CN108306017A - A method of preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod - Google Patents
A method of preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod Download PDFInfo
- Publication number
- CN108306017A CN108306017A CN201810156231.XA CN201810156231A CN108306017A CN 108306017 A CN108306017 A CN 108306017A CN 201810156231 A CN201810156231 A CN 201810156231A CN 108306017 A CN108306017 A CN 108306017A
- Authority
- CN
- China
- Prior art keywords
- nickel cobalt
- screw rod
- nitrate
- electrode material
- lithium
- 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.)
- Withdrawn
Links
Classifications
-
- 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
- H01M4/52—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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The present invention relates to nickel cobalt lithium aluminate ternary electrode field of material technology, and in particular to a method of preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod.A kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod of the present invention includes the following steps：Nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution are disperseed after forming jelly to be re-fed into three-screw extruder, by being fed to discharging successively by dispersion, sodium hydroxide pellets reaction, alumine hydroxide colloid cladding, lithium salts grinding distribution in three-screw extruder, it is discharged to obtain nickel cobalt lithium aluminate precursor from screw rod；Nickel cobalt lithium aluminate precursor is sintered in oxygen atmosphere, obtains nickel cobalt aluminium ternary electrode material.The present invention forms high nickel dispersion material using screw rod continuous conveying, shearing and the characteristic that can persistently feed at different sections, by nickel nitrate, cobalt nitrate, aluminum nitrate, then coats aluminium, grinding so that nickelic ternary material prepares controllability promotion.
Description
Technical field
The present invention relates to nickel cobalt lithium aluminate ternary electrode field of material technology, and in particular to it is a kind of using screw rod prepare it is nickelic
The method of type nickel cobalt lithium aluminate ternary electrode material.
Background technology
Lithium battery tertiary material (NMC) is to combine LiCoO2、LiNiO2And LiMnO2The advantages of three kinds of materials, due to Ni
, there are apparent synergistic effects between Co and Mn, therefore the performance of NMC is better than one-component layered cathode material, and is considered
It is one of the novel anode material for most having application prospect.In ternary material, according to the difference that each element matches, Ni can be+2
With+trivalent, Co is commonly considered as+trivalent, and Mn is then+4 valences.Three kinds of elements serve different in the material, and charging voltage is less than
When 4.4V (relative to lithium anode), it is considered that mainly Ni2+It participates in electrochemical reaction and forms Ni4+；Continue charging compared with
Co under high voltage3+It participates in reaction and is oxidized to Co4+, and Mn is then generally acknowledged that and is not involved in electrochemical reaction.
Application No. is 201610976934.8 Chinese patent application disclose a kind of nickel cobalt aluminic acid lithium electrode material and its
Preparation method and application.The nickel cobalt aluminic acid lithium electrode material be by two-dimension nano materials and stratiform nickel cobalt lithium aluminate in a manner of interlayer
Stacking is combined, and stratiform nickel cobalt lithium aluminate, which is located among two layers of two-dimension nano materials, forms sandwich structure, two-dimensional nano material
Expect that the molar ratio with nickel cobalt lithium aluminate is（2-5）：1.The present invention also provides the preparation sides of above-mentioned nickel cobalt aluminic acid lithium electrode material
Method, using two-dimension nano materials as the derivant of nickel cobalt lithium aluminate growth synthesis, in the preparation process of nickel cobalt lithium aluminate,
The nano material for introducing tungsten disulfide, molybdenum disulfide or graphene two-dimensional layer structure, utilizes the surface-active of two-dimension nano materials
The nickel cobalt lithium aluminate for luring synthesis stabilized zone structure into layer structure, overcomes the flocculation of aluminium, makes the preparation process of nickel cobalt lithium aluminate
Stable, uniform, easily-controllable, nickel cobalt lithium aluminate crystallization obtained is complete, and close structure, tap density is high, and conductivity is high.
