalt lithium manganate material that embodiment 1 is prepared；
Fig. 2 is the charging and discharging curve figure of embodiment and comparative example；
Fig. 3 is the cycle performance figure of embodiment and comparative example.
Specific embodiment
A kind of preparation method of power battery nickel-cobalt lithium manganate material, comprising the following steps:
1) precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is put into electric field arrangement, be subsequently placed in sintering furnace, be passed through protection gas；
2) furnace temperature is gradually heated to 500 DEG C~650 DEG C from room temperature, keeps constant temperature；
3) to electric field arrangement loading current, be powered processing agglomerated material, continues to keep constant temperature after power-off；
4) it is first passed through oxygen-protection gas gaseous mixture, then is passed through oxygen, is continuously heating to 700 DEG C~950 DEG C, keeps constant temperature,
Obtain nickel-cobalt lithium manganate material.
Preferably, in preparation method, electric field arrangement is the crucible boat that both ends are equipped with platinized platinum, and platinized platinum connects DC plant.
Preferably, the crucible boat material of electric field arrangement is any one in ceramic, quartz, corundum.
Preferably, in the step 1) of preparation method, precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is by nickel cobalt manganese hydroxide
By elemental mole ratios (Ni+Co+Mn): Li it is 1:(1.1~1.3 with lithium source) it is mixed.
It is further preferred that precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is by nickel cobalt manganese hydrogen in the step 1) of preparation method
Oxide and lithium source are 1:(1.1~1.3 by elemental mole ratios (Ni+Co+Mn): Li) after mixing, then by solid-to-liquid ratio 1:(0.01~
0.2) assistant research fellow's agent is added, ball milling 1h~10h is obtained.
Preferably, nickel, cobalt, manganese element ratio in precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material, in nickel cobalt manganese hydroxide
For x:y:(100-x-y), wherein 20≤x≤80,0≤y≤20.
Preferably, in precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material, lithium source is lithium carbonate, lithium nitrate, lithium hydroxide, oxidation
At least one of lithium, lithium oxalate, lithium acetate；It is further preferred that lithium source is at least one of lithium carbonate, lithium hydroxide.
Preferably, in precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material, assistant research fellow's agent is water, ethyl alcohol, propyl alcohol, at least one in acetone
Kind.
Preferably, in the step 2) of preparation method, the process of heating specifically: first with 0.5 DEG C/min~4 DEG C/min heating
To 120 DEG C, constant temperature 0.5h~1h；500 DEG C~650 DEG C are warming up to 0.5 DEG C/min~10 DEG C/min again, constant temperature 0.5h~1h.
Preferably, in the step 3) of preparation method, the voltage for the processing that is powered is 6V~9V, and electric current is 100A~2000A, is led to
The time of electricity is 0.5h~1h；The time for continuing to keep constant temperature after power-off is 1h~2h.
Preferably, in the step 4) of preparation method, specifically: it is first passed through oxygen-protection gas gaseous mixture 0.5h~1h, then is led to
Enter oxygen, is continuously heating to 700 DEG C~950 DEG C with 1 DEG C/min~5 DEG C/min, constant temperature 1h~20h.
Preferably, in the step 4) of preparation method, the concentration of oxygen is 2ppm~20ppm in oxygen-protection gas gaseous mixture.
Preferably, in the step 1) or step 4) of preparation method, protection gas is at least one of nitrogen, inert gas；
It is further preferred that protection gas is at least one of nitrogen, argon gas；Still more preferably, the protection gas in step 1) is
Argon gas；Oxygen-protection gas gaseous mixture in step 4) is oxygen-argon gas gaseous mixture.
Preferably, preparation method further includes step 5), and nickel-cobalt lithium manganate material is crushed, and control partial size D50 is 2 μm~20
μm, obtain nickel-cobalt lithium manganate cathode material.
Preferably, in preparation method, sintering furnace is closed sintering furnace, and sintering furnace has air inlet and exhaust outlet, exhaust
Mouth is equipped with check (non-return) valve.
A kind of power battery nickel-cobalt lithium manganate material is made by preparation method above-mentioned.
A kind of power battery, nickel-cobalt lithium manganate material just extremely above-mentioned.
The contents of the present invention are described in further detail below by way of specific embodiment.Original used in embodiment
Material unless otherwise specified, can be obtained from routine business approach.
Embodiment 1:
A kind of preparation method of power type nickle cobalt lithium manganate, comprising the following specific steps
S1: nickel cobalt manganese hydroxide and lithium carbonate are mixed by elemental mole ratios (Ni+Co+Mn): Li for 1:1.1, are added
Ethyl alcohol, ball milling 4h obtain material to be sintered.Nickel, cobalt, manganese element molar ratio are 55:20:25 in nickel cobalt manganese hydroxide.
