CN107611371A - A kind of high circulation and constitutionally stable ternary material preparation method - Google Patents
A kind of high circulation and constitutionally stable ternary material preparation method Download PDFInfo
- Publication number
- CN107611371A CN107611371A CN201710706178.1A CN201710706178A CN107611371A CN 107611371 A CN107611371 A CN 107611371A CN 201710706178 A CN201710706178 A CN 201710706178A CN 107611371 A CN107611371 A CN 107611371A
- Authority
- CN
- China
- Prior art keywords
- ternary material
- ternary
- lithium
- constitutionally stable
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention is applied to anode material of lithium battery field, there is provided a kind of high circulation and constitutionally stable ternary material preparation method, including：Using the nickel-cobalt-manganese ternary material precursor of different-grain diameter with being mixed respectively with lithium source, and doping F salt, Co salt, Si oxide, obtain the ternary material of different medians, then the ternary material of same median is mixed in proportion, material coats lithium metasilicate, obtains final high circulation and constitutionally stable nickel-cobalt-manganese ternary material.High density of material, high capacity can be realized using the presoma of different-grain diameter；Adulterated using different ions, the features such as to reduce cation mixing, the structure of stabilizing material; the electrical conductivity of material is improved, and improves the cycle performance of material, lithium metasilicate finally is coated to material; lithium metasilicate diaphragm can be formed on the top layer of material, increase the electrical conductance of material and the structure of stabilizing material.
Description
Technical field
The invention belongs to anode material of lithium battery technical field, more particularly to a kind of high circulation and constitutionally stable ternary material
Preparation method for material.
Background technology
For NCM nickel-cobalt-manganese ternaries material because of big, the good cycle with discharge capacity, the advantages such as manufacturing cost is low, are current
Widely used anode material for lithium-ion batteries, particularly in electrokinetic cell, there are wide market and application prospect.
In order to further meet requirement of the market to ternary material, ternary material is just towards high power capacity, high circulation, security
Can high and constitutionally stable direction develop.Research shows：NCM ternary materials are with the performance meeting of the increase material of cycle-index
That decays is more and more faster.In order to overcome this problem, the current widely used method for being doped, coating to ternary material is come steady
The structure of material is determined, so as to improve the stability of material and cycle performance.
Nowadays under the conditions of 25 DEG C of conventional 4.3V, half-cell charges the main NCM523 ternary materials of in the market in 1.2C
Discharge capacity is 168mAh/g first in the case of multiplying power and 0.25C discharge-rate, and half-cell is in 1.2C rate of charge and 1.0C
Circulated under discharge-rate, the capacity of the 50th circle is 153mAh/g, and capability retention is 95% or so, and this also has one with the market demand
Fixed gap.
The content of the invention
In view of the above problems, it is an object of the invention to provide a kind of high circulation and constitutionally stable ternary material preparation side
Method, it is intended to solve the poor technical problem of the capacity, cycle performance, high-temperature storage performance of existing NCM523 ternary materials.
The present invention adopts the following technical scheme that：
The high circulation and constitutionally stable ternary material preparation method, comprise the steps：
S1, the nickel-cobalt-manganese ternary material precursor for preparing different medians, by the nickel-cobalt-manganese ternary of every kind of median
Material precursor and lithium source, doped compound carry out mixing and ball milling, then through oversintering, broken, sieving, finally obtain it is a variety of not
With the ternary material of median；
S2, the ternary material of obtained a variety of different medians mixed in proportion, obtain mixing ternary material；
S3, the mixing ternary material is added and stirred into deionized water, lithium silicate aqueous solution is then added dropwise and continues
Stirring, obtained slurries are filtered after the completion of reaction, are evaporated, are dried, is finally sintered, crushes, sieving obtains target
Ternary material.
Further, in step sl, by before the nickel-cobalt-manganese ternary material of M μm of lithium source, doped compound and median
Drive body and carry out mixing and ball milling, then obtain ternary material B1 through oversintering, broken, sieving；By lithium source, doped compound and middle position
The nickel-cobalt-manganese ternary material precursor of N μm of particle diameter carries out mixing and ball milling, then obtains ternary material through oversintering, broken, sieving
B2, here M be more than N；In step s 2, by ternary material B1, B2 according to 5:5~8:2 ratio carries out being mixed to get mixing three
First material B3.