Application No. is the Chinese patent application of 201510292977.X disclose a kind of nickel cobalt aluminic acid lithium composite material and its
Preparation method and application.Nickel cobalt aluminic acid lithium composite material includes nickel cobalt lithium aluminate and is coated on the ferric phosphate on nickel cobalt lithium aluminate surface
Lithium material, iron manganese phosphate for lithium are bonded together with nickel cobalt lithium aluminate by polytetrafluoroethylene (PTFE).It is swollen that this material can improve battery
The problem of gas.The preparation method of nickel cobalt aluminic acid lithium composite material, includes the following steps：Ptfe emulsion is sprayed in nickel cobalt
The surface of aluminic acid powder for lithium is added LiFePO 4 material powder after being sufficiently mixed, mixing material is obtained after being sufficiently mixed again
Material；Mixing material is dried to remove moisture, then crushes, obtains nickel cobalt aluminic acid lithium composite material.This method does not need
To material carry out double sintering, avoid because sintering cause nickel cobalt aluminic acid lithium composite material performance decline the problem of, be conducive to answer
With.In addition, a kind of anode pole piece and preparation method thereof including above-mentioned composite material is also provided, and including the anode pole piece
Lithium ion battery.
Application No. is 201410852239.1 Chinese patent applications to disclose a kind of nickel cobalt lithium aluminate composite positive pole
And preparation method thereof, the nickel cobalt lithium aluminate composite positive pole includes following components：A) nickel cobalt lithium aluminate cathode material；b)
Metal oxide；C) carbon source；The present invention by the surface of nickel cobalt lithium aluminate cathode material successively metal composite oxide and carbon,
It can be obtained the nickel cobalt lithium aluminate composite positive pole.The composite material of the present invention can significantly improve following for positive electrode
Ring performance and high rate performance, can be used for motive-power battery.
Application No. is 201610315712.1 Chinese patent applications to disclose lithium ion nickel cobalt lithium aluminate anode composite
The preparation method of material.The composite positive pole of the present invention includes mainly following components：Nickel cobalt lithium aluminate, nanometer Li2MnO3Phase.
Pass through part Li2MnO3Stable composition nickel cobalt aluminic acid lithium layer shape material is applied to high voltage charge-discharge test, and preparation method is：It will
Soluble lithium, nickel, cobalt, aluminium, manganese salt are dissolved in by a certain percentage in the mixed solution of water/complexing agent, and heating stirring is molten to being formed
Glue；Then pass through drying, calcining forms the presoma of lithium nickel cobalt dioxide compound；It transfers to calcining under oxygen atmosphere and obtains nickel cobalt
Sour lithium anode material.Charge and discharge cycles are stablized under the nickel cobalt lithium aluminate composite positive pole high voltage that the present invention is prepared, tool
There is better chemical property.
Application No. is the Chinese patent application of 201610175994.X disclose a kind of nickel cobalt aluminic acid lithium electrode material and its
Preparation method and application.Method provided by the invention includes the following steps：A), Li source compound, nickel source compound, cobalt source chemical combination
After object, aluminum source compound, citric acid, diethylene triamine pentacetic acid (DTPA) and solvent mixing, pH value is adjusted, colloidal sol is obtained；B), described molten
Glue is aged, and wet gel is obtained；C), the wet gel is sintered, and obtains nickel cobalt aluminic acid lithium electrode material；The nickel cobalt aluminium
The general formula of sour lithium electrode material is LiNi1-x-yCoxAlyO2, wherein x ＞ 0, y ＞ 0, x+y ＜ 1.The present invention uses sol-gel
Method significantly improves nickel cobalt aluminic acid lithium electrode material obtained using citric acid and diethylene triamine pentacetic acid (DTPA) as complexing agent
Specific capacity and cycle performance.
The capacity of nickelic positive electrode is mainly by Ni2+/Ni4+Redox couple is contributed, so the material capacity contains with nickel
The raising of amount and increase, but the cycle performance of material and security performance but run down with the increase of nickel content.Due to
Ni contents are high, and nickelic positive electrode also inherits LiNiO2The shortcomings that material.
The especially material synthesis processes of stoichiometric ratio are at present interruption reaction, in coprecipitation method, main former material
Material has cobaltous sulfate, nickel sulfate, lithium sulfate and sodium bicarbonate to be dissolved in deionized water, and is slowly added to ammonium bicarbonate soln, and
It is stirred continuously, needs rate of addition, mixing speed, reaction environment of control material etc., not only technique is difficult to control, and every batch of
Inferior quality difference is big, unstable.As stablizing the obstacle of the nickelic ternary of prepare with scale.