S2: above-mentioned material to be sintered is put into ceramic crucible boat, platinized platinum is inserted into respectively at crucible boat both ends, by crucible boat
It is put into closed sintering furnace, is passed through argon gas from air inlet.
S3: being heated to 120 DEG C, constant temperature 0.5h from room temperature with 0.5 DEG C/min, continued to be heated to 550 DEG C with 0.5 DEG C/min,
Constant temperature 1h.
S4: direct current, voltage 6V, electric current 100A, energization 1h are loaded on platinized platinum.Continue constant temperature 1h after power-off.
S5: at the temperature disclosed above, oxygen-argon gas gaseous mixture that oxygen concentration is 2ppm, duration of ventilation 1h are passed through.It is passed through
Oxygen continues to be heated to 800 DEG C with 1 DEG C/min, and constant temperature 1h obtains nickle cobalt lithium manganate.
S6: above-mentioned nickle cobalt lithium manganate is crushed, and control partial size to D50 is 10 μm, is obtaining the nickle cobalt lithium manganate of embodiment 1 just
Pole material.The nickel-cobalt lithium manganate cathode material SEM of embodiment 1 schemes visible attached drawing 1.
Embodiment 2:
A kind of preparation method of power type nickle cobalt lithium manganate, comprising the following specific steps
S1: nickel cobalt manganese hydroxide and lithium hydroxide are mixed by elemental mole ratios (Ni+Co+Mn): Li for 1.2, are added
Ethyl alcohol, ball milling 1h obtain material to be sintered.Nickel, cobalt, manganese element molar ratio are 20:20:60 in nickel cobalt manganese hydroxide.
S2: above-mentioned material to be sintered is put into silica crucible boat, platinized platinum is inserted into respectively at crucible boat both ends, by crucible boat
It is put into closed sintering furnace, is passed through argon gas from air inlet.
S3: 120 DEG C, constant temperature 1h are heated to from room temperature with 2 DEG C/min, continues to be heated to 650 DEG C with 3 DEG C/min, constant temperature
0.7h。
S4: direct current, voltage 8V, electric current 500A, energization 0.7h are loaded on platinized platinum.Continue constant temperature after power-off
1.5h。
S5: at the temperature disclosed above, oxygen-argon gas gaseous mixture that oxygen concentration is 10ppm, duration of ventilation 0.7h are passed through.
It is passed through oxygen, continues to be heated to 700 DEG C with 3 DEG C/min, constant temperature 8h obtains nickle cobalt lithium manganate.
S6: above-mentioned nickle cobalt lithium manganate is crushed, and control partial size to D50 is 20 μm, is obtaining the nickle cobalt lithium manganate of embodiment 2 just
Pole material.
Embodiment 3:
A kind of preparation method of power type nickle cobalt lithium manganate, comprising the following specific steps
S1: nickel cobalt manganese hydroxide and lithium hydroxide are mixed by elemental mole ratios (Ni+Co+Mn): Li for 1.3, are added
Ethyl alcohol, ball milling 10h obtain material to be sintered.Nickel, cobalt, manganese element molar ratio are 80:5:15 in nickel cobalt manganese hydroxide.
S2: above-mentioned material to be sintered is put into corundum crucible boat, platinized platinum is inserted into respectively at crucible boat both ends, by crucible boat
It is put into closed sintering furnace, is passed through argon gas from air inlet.
S3: 120 DEG C, constant temperature 0.8h are heated to from room temperature with 4 DEG C/min, continues to be heated to 500 DEG C with 10 DEG C/min, constant temperature
0.5h。
S4: direct current, voltage 9V, electric current 2000A, energization 0.5h are loaded on platinized platinum.Continue constant temperature 2h after power-off.
S5: at the temperature disclosed above, oxygen-argon gas gaseous mixture that oxygen concentration is 20ppm, duration of ventilation 0.5h are passed through.
It is passed through oxygen, continues to be heated to 950 DEG C with 5 DEG C/min, constant temperature 20h obtains nickle cobalt lithium manganate.
S6: above-mentioned nickle cobalt lithium manganate is crushed, and control partial size to D50 is 2 μm, is obtaining the nickle cobalt lithium manganate of embodiment 3 just
Pole material.