Further, when preparing ternary material B1 and B2, mol ratio Ni in the nickel-cobalt-manganese ternary material precursor：
Co：Mn=0.5：0.2:0.3, the mol ratio Li/ (Ni+Co+Mn)=1.01 of lithium source and nickel-cobalt-manganese ternary material precursor~
1.05, by lithium source, doped compound and nickel-cobalt-manganese ternary material precursor in planet-shaped ball mill with 300r/min from rotating speed
Degree and 10r/min revolution speeds carry out 1~3h of batch mixing and obtain reconciling powder, and powder will be reconciled during sintering with 1.5~5 DEG C/min speed
T1 and 1~3h of constant temperature are warming up to, then proceedes to be warming up to T2 and 8~15h of constant temperature with 1.5~5 DEG C/min speed, then breaks
Broken, sieving obtains ternary material；The ternary material B1 wherein obtained median is 12~16 μm, obtained ternary material B2
Median be 5~9 μm.
Further, M is 12~16 μm, and N is 5~9 μm, and the doped compound is nanometer materials, median ＜
50nm。
Further, in the doped compound for F salt, Co salt, Si oxide mixing, wherein F salt be NaF,
LiF、MgF2、CaF2In one or more, Co salt be Co3O4, CoC2O4, CoCO3, Co (OH) 3 in one or more, Si
Oxide one or both of for α-SiO2, β-SiO2.
Further, temperature T1 is 180~250 DEG C, and T2 is 890~950 DEG C.
Further, the lithium silicate aqueous solution preparation process that step S3 is added dropwise is as follows：
Silicate is obtained into SiO2 solution through cationic ion-exchange resin, the SiO2 solution and lithium hydroxide aqueous solution is anti-
Should, 20~60min of stirring obtains lithium metasilicate weak solution, then evaporates obtained lithium metasilicate weak solution at a temperature of 50~90 DEG C
It is concentrated to give the lithium silicate aqueous solution that concentration is 10%~50%.
Further, the silicate be MgSiO3, K2SiO3, Na2SiO3 in one or more, the SiO2 solution
Concentration is that SiO2 particle diameters are 1~4nm in 2%~5%, SiO2 solution.
Further, step S3 is specially：
The mixing ternary material is added and stirs 5~20min in magnetic stirring apparatus into deionized water, by lithium metasilicate
Solution is uniformly slowly added thereto within 3~5min times with dropper, then proceed to magnetic agitation and meanwhile heating 20~
60min, it is 60~90 DEG C to control water temperature, then the material after heating stirring is poured into Buchner funnel and filtered, will after suction filtration
Material is transferred in Rotary Evaporators and is evaporated material, and it is 70~85 DEG C to control water temperature, then the material being evaporated is taken out and is placed in vacuum
100~180 DEG C of 6~12h of vacuum drying in drying box, by the material after vacuum drying with 1.5~3.5 DEG C/min speed during sintering
Rate is warming up to T3 and 1~3h of constant temperature, continues to be warming up to T4 and 4~8h of constant temperature with 1.5~3.5 DEG C/min speed, most afterwards through broken
Target ternary material is obtained after broken, sieving.
Further, Rotary Evaporators evaporation water temperature is 70~85 DEG C, and temperature T3 is 180~250 DEG C, and T4 is 550~650
℃。
The beneficial effects of the invention are as follows：The present invention using different-grain diameter nickel-cobalt-manganese ternary material precursor with respectively with lithium
Source mixes, and adulterates F salt, Co salt, Si oxide, realizes densification, high capacity；Adulterated using different ions, to subtract
The features such as few cation mixing, the structure of stabilizing material improves the electrical conductivity of material, and improves the cycle performance of material, and
In coating, slurry is unlikely to form g., jelly-like, improves the performance of coating process and material；Lithium metasilicate finally is coated to material, can
To form lithium metasilicate diaphragm on the top layer of material, increase the electrical conductance of material and the structure of stabilizing material.Modified ternary material
The capacity of material, cycle performance, high-temperature storage performance etc. have a distinct increment, and manufacture craft is simple, easy to process.
Brief description of the drawings
Fig. 1 is the flow chart that the present invention is high circulation and constitutionally stable ternary material preparation method；
Fig. 2 is the electromicroscopic photograph figure of the gained ternary material of embodiment one；
Fig. 3 is the button cell of the ternary material preparation prepared by embodiment one, embodiment two and comparative example one in 4.3V
Voltage under the graph of a relation of cycle-index and discharge capacity.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.