The prior art does not disclose prepares high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod continuous-stable
Method.
Invention content
Unstable, uppity defect of technique etc. is prepared for the above nickelic ternary material interruption of the existing technology
Problem preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode the first purpose of the invention is to provide a kind of using screw rod continuous-stable
The method of material.
In order to solve the above technical problems, a kind of of the present invention prepares high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod
The method of material includes the following steps：
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；
（2）, by step（1）The jelly is sent into three-screw extruder, in three-screw extruder by be fed to discharging according to
It is secondary sodium hydroxide pellets reaction is added by the dispersion of dispersion section, precipitating phase, alumine hydroxide colloid cladding is added in cladding section, lithium source grinds
It grinds section and lithium salts grinding distribution is added, be discharged to obtain nickel cobalt lithium aluminate precursor from screw rod；
（3）, by step（2）The nickel cobalt lithium aluminate precursor is sintered in oxygen atmosphere, obtains the high ni-type nickel cobalt of high solidity
Aluminium ternary electrode material；
In order to prepare the high ni-type nickel cobalt aluminium ternary electrode material of high solidity, nickel nitrate, cobalt nitrate, aluminum nitrate and lithium salts contain
Amount has certain relationship, wherein the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium salts molar ratio in terms of Ni, Co, Al, Li is：0.7
~1.2:0.1~0.3:0.03~0.08：1.
The present invention, as reactor, is the pressure and shearing force generated by screw rod rotation, can made using screw extruder
Plasticizing and uniformly mixing can fully be carried out by obtaining material, be a kind of outstanding successive reaction extruder.Screw extruder is main
Including：Six parts such as transmission, feeding device, barrel, screw rod, head and mouth mold.The three-screw extruder uses flat raft
Three screw rods, screw rod engage in the same direction, realize high Strong shear successive reaction；The three-screw extruder disperses section, precipitating phase, packet
It covers section, ground section and designs conveying screwing element, tooth form screwing element, 90 ° of engagement screwing elements, compression screwing element successively.
Polyacrylamide is a kind of linear macromolecule polymer, and product is broadly divided into two kinds of forms of dry powder and colloid.By it
Average molecular weight can be divided into the high molecular weight of the middle-molecular-weihydroxyethyl and 7,000,000 or more less than 1,000,000 low molecular weights, 200~4,000,000
Three classes.It can be divided into nonionic, anionic and cationic again by its structure.Anionic is mostly the hydrolysis body of PAM
HPAM.A large amount of amide groups is carried on the main chain of polyacrylamide, chemism is very high.Polyacrylamide of the present invention can
To use commercially available polyacrylamide, it is preferred to use the polyacrylamide of middle-molecular-weihydroxyethyl of the molecular weight less than 3,000,000 or low molecular weight
Amine.The polyacrylamide of nonionic, anionic and cationic, it is preferred to use anionic or cationic it is poly-
Acrylamide.
Alumine hydroxide colloid of the present invention uses commercially available alumine hydroxide colloid, mass concentration 20-25%.
Step（1）The molar ratio of ammonia is in the nickel nitrate and ammonium hydroxide：0.7~1.2:1.0~2.1.
Step（1）The molar ratio of polyacrylamide in the nickel nitrate and polyacrylamide solution is：0.9~1.1:
1.2~1.9.
Step（1）Concentration of polyacrylamide in the polyacrylamide solution is 50~120g/L, the polypropylene
The molecular weight of amide is 3,000,000 or less.
Step（2）The precipitating phase, cladding section, lithium source ground section are both provided with charge door, are respectively used to that hydrogen-oxygen is added
Change sodium, alumine hydroxide colloid, lithium salts；Wherein addition amount of sodium hydroxide is the 3-5% of jelly quality, and alumine hydroxide colloid is added
Measure the 0.5-3% of jelly quality.
Step（2）The lithium salts is lithium nitrate.
Step（2）Granularity after the lithium salts grinding is less than 500 μm.
Step（3）The temperature of the sintering is 800~1250 DEG C.