Embodiment 4:
A kind of preparation method of power type nickle cobalt lithium manganate, comprising the following specific steps
S1: nickel cobalt manganese hydroxide and lithium carbonate are mixed by elemental mole ratios (Ni+Co+Mn): Li for 1:1.1, are added
Ethyl alcohol, ball milling 2h obtain material to be sintered.Nickel, cobalt, manganese element molar ratio are 55:15:30 in nickel cobalt manganese hydroxide.
S2: above-mentioned material to be sintered is put into ceramic crucible boat, platinized platinum is inserted into respectively at crucible boat both ends, by crucible boat
It is put into closed sintering furnace, is passed through argon gas from air inlet.
S3: being heated to 120 DEG C, constant temperature 0.5h from room temperature with 1 DEG C/min, continues to be heated to 600 DEG C with 0.5 DEG C/min, perseverance
Warm 0.8h.
S4: direct current, voltage 7V, electric current 100A, energization 1h are loaded on platinized platinum.Continue constant temperature 1h after power-off.
S5: at the temperature disclosed above, oxygen-argon gas gaseous mixture that oxygen concentration is 2ppm, duration of ventilation 1h are passed through.It is passed through
Oxygen continues to be heated to 750 DEG C with 1 DEG C/min, and constant temperature 5h obtains nickle cobalt lithium manganate.
S6: above-mentioned nickle cobalt lithium manganate is crushed, and control partial size to D50 is 4 μm, is obtaining the nickle cobalt lithium manganate of embodiment 4 just
Pole material.
Embodiment 5:
A kind of preparation method of power type nickle cobalt lithium manganate, comprising the following specific steps
S1: nickel cobalt manganese hydroxide and lithium carbonate are mixed by elemental mole ratios (Ni+Co+Mn): Li for 1:1.1, are added
Ethyl alcohol, ball milling 8h obtain material to be sintered.Nickel, cobalt, manganese element molar ratio are 55:12:33 in nickel cobalt manganese hydroxide.
S2: above-mentioned material to be sintered is put into ceramic crucible boat, platinized platinum is inserted into respectively at crucible boat both ends, by crucible boat
It is put into closed sintering furnace, is passed through argon gas from air inlet.
S3: being heated to 120 DEG C, constant temperature 0.5h from room temperature with 3 DEG C/min, continues to be heated to 550 DEG C with 0.5 DEG C/min, perseverance
Warm 0.6h.
S4: direct current, voltage 6V, electric current 100A, energization 1h are loaded on platinized platinum.Continue constant temperature 1h after power-off.
S5: at the temperature disclosed above, oxygen-argon gas gaseous mixture that oxygen concentration is 2ppm, duration of ventilation 1h are passed through.It is passed through
Oxygen continues to be heated to 850 DEG C with 1 DEG C/min, and constant temperature 15h obtains nickle cobalt lithium manganate.
S6: above-mentioned nickle cobalt lithium manganate is crushed, and control partial size to D50 is 14 μm, is obtaining the nickle cobalt lithium manganate of embodiment 5 just
Pole material.
Comparative example 1:
Nickel cobalt manganese hydroxide (nickel, cobalt, manganese element ratio are 55:20:25) and lithium carbonate are pressed into elemental mole ratios respectively
(Ni+Co+Mn): Li is 1:1 mixing, and ethyl alcohol is added, and obtained powder is placed in Muffle furnace after 120 DEG C of baking oven drying by ball milling 4h
It is sintered in oxygen, sintering temperature is 800 DEG C, constant temperature 8h, obtains the nickle cobalt lithium manganate contrast sample of comparative example 1.Comparison
Example 2:
The nickel-cobalt lithium manganate cathode material preparation method of comparative example 2 comprising the following specific steps
S1: nickel cobalt manganese hydroxide and lithium carbonate are mixed by elemental mole ratios (Ni+Co+Mn): Li for 1:1.1, are added
Ethyl alcohol, ball milling 4h is dry, obtains material to be sintered.Nickel, cobalt, manganese element molar ratio are 55:20:25 in nickel cobalt manganese hydroxide.
S2: above-mentioned material to be sintered is put into mold, is inserted into platinized platinum respectively in both mold ends, is put after compacting together with mold
Enter in ceramic crucible boat.
S3: under an argon atmosphere, being heated to 120 DEG C, constant temperature 0.5h from room temperature with 0.5 DEG C/min, with 0.5 DEG C/min continuation
550 DEG C are heated to, constant temperature 1h.
S4: direct current, voltage 6V, electric current 100A, energization 1h are loaded on platinized platinum.Continue constant temperature 1h after power-off.
S5: at the temperature disclosed above, oxygen-argon gas gaseous mixture that oxygen concentration is 2ppm, duration of ventilation 1h are passed through.It is passed through
Oxygen, constant temperature 1h are crushed after cooling, obtain the nickel-cobalt lithium manganate cathode material of comparative example 2.