As shown in figure 1, high circulation provided by the invention and constitutionally stable ternary material preparation method, including following steps
Suddenly：
S1, the nickel-cobalt-manganese ternary material precursor for preparing different medians, by the nickel-cobalt-manganese ternary of every kind of median
Material precursor and lithium source, doped compound carry out mixing and ball milling, then through oversintering, broken, sieving, finally obtain it is a variety of not
With the ternary material of median；
S2, the ternary material of obtained a variety of different medians mixed in proportion, obtain mixing ternary material；
S3, the mixing ternary material is added and stirred into deionized water, lithium silicate aqueous solution is then added dropwise and continues
Stirring, obtained slurries are filtered after the completion of reaction, are evaporated, are dried, is finally sintered, crushes, sieving obtains target
Ternary material.
The present invention prepares the nickel-cobalt-manganese ternary material precursor of a variety of different medians first, then by these ternary materials
Lithium source and doped compound are added in material material precursor, a variety of different middle positions are obtained by ball milling, sintering, broken, sieving
The ternary material of particle diameter.Then the ternary material of these different medians is mixed to get to mixing ternary material according to a certain percentage
Material, wet method cladding lithium metasilicate is finally carried out to mixing ternary material, so as to obtain the more superior NCM523 positive electrodes of performance.
Due in mixing ternary material being mixed to get by the nickel-cobalt-manganese ternary material of different medians, bulky grain ternary
Little particle ternary material can be filled in the gap of material so that mixing ternary material is more closely knit, finally the lithium battery of quilt processed
Capacity is higher.And precursor doped F salt, Co salt, Si oxide, Me-F keys and Si-O keys are formed, is mixed with reducing cation
The features such as row, the structure of stabilizing material improves the electrical conductivity of material, and improves the cycle performance of material.Finally also to material bag
Lithium metasilicate is covered, lithium metasilicate diaphragm can be formed on the top layer of material, increase the electrical conductance of material and the structure of stabilizing material.
Generally, the nickel-cobalt-manganese ternary material precursor and lithium source, doping chemical combination of two kinds of medians can be selected
Thing mixes, and obtains two kinds of median ternary materials B1 and B2.Can also actually select as needed three kinds or it is more in
The nickel-cobalt-manganese ternary material precursor of position particle diameter, obtains the ternary material of three kinds or more medians, this is all in the present invention
Protection domain within.
In step S1, when lithium source, nickel-cobalt-manganese ternary material precursor and doped compound are mixed, Li/Me=1.01~
1.05, i.e. Li/ (Ni+Co+Mn)=1.01~1.05, Ni in nickel-cobalt-manganese ternary material precursor：Co：Mn=0.5：0.2:0.3.
In the nickel-cobalt-manganese ternary material precursor of two kinds of medians, a kind of median is 12~16 μm, and another median is 5
~9 μm.The ternary material B1 finally obtained median is 12~16 μm, and obtained ternary material B2 median is 5
~9 μm.
In order to illustrate technical solutions according to the invention, illustrated below by specific embodiment.
Embodiment one：
Median is selected as 15 μm of Ni0.5Co0.2Mn0.3(OH)2, by Li/Me=1.03, weigh Ni0.5Co0.2Mn0.3
(OH)2、Li2CO3And doped compound, the doping of F elements is 1500ppm in doped compound, and the doping of Si elements is
The doping of 1500ppm, Co element is 12000ppm.It will be placed in after their ball milling mixing 2h in roaster, in air atmosphere
910 DEG C of roasting 10h, after the product after roasting is pulverized and sieved, obtain D50For 14.0 μm of NCM523 ternary materials.
Median is selected as 6 μm of Ni0.5Co0.2Mn0.3(OH)2, by Li/Me=1.03, weigh Ni0.5Co0.2Mn0.3
(OH)2、Li2CO3And doped compound, the doping of F elements is 1500ppm in doped compound；The doping of Si elements is
The doping of 1500ppm, Co element is 12000ppm.By their ball milling mixing 2h, 900 DEG C of roasting 10h in air atmosphere；Will
After product after roasting pulverizes and sieves, D is obtained50For 8.0 μm of NCM523 ternary materials.