Second object of the present invention is to provide a kind of high ni-type nickel cobalt aluminium acid lithium ternary electrode material, the high ni-type
Nickel cobalt lithium aluminate ternary electrode material is by a kind of above-mentioned side preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod
Method is prepared, and the material is uniform, and particle diameter distribution is narrow.
Advantageous effect：The present invention is by nickel nitrate, cobalt nitrate, aluminum nitrate according to nickelic requirement and ammonium hydroxide, polyacrylamide
Solution disperses to form jelly, is then fed into three-screw extruder, is passed through successively by being fed to discharging in three-screw extruder
Sodium hydroxide pellets reaction is added in the dispersion of dispersion section, precipitating phase, alumine hydroxide colloid cladding is added in cladding section, lithium source ground section adds
Enter lithium salts grinding distribution, excludes to obtain nickel cobalt lithium aluminate precursor from screw rod；It is sintered through oxygen atmosphere, obtains the nickelic of high solidity
Type nickel cobalt aluminium ternary electrode material.The present invention utilizes screw rod continuous conveying, shearing and the characteristic that can persistently feed at different sections,
Nickel nitrate, cobalt nitrate, aluminum nitrate are formed into high nickel dispersion material, then coat aluminium, grinding so that the preparation of nickelic ternary material can
Performance boost is controlled, current discontinuous is overcome and prepares uneven, control unstable defect, solve conventional solid-state method batch mixing not
, particle diameter distribution is wide, material concentration, rate of addition, mixing speed are difficult to the defect of stability contorting, is mass, scale
Stabilization prepares nickelic ternary electrode material and provides an efficient technological approaches.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；Nickel nitrate and ammonia
The molar ratio of ammonia is in water：0.7:1；The molar ratio of sour nickel and the polyacrylamide in polyacrylamide solution is：0.9: 1.2；
（2）, by step（1）The jelly is sent into three-screw extruder, and three-screw extruder uses three screw rods of flat raft, spiral shell
Bar engages in the same direction, 300 bricks of rotating speed/min, realizes high Strong shear successive reaction；The three-screw extruder disperses section, precipitation
Section, cladding section, ground section design conveying screwing element, tooth form screwing element, 90 ° of engagement screwing elements, compression screw thread member successively
Part；In three-screw extruder by be fed to discharging successively by dispersion section dispersion, precipitating phase be added sodium hydroxide pellets reaction,
It coats section and alumine hydroxide colloid cladding, lithium source ground section addition nitric acid lithium salts grinding distribution is added, screw rod is discharged from screw rod and cleans
Obtain nickel cobalt lithium aluminate precursor；Wherein addition amount of sodium hydroxide is the 3% of jelly quality, and alumine hydroxide colloid is commercially available matter
The colloid of concentration 20% is measured, addition is the 0.5% of jelly quality；
（3）, by step（2）The nickel cobalt lithium aluminate precursor 800 DEG C of sintering 2h in oxygen atmosphere, obtain the nickelic of high solidity
Type nickel cobalt aluminium ternary electrode material；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium nitrate molar ratio in terms of Ni, Co, Al, Li are：0.75:0.2:
0.05：1.
Embodiment 2
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；Nickel nitrate and ammonia
The molar ratio of ammonia is in water：1:1；The molar ratio of sour nickel and the polyacrylamide in polyacrylamide solution is 1: 1.2；
（2）, by step（1）The jelly is sent into three-screw extruder, and three-screw extruder uses three screw rods of flat raft, spiral shell
400 bricks of bar engagement screws rotating speed in the same direction/min, realize high Strong shear successive reaction；The three-screw extruder disperses section, sinks
Shallow lake section, cladding section, ground section design conveying screwing element, tooth form screwing element, 90 ° of engagement screwing elements, compression screw thread successively
Element；It is anti-by the dispersion of dispersion section, precipitating phase addition sodium hydroxide pellets successively by being fed to discharging in three-screw extruder
It answers, coat section addition alumine hydroxide colloid cladding, lithium source ground section addition nitric acid lithium salts grinding distribution, cleaned from screw rod discharge
To nickel cobalt lithium aluminate precursor；Wherein addition amount of sodium hydroxide is the 4% of jelly quality, and alumine hydroxide colloid is commercial available quality
The colloid of concentration 20%, addition are the 1% of jelly quality；
（3）, by step（2）The nickel cobalt lithium aluminate precursor 900 DEG C of sintering 1h in oxygen atmosphere, obtain the nickelic of high solidity
Type nickel cobalt aluminium ternary electrode material；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium nitrate molar ratio in terms of Ni, Co, Al, Li are：0.8:0.15:
0.05：1.