Performance detection:
Tap density is carried out to nickle cobalt lithium manganate made from nickle cobalt lithium manganate made from Examples 1 to 5 and comparative example 1~2
Test, the results are shown in Table 1.The results show that nickle cobalt lithium manganate tap density prepared by Examples 1 to 5 be significantly larger than comparative example 1~
2。
The tap density of 1 nickel-cobalt lithium manganate material of table
| Sample | Tap density (g/cm3) |
| Embodiment 1 | 2.6 |
| Embodiment 2 | 2.6 |
| Embodiment 3 | 2.5 |
| Embodiment 4 | 2.6 |
| Embodiment 5 | 2.5 |
| Comparative example 1 | 2.2 |
| Comparative example 2 | 1.8 |
It is respectively anode with lithium nickel cobalt dioxide made from above-described embodiment 1 and comparative example 1-2, using lithium metal as cathode, assembling
At battery.Respectively battery obtained is subjected to discharge test for the first time with 1C multiplying power, as a result as shown in Fig. 2.The results show that in 1C
Under multiplying power, the comparative example 1 of the first discharge specific capacity of the power type nickel-cobalt lithium manganate cathode material of embodiment 1 than common solid phase method
The specific capacity of height, embodiment 1 is 185.4mAh/g, and the specific capacity of comparative example 1 only has 172.2mAh/g, the specific volume of comparative example 2
Amount only has 175.2mAh/g.
With 1000 charge and discharge cycles tests of 0.5C multiplying power progress, as a result as shown in Fig. 3.The results show that of the invention
The specific capacity of nickel-cobalt lithium manganate cathode material is higher than common solid phase method after 1000 circulations, and the capacity of embodiment 1 is kept
Rate is 93.6%, and the capacity retention ratio of comparative example 1 only has 85.5%.Embodiment 1 is also than the comparative example 2 of increase pressing process
The capacity retention ratio of height, comparative example 2 only has 87.4%.
Claims (10)
1. a kind of preparation method of power battery nickel-cobalt lithium manganate material, it is characterised in that: the following steps are included:
1) precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is put into electric field arrangement, be subsequently placed in sintering furnace, be passed through protection gas；
2) furnace temperature is gradually heated to 500 DEG C~650 DEG C from room temperature, keeps constant temperature；
3) to electric field arrangement loading current, be powered processing agglomerated material, continues to keep constant temperature after power-off；
4) it is first passed through oxygen-protection gas gaseous mixture, then is passed through oxygen, is continuously heating to 700 DEG C~950 DEG C, constant temperature is kept, obtains
Nickel-cobalt lithium manganate material.
2. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 1, it is characterised in that: electricity
Field device is the crucible boat that both ends are equipped with platinized platinum, and platinized platinum connects DC plant.
3. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 1, it is characterised in that: step
It is rapid 1) in, precursor of nickel-cobalt-lithium-manganese-oxide agglomerated material is by nickel cobalt manganese hydroxide and lithium source by elemental mole ratios (Ni+Co+
Mn): Li is 1:(1.1~1.3) it is mixed；Nickel, cobalt, manganese element ratio in nickel cobalt manganese hydroxide are x:y:(100-
X-y), wherein 20≤x≤80,0≤y≤20.
4. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 1, it is characterised in that: step
It is rapid 2) in, the process of heating specifically: first with 0.5 DEG C/min~4 DEG C/min be warming up to 120 DEG C, constant temperature 0.5h~1h；Again with
0.5 DEG C/min~10 DEG C/min is warming up to 500 DEG C~650 DEG C, constant temperature 0.5h~1h.
5. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 1 or 2, feature exist
In: in step 3), the voltage for the processing that is powered is 6V~9V, and electric current is 100A~2000A, and the time of energization is 0.5h~1h；It is disconnected
The time for continuing to keep constant temperature after electricity is 1h~2h.
6. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 1, it is characterised in that: step
It is rapid 4) in, specifically: be first passed through oxygen-protection gas gaseous mixture 0.5h~1h, then be passed through oxygen, with 1 DEG C/min~5 DEG C/min after
It is continuous to be warming up to 700 DEG C~950 DEG C, constant temperature 1h~20h.
7. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 6, it is characterised in that: step
It is rapid 4) in, in oxygen-protection gas gaseous mixture the concentration of oxygen be 2ppm~20ppm.
8. a kind of preparation method of power battery nickel-cobalt lithium manganate material according to claim 1 or claim 7, feature exist
In: protection gas is at least one of nitrogen, inert gas.