By D50=14.0 μm and D50=8.0 μm of two kinds of ternary materials are 7 according to mass ratio:3 ratio mixes after weighing
Uniformly, take compound 300g add 200g deionized waters in be placed on magnetic stirring apparatus stir 15min will be configured with dropper again
Concentration be 25% lithium metasilicate solution be uniformly added into wherein in the 3min times, then start heat in magnetic agitation, stirring
Time is 30min, and water temperature is 70 DEG C.
Material on magnetic stirring apparatus is poured into 20min is filtered in Buchner funnel, then filtered material is imported and revolved
Turn 80 DEG C of water temperatures in evaporimeter to be evaporated, the material after being evaporated is placed in 120 DEG C of vacuum drying 10h in vacuum drying chamber.Again will be true
Empty dried material is put into batch-type furnace, and the material after vacuum drying finally is warming up into 220 DEG C of constant temperature 2h with 3 DEG C/min,
600 DEG C of constant temperature 5h are warming up to 2 DEG C/min to be calcined, D is obtained after broken, sieving again50For 12.2 μm of NCM523 ternarys
Material.Its electromicroscopic photograph is as shown in Figure 2.
Embodiment two：
Median is selected as 15 μm of Ni0.5Co0.2Mn0.3(OH)2, according to Li/Me=1.03, weigh
Ni0.5Co0.2Mn0.3O2、Li2CO3And doped compound, the doping of F elements is 2000ppm in doped compound；Si elements
Doping is 2000ppm.It will be placed in after their ball milling mixing 3h in roaster, 930 DEG C of roasting 10h in air atmosphere；Will roasting
After product after burning pulverizes and sieves, D is obtained50For 14.0 μm of NCM523 ternary materials.
Median is selected as 6 μm of Ni0.5Co0.2Mn0.3(OH)2, according to Li/Me=1.03, weigh Ni0.5Co0.2Mn0.3
(OH)2、Li2CO3With the derived compound of each doped chemical, the wherein doping of F elements is 2000ppm；The doping of Si elements
For 2000ppm, the doping of Co elements is 12000ppm.It will be placed in after their ball milling mixing 3h in roaster, in air atmosphere
In 920 DEG C roasting 10h；After product after roasting is pulverized and sieved, D is obtained50For 8.0 μm of NCM523 ternary materials.
By D50=14.0 μm and D50=8.0 μm of material is 6 according to mass ratio:4 ratio is well mixed, and takes compound
It is again 25% by the concentration configured with dropper that 300g, which is added in 200g deionized waters and is placed in stirring 15min on magnetic stirring apparatus,
Lithium metasilicate solution is uniformly added into wherein in the 3min times, then starts to heat in magnetic agitation, mixing time 20min, water
Temperature is 80 DEG C.
Material on magnetic stirring apparatus is poured into 20min is filtered in Buchner funnel, then filtered material is imported and revolved
Turn 80 DEG C of water temperatures in evaporimeter to be evaporated, the material after being evaporated is placed in 150 DEG C of vacuum drying 6h in vacuum drying chamber.Again by vacuum
Dried material is put into batch-type furnace and is warming up to 220 DEG C of constant temperature 2h with 3 DEG C/min, then is warming up to 700 DEG C of constant temperature with 2 DEG C/min
5h is calcined, and D is obtained after broken, sieving50For 11.6 μm of NCM523 ternary materials.
Comparative example one：
The Ni of 15 μm of selection0.5Co0.2Mn0.3(OH)2With 6 μm of Ni0.5Co0.2Mn0.3(OH)2Both mass ratioes are 7:3,
And Li2CO3According to Li/Me=1.03 ball milling mixings 3h.It is placed in roaster, 920 DEG C of roasting 10h in dry air atmosphere；Will
After product after roasting pulverizes and sieves, D is obtained50For 12.2 μm of NCM523 ternary materials.
The NCM523 ternary materials that above-described embodiment one, embodiment two and comparative example one are finally prepared are under
Method is stated to test resulting materials progress chemical property：Using NCM523 ternary materials as positive active material, lithium piece is
Negative pole, assemble button cell.M (active material) in positive plate：M (acetylene black)：M (PVDF)=8:1:1, using blue electrical testing system
System is tested, and charging/discharging voltage is 2.7~4.3V, and cycle performance test is carried out under 25 DEG C of environment.Embodiment one, embodiment
Two and comparative example one prepared by the button cell for preparing of ternary material under 4.3V voltage cycle-index and discharge capacity
Graph of a relation is as shown in Figure 3.