Embodiment 3
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；Nickel nitrate and ammonia
The molar ratio of ammonia is in water：0.7:2.1；The molar ratio of sour nickel and the polyacrylamide in polyacrylamide solution is：1.1:
1.9；
（2）, by step（1）The jelly is sent into three-screw extruder, and three-screw extruder uses three screw rods of flat raft, spiral shell
Bar engages in the same direction, and 450 turns/min of rotating speed realizes high Strong shear successive reaction；The three-screw extruder disperses section, precipitation
Section, cladding section, ground section design conveying screwing element, tooth form screwing element, 90 ° of engagement screwing elements, compression screw thread member successively
Part；In three-screw extruder by be fed to discharging successively by dispersion section dispersion, precipitating phase be added sodium hydroxide pellets reaction,
It coats section and alumine hydroxide colloid cladding, lithium source ground section addition nitric acid lithium salts grinding distribution is added, obtained from screw rod discharge cleaning
Nickel cobalt lithium aluminate precursor；Wherein addition amount of sodium hydroxide is the 5% of jelly quality, and alumine hydroxide colloid is that commercial available quality is dense
The colloid of degree 25%, addition are jelly quality 2%；
（3）, by step（2）The nickel cobalt lithium aluminate precursor 950 DEG C of sintering 1.5h in oxygen atmosphere, obtain the height of high solidity
Ni-type nickel cobalt aluminium ternary electrode material；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium nitrate molar ratio in terms of Ni, Co, Al, Li are：0.7:0.25:
0.05：1.
Embodiment 4
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；Nickel nitrate and ammonia
The molar ratio of ammonia is in water：0.7:1.0；The molar ratio of sour nickel and the polyacrylamide in polyacrylamide solution is：0.9:
1.2；
（2）, by step（1）The jelly is sent into three-screw extruder, and three-screw extruder uses three screw rods of flat raft, spiral shell
Bar engages in the same direction, and 250 turns/min of rotating speed realizes high Strong shear successive reaction；The three-screw extruder disperses section, precipitation
Section, cladding section, ground section design conveying screwing element, tooth form screwing element, 90 ° of engagement screwing elements, compression screw thread member successively
Part；In three-screw extruder by be fed to discharging successively by dispersion section dispersion, precipitating phase be added sodium hydroxide pellets reaction,
It coats section and alumine hydroxide colloid cladding, lithium source ground section addition nitric acid lithium salts grinding distribution is added, obtained from screw rod discharge cleaning
Nickel cobalt lithium aluminate precursor；Wherein addition amount of sodium hydroxide is the 5% of jelly quality, and alumine hydroxide colloid is that commercial available quality is dense
The colloid of degree 25%, addition are the 3% of jelly quality；
（3）, by step（2）The nickel cobalt lithium aluminate precursor 1000 DEG C of sintering 1h in oxygen atmosphere, obtain the height of high solidity
Ni-type nickel cobalt aluminium ternary electrode material；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium nitrate molar ratio in terms of Ni, Co, Al, Li are：0.7:0.25:
0.05：1.