9. a kind of power battery nickel-cobalt lithium manganate material, it is characterised in that: be by system according to any one of claims 1 to 8
Preparation Method is made.
10. a kind of power battery, it is characterised in that: nickel-cobalt lithium manganate material just extremely as claimed in claim 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282664A (en) * | 2019-06-25 | 2019-09-27 | 广东邦普循环科技有限公司 | A kind of production method and consecutive production equipment of nickel-cobalt lithium manganate cathode material |
| CN112079396A (en) * | 2020-08-25 | 2020-12-15 | 北方奥钛纳米技术有限公司 | Nickel-containing cathode material, preparation method thereof and lithium ion battery comprising nickel-containing cathode material |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007137980A (en) * | 2005-11-17 | 2007-06-07 | National Institute Of Advanced Industrial & Technology | High-density acetylene black and method for producing the same |
| JP2007273273A (en) * | 2006-03-31 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | Composite powder for electrode, and method of manufacturing same |
| JP2013214421A (en) * | 2012-04-02 | 2013-10-17 | National Institute Of Advanced Industrial & Technology | Carbon-solid electrolyte complex and manufacturing method of the same |
| CN105518913A (en) * | 2013-09-13 | 2016-04-20 | 独立行政法人产业技术综合研究所 | Lithium sulfide-iron-carbon composite body |
| CN105655572A (en) * | 2014-11-12 | 2016-06-08 | 中国电子科技集团公司第十八研究所 | Spherical lithium nickel manganese positive electrode material preparation method |
| CN106099148A (en) * | 2016-07-21 | 2016-11-09 | 北京理工大学 | A kind of preparation method of solid-oxide fuel battery electrolyte |
| CN106992296A (en) * | 2017-05-25 | 2017-07-28 | 宁波工程学院 | A kind of electromagnetic field containment plasma fortified oxidizing roasting method of the nickelic positive electrode of lithium ion battery |
| CN107074585A (en) * | 2014-11-18 | 2017-08-18 | 国立研究开发法人产业技术综合研究所 | Lithium iron phosphorus sulphur carbon complex and its manufacture method |
| CN107611414A (en) * | 2017-10-25 | 2018-01-19 | 北京理工大学 | A kind of preparation method of anode material for lithium-ion batteries |
-
2018
- 2018-09-13 CN CN201811065579.4A patent/CN109037672B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007137980A (en) * | 2005-11-17 | 2007-06-07 | National Institute Of Advanced Industrial & Technology | High-density acetylene black and method for producing the same |
| JP2007273273A (en) * | 2006-03-31 | 2007-10-18 | National Institute Of Advanced Industrial & Technology | Composite powder for electrode, and method of manufacturing same |
| JP2013214421A (en) * | 2012-04-02 | 2013-10-17 | National Institute Of Advanced Industrial & Technology | Carbon-solid electrolyte complex and manufacturing method of the same |
| CN105518913A (en) * | 2013-09-13 | 2016-04-20 | 独立行政法人产业技术综合研究所 | Lithium sulfide-iron-carbon composite body |
| CN105655572A (en) * | 2014-11-12 | 2016-06-08 | 中国电子科技集团公司第十八研究所 | Spherical lithium nickel manganese positive electrode material preparation method |
| CN107074585A (en) * | 2014-11-18 | 2017-08-18 | 国立研究开发法人产业技术综合研究所 | Lithium iron phosphorus sulphur carbon complex and its manufacture method |
| CN106099148A (en) * | 2016-07-21 | 2016-11-09 | 北京理工大学 | A kind of preparation method of solid-oxide fuel battery electrolyte |
| CN106992296A (en) * | 2017-05-25 | 2017-07-28 | 宁波工程学院 | A kind of electromagnetic field containment plasma fortified oxidizing roasting method of the nickelic positive electrode of lithium ion battery |
| CN107611414A (en) * | 2017-10-25 | 2018-01-19 | 北京理工大学 | A kind of preparation method of anode material for lithium-ion batteries |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110282664A (en) * | 2019-06-25 | 2019-09-27 | 广东邦普循环科技有限公司 | A kind of production method and consecutive production equipment of nickel-cobalt lithium manganate cathode material |
| CN110282664B (en) * | 2019-06-25 | 2024-05-10 | 广东邦普循环科技有限公司 | Production method and continuous production equipment of nickel cobalt lithium manganate anode material |
| CN112079396A (en) * | 2020-08-25 | 2020-12-15 | 北方奥钛纳米技术有限公司 | Nickel-containing cathode material, preparation method thereof and lithium ion battery comprising nickel-containing cathode material |
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