In embodiment one, discharge capacity can reach battery first under 1.2C rate of charge and 0.25C discharge-rates
171.1mAh/g, first charge-discharge efficiency reach 87%, are circulated under 1.2C rate of charge and 1.0C discharge-rates, the 50th circle
Discharge capacity is 156.8mAh/g, and capability retention 96.9%, cycle performance is obviously improved.
In embodiment one, discharge capacity can reach battery first under 1.2C rate of charge and 0.25C discharge-rates
170.8mAh/g, first charge-discharge efficiency reach 87.1%, are circulated under 1.2C rate of charge and 1.0C discharge-rates, the 50th circle
Discharge capacity be 156.6mAh/g, capability retention 97.0%, cycle performance is obviously improved.
In comparative example one, discharge capacity can reach battery first under 1.2C rate of charge and 0.25C discharge-rates
168.3mAh/g, first charge-discharge efficiency reach 86.2%, are circulated under 1.2C rate of charge and 1.0C discharge-rates, the 50th circle
Discharge capacity be 152.2mAh/g, capability retention 94.6%, cycle performance is poor.
From the point of view of accompanying drawing 3 and embodiment one, embodiment two, the result of the test of comparative example one, the forerunner of two embodiments
Body employ F salt, Co salt, Si oxide doping, and comparative example is in the lump undoped with can obviously improve following for material after doping
Ring performance.Additional embodiment one, embodiment two, comparative example one employ the nickel-cobalt-manganese ternary material forerunner of two kinds of medians
Body prepares ternary material, and discharge capacity and first charge-discharge efficiency be all very first for the NCM523 ternary materials finally obtained
Height, be advantageous to improve battery capacity.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should be included in the scope of the protection.
Claims (10)
1. a kind of high circulation and constitutionally stable ternary material preparation method, it is characterised in that methods described comprises the steps：
S1, the nickel-cobalt-manganese ternary material precursor for preparing different medians, by the nickel-cobalt-manganese ternary material of every kind of median
Presoma carries out mixing and ball milling with lithium source, doped compound, then through oversintering, broken, sieving, finally obtains in a variety of differences
The ternary material of position particle diameter；
S2, the ternary material of obtained a variety of different medians mixed in proportion, obtain mixing ternary material；
S3, the mixing ternary material is added and stirred into deionized water, lithium silicate aqueous solution is then added dropwise and continues to stir,
Obtained slurries are filtered after the completion of reaction, are evaporated, are dried, is finally sintered, crushes, sieving obtains target ternary material
Material.
2. high circulation as claimed in claim 1 and constitutionally stable ternary material preparation method, it is characterised in that in step S1
In, the nickel-cobalt-manganese ternary material precursor of M μm of lithium source, doped compound and median is subjected to mixing and ball milling, then passed through
Sintering, broken, sieving obtain ternary material B1；Before the nickel-cobalt-manganese ternary material of N μm of lithium source, doped compound and median
Drive body and carry out mixing and ball milling, then obtain ternary material B2 through oversintering, broken, sieving, M is more than N here；In step s 2,
By ternary material B1, B2 according to 5:5~8:2 ratio carries out being mixed to get mixing ternary material B3.
3. high circulation as claimed in claim 2 and constitutionally stable ternary material preparation method, it is characterised in that preparing ternary
During material B1 and B2, mol ratio Ni in the nickel-cobalt-manganese ternary material precursor：Co：Mn=0.5：0.2:0.3, lithium source and nickel cobalt
The mol ratio Li/ (Ni+Co+Mn)=1.01~1.05 of manganese ternary material precursor, by lithium source, doped compound and nickel cobalt manganese three
First material precursor carries out 1~3h of batch mixing in planet-shaped ball mill with 300r/min rotational velocities and 10r/min revolution speeds
Obtain reconciling powder, the powder that will reconcile during sintering is warming up to T1 simultaneously 1~3h of constant temperature with 1.5~5 DEG C/min speed, then proceed to
1.5~5 DEG C/min speed is warming up to T2 and 8~15h of constant temperature, then crushes, sieving obtains ternary material；Three wherein obtained
First material B1 median is 12~16 μm, and obtained ternary material B2 median is 5~9 μm.
4. high circulation as claimed in claim 3 and constitutionally stable ternary material preparation method, it is characterised in that M is 12~16 μ
M, N are 5~9 μm, and the doped compound is nanometer materials, median ＜ 50nm.
5. high circulation as claimed in claim 4 and constitutionally stable ternary material preparation method, it is characterised in that the dopingization
It is F salt in compound, the mixing of Co salt, Si oxide, wherein F salt is NaF, LiF, MgF2、CaF2In one or more, Co
Salt is Co3O4、CoC2O4、CoCO3、Co(OH)3In one or more, Si oxide is α-SiO2、β-SiO2In one kind or
Two kinds.
6. high circulation as claimed in claim 3 and constitutionally stable ternary material preparation method, it is characterised in that temperature T1 is
180~250 DEG C, T2 is 890~950 DEG C.
7. high circulation as claimed in claim 1 and constitutionally stable ternary material preparation method, it is characterised in that step S3 is added dropwise
Lithium silicate aqueous solution preparation process it is as follows：
Silicate is obtained into SiO through cationic ion-exchange resin2Solution, by the SiO2Solution reacts with lithium hydroxide aqueous solution, stirs
Mix 20~60min and obtain lithium metasilicate weak solution, be then concentrated by evaporation obtained lithium metasilicate weak solution at a temperature of 50~90 DEG C
Obtain the lithium silicate aqueous solution that concentration is 10%~50%.
8. high circulation as claimed in claim 7 and constitutionally stable ternary material preparation method, it is characterised in that the silicate
For MgSiO3、K2SiO3、Na2SiO3In one or more, the SiO2Solution concentration is 2%~5%, SiO2SiO in solution2
Particle diameter is 1~4nm.
9. high circulation as claimed in claim 1 and constitutionally stable ternary material preparation method, it is characterised in that step S3 is specific
For：
The mixing ternary material is added and stirs 5~20min in magnetic stirring apparatus into deionized water, by lithium metasilicate solution
Uniformly slowly it is added thereto with dropper within 3~5min times, then proceedes to magnetic agitation while heat 20~60min, control
Water temperature processed is 60~90 DEG C, then the material after heating stirring is poured into Buchner funnel and filtered, and is transferred to material after suction filtration
Material is evaporated in Rotary Evaporators, it is 70~85 DEG C to control water temperature, then the material being evaporated is taken out and is placed in vacuum drying chamber
Material after vacuum drying, is warming up to during sintering by 100~180 DEG C of 6~12h of vacuum drying with 1.5~3.5 DEG C/min speed
T3 and 1~3h of constant temperature, continue to be warming up to T4 and 4~8h of constant temperature with 1.5~3.5 DEG C/min speed, most afterwards after broken, sieving
Obtain target ternary material.
10. high circulation as claimed in claim 9 and constitutionally stable ternary material preparation method, it is characterised in that rotary evaporation
Instrument evaporation water temperature is 70~85 DEG C, and temperature T3 is 180~250 DEG C, and T4 is 550~650 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706178.1A CN107611371A (en) | 2017-08-17 | 2017-08-17 | A kind of high circulation and constitutionally stable ternary material preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710706178.1A CN107611371A (en) | 2017-08-17 | 2017-08-17 | A kind of high circulation and constitutionally stable ternary material preparation method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN107611371A true CN107611371A (en) | 2018-01-19 |
Family
ID=61065027
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710706178.1A Pending CN107611371A (en) | 2017-08-17 | 2017-08-17 | A kind of high circulation and constitutionally stable ternary material preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107611371A (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108963218A (en) * | 2018-07-09 | 2018-12-07 | 王丹亮 | A kind of preparation method and application of the nickelic ternary lithium of low cobalt |
| CN109616652A (en) * | 2018-12-11 | 2019-04-12 | 欣旺达电子股份有限公司 | Modified complex ternary material and preparation method thereof |
| CN109686929A (en) * | 2018-11-29 | 2019-04-26 | 兰州金通储能动力新材料有限公司 | A kind of nickel-cobalt-manganese ternary presoma and preparation method thereof |
| CN110534736A (en) * | 2019-08-28 | 2019-12-03 | 电子科技大学 | A kind of high potential lithium ion battery NCM tertiary cathode material and preparation method thereof |
| CN110808370A (en) * | 2019-10-25 | 2020-02-18 | 合肥国轩高科动力能源有限公司 | Ternary cathode material of lithium ion battery and preparation method and application thereof |
| CN110993936A (en) * | 2019-12-02 | 2020-04-10 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN111668462A (en) * | 2019-03-05 | 2020-09-15 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN112349885A (en) * | 2019-08-06 | 2021-02-09 | 湖南杉杉能源科技股份有限公司 | Modified lithium ion battery positive electrode material and preparation method thereof |
| CN113620353A (en) * | 2021-08-06 | 2021-11-09 | 合肥国轩高科动力能源有限公司 | Strontium titanate modified nickel cobalt lithium manganate positive electrode material and lithium ion battery containing same |
| WO2023184563A1 (en) * | 2022-03-31 | 2023-10-05 | 天津巴莫科技有限责任公司 | Nickel cobalt lithium manganate material and preparation method therefor, positive electrode material and lithium ion battery |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000870A (en) * | 2012-11-22 | 2013-03-27 | 中国电子科技集团公司第十八研究所 | Compounding method for LizNixCoyMn (1-x-y) O2 material |
| CN103296260A (en) * | 2013-06-06 | 2013-09-11 | 南通瑞翔新材料有限公司 | Positive active substance for non-aqueous electrolyte secondary battery and manufacturing method of positive active substance |
| CN103794751A (en) * | 2014-01-22 | 2014-05-14 | 南通瑞翔新材料有限公司 | Lithium manganate based lithium ion battery positive electrode material as well as preparation method thereof |
| CN103904310A (en) * | 2012-12-28 | 2014-07-02 | 北京当升材料科技股份有限公司 | Preparation method for mixed nickel-cobalt-lithium manganate material |
| CN106887587A (en) * | 2017-03-20 | 2017-06-23 | 成都新柯力化工科技有限公司 | The stability lithium manganate battery electrode material and preparation method of a kind of glass fluxing technique |
-
2017
- 2017-08-17 CN CN201710706178.1A patent/CN107611371A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103000870A (en) * | 2012-11-22 | 2013-03-27 | 中国电子科技集团公司第十八研究所 | Compounding method for LizNixCoyMn (1-x-y) O2 material |
| CN103904310A (en) * | 2012-12-28 | 2014-07-02 | 北京当升材料科技股份有限公司 | Preparation method for mixed nickel-cobalt-lithium manganate material |
| CN103296260A (en) * | 2013-06-06 | 2013-09-11 | 南通瑞翔新材料有限公司 | Positive active substance for non-aqueous electrolyte secondary battery and manufacturing method of positive active substance |
| CN103794751A (en) * | 2014-01-22 | 2014-05-14 | 南通瑞翔新材料有限公司 | Lithium manganate based lithium ion battery positive electrode material as well as preparation method thereof |
| CN106887587A (en) * | 2017-03-20 | 2017-06-23 | 成都新柯力化工科技有限公司 | The stability lithium manganate battery electrode material and preparation method of a kind of glass fluxing technique |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108963218A (en) * | 2018-07-09 | 2018-12-07 | 王丹亮 | A kind of preparation method and application of the nickelic ternary lithium of low cobalt |
| CN109686929A (en) * | 2018-11-29 | 2019-04-26 | 兰州金通储能动力新材料有限公司 | A kind of nickel-cobalt-manganese ternary presoma and preparation method thereof |
| CN109686929B (en) * | 2018-11-29 | 2021-08-03 | 兰州金通储能动力新材料有限公司 | Nickel-cobalt-manganese ternary precursor and preparation method thereof |
| CN109616652A (en) * | 2018-12-11 | 2019-04-12 | 欣旺达电子股份有限公司 | Modified complex ternary material and preparation method thereof |
| CN111668462B (en) * | 2019-03-05 | 2023-11-17 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| US11552293B2 (en) | 2019-03-05 | 2023-01-10 | Samsung Sdi Co., Ltd. | Positive active material for rechargeable lithium battery, method of preparing the same and rechargeable lithium battery including the same |
| CN111668462A (en) * | 2019-03-05 | 2020-09-15 | 三星Sdi株式会社 | Positive active material for rechargeable lithium battery, method of preparing the same, and rechargeable lithium battery including the same |
| CN112349885B (en) * | 2019-08-06 | 2022-05-03 | 巴斯夫杉杉电池材料有限公司 | Modified lithium ion battery positive electrode material and preparation method thereof |
| CN112349885A (en) * | 2019-08-06 | 2021-02-09 | 湖南杉杉能源科技股份有限公司 | Modified lithium ion battery positive electrode material and preparation method thereof |
| CN110534736A (en) * | 2019-08-28 | 2019-12-03 | 电子科技大学 | A kind of high potential lithium ion battery NCM tertiary cathode material and preparation method thereof |
| CN110808370A (en) * | 2019-10-25 | 2020-02-18 | 合肥国轩高科动力能源有限公司 | Ternary cathode material of lithium ion battery and preparation method and application thereof |
| CN110993936B (en) * | 2019-12-02 | 2021-08-27 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN110993936A (en) * | 2019-12-02 | 2020-04-10 | 当升科技(常州)新材料有限公司 | High-energy density type nickel cobalt lithium manganate positive electrode material and preparation method thereof |
| CN113620353A (en) * | 2021-08-06 | 2021-11-09 | 合肥国轩高科动力能源有限公司 | Strontium titanate modified nickel cobalt lithium manganate positive electrode material and lithium ion battery containing same |
| WO2023184563A1 (en) * | 2022-03-31 | 2023-10-05 | 天津巴莫科技有限责任公司 | Nickel cobalt lithium manganate material and preparation method therefor, positive electrode material and lithium ion battery |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107611371A (en) | A kind of high circulation and constitutionally stable ternary material preparation method | |
| CN104282880B (en) | Lithium-cobalt composite oxide lithium ion positive material and preparation method thereof | |
| CN103956485B (en) | Lithium iron phosphate electrode material of a kind of three-dimensional hierarchical structure and preparation method thereof | |
| CN108493435B (en) | Lithium ion battery anode material Li (Ni)0.8Co0.1Mn0.1)1-xYxO2And preparation method | |
| CN101504979A (en) | A novel preparation method for LiFePO4/C composite positive pole material | |
| CN114361440A (en) | High-voltage ternary cathode material with core-shell structure and preparation method thereof | |
| CN102790203B (en) | A kind of preparation method of anode material for lithium-ion batteries | |
| CN107394155A (en) | A kind of doping modification method of lithium cobalt oxide cathode material for lithium ion battery | |
| CN105280898B (en) | Vanadium doping lithium nickel cobalt manganese oxide nano material and its preparation method and application | |
| CN108172825A (en) | Real inexpensive lithium cobaltate cathode material of a kind of high voltage and preparation method thereof | |
| CN108550802A (en) | A kind of nickel-cobalt-manganternary ternary anode material and preparation method that Y/La doping Co/B is coated altogether | |
| CN107204429A (en) | The preparation method and anode material for lithium-ion batteries and lithium ion battery of nickel-cobalt-manganese ternary material | |
| CN107591529A (en) | A kind of titanium phosphate lithium cladding nickel-cobalt-manganternary ternary anode material and preparation method thereof | |
| CN109390553B (en) | Composite positive electrode material, positive plate and all-solid-state lithium battery | |
| CN104134799B (en) | Carbon modifies porous calcium phosphate vanadium lithium nanosphere material and its preparation method and application | |
| CN113353995A (en) | Cathode material with low cobalt content and preparation method and application thereof | |
| CN108400321A (en) | A kind of nickel cobalt ferrous acid lithium anode material and preparation method thereof | |
| CN103441238A (en) | Mg-doped Li-rich anode material and preparation method for same | |
| CN108598386A (en) | Iron manganese phosphate for lithium base composite positive pole and preparation method thereof | |
| CN107658432A (en) | The preparation method and its positive electrode of modified metal-oxide positive electrode | |
| CN103094572B (en) | Lithium vanadate anode material and preparation method thereof | |
| CN106745337A (en) | A kind of LiNi1/3Co1/3Mn1/3O2Preparation method | |
| CN106744778A (en) | A kind of method that molten-salt growth method prepares lithium iron phosphate cathode material | |
| CN106654255A (en) | Aluminum-doped and modified cathode material for high-capacity lithium ion batteries | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20180119 |
|
| RJ01 | Rejection of invention patent application after publication |