Embodiment 5
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；Nickel nitrate and ammonia
The molar ratio of ammonia is in water： 1.2:1.0；The molar ratio of sour nickel and the polyacrylamide in polyacrylamide solution is：0.9:
1.2；
（2）, by step（1）The jelly is sent into three-screw extruder, and three-screw extruder uses three screw rods of flat raft, spiral shell
Bar engages in the same direction, and 350 turns/min of rotating speed realizes high Strong shear successive reaction；The three-screw extruder disperses section, precipitation
Section, cladding section, ground section design conveying screwing element, tooth form screwing element, 90 ° of engagement screwing elements, compression screw thread member successively
Part；In three-screw extruder by be fed to discharging successively by dispersion section dispersion, precipitating phase be added sodium hydroxide pellets reaction,
It coats section and alumine hydroxide colloid cladding, lithium source ground section addition nitric acid lithium salts grinding distribution is added, obtained from screw rod discharge cleaning
Nickel cobalt lithium aluminate precursor；Wherein addition amount of sodium hydroxide is the 5% of jelly quality, and alumine hydroxide colloid is commercial available quality 25%
Colloid, addition be jelly quality 3%；
（3）, by step（2）The nickel cobalt lithium aluminate precursor 1250 DEG C of sintering 1h in oxygen atmosphere, obtain the height of high solidity
Ni-type nickel cobalt aluminium ternary electrode material；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium nitrate molar ratio in terms of Ni, Co, Al, Li are：0.75:0.2:
0.05：1.
Comparative example 1
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；Nickel nitrate and ammonia
The molar ratio of ammonia is in water： 1.2:1.0；The molar ratio of sour nickel and the polyacrylamide in polyacrylamide solution is：0.9:
1.2；
（2）, by step（1）The jelly hydro-thermal process is added sodium hydroxide pellets reaction, alumine hydroxide colloid packet is added
Dispersion is covered, wherein addition amount of sodium hydroxide is the 5% of jelly quality, and alumine hydroxide colloid is the colloid of commercial available quality 25%, is added
Enter 3% that amount is jelly quality；
（3）, by step（2）The nickel cobalt lithium aluminate precursor 1250 DEG C of sintering in oxygen atmosphere with nitric acid lithium salts grinding distribution
1h obtains the high ni-type nickel cobalt aluminium ternary electrode material of high solidity；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium nitrate molar ratio in terms of Ni, Co, Al, Li are：0.75:0.2:
0.05：1.
High ni-type nickle cobalt lithium manganate tertiary cathode material prepared by embodiment 1-5, comparative example 1 tests crystal grain distribution, such as
Shown in table 1；It under equal conditions mixes to be arranged with conductive agent, binder respectively and forms anode in positive pole aluminium foil collection liquid surface,
It is diaphragm that cathode, which uses graphitic carbon, polypropylene, and LiPF6 is that electrolyte assembles lithium ion battery, its performance is tested, in 100mA/g
Under, the specific capacity after charge-discharge test first discharge specific capacity and 100 cycles.Such as table 1.
The product test result of 1 embodiment of table and comparative example
By test analysis, the present invention is using screw rod as reactor so that and predecessor is uniformly dispersed, and grain size continuously coats,
Uniform to the final product particle size dispersion of water, moreover, by battery testing, stable circulation performance is excellent, solves tradition
Solid phase method batch mixing is uneven, particle diameter distribution is wide, material concentration, rate of addition, mixing speed are difficult to the defect of stability contorting, for batch
Quantization, scale stabilization prepare nickelic ternary electrode material and provide an efficient technological approaches.
Claims (10)
1. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod, which is characterized in that specifically include
Following steps：
（1）, disperse nickel nitrate, cobalt nitrate, aluminum nitrate and ammonium hydroxide, polyacrylamide solution to form jelly；
（2）, by step（1）The jelly is sent into three-screw extruder, in three-screw extruder by be fed to discharging according to
It is secondary sodium hydroxide pellets reaction is added by the dispersion of dispersion section, precipitating phase, alumine hydroxide colloid cladding is added in cladding section, lithium source grinds
It grinds section and lithium salts grinding distribution is added, be discharged from screw rod, cleaning obtains nickel cobalt lithium aluminate precursor；
（3）, by step（2）The nickel cobalt lithium aluminate precursor is sintered in oxygen atmosphere, obtains the high ni-type nickel cobalt of high solidity
Aluminium ternary electrode material；
Wherein, the nickel nitrate, cobalt nitrate, aluminum nitrate, the lithium salts molar ratio in terms of Ni, Co, Al, Li are：0.7~1.2:0.1~
0.3:0.03~0.08：1.
2. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（1）The molar ratio of ammonia is in the nickel nitrate and ammonium hydroxide：0.7~1.2:1.0~2.1.
3. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（1）The molar ratio of polyacrylamide in the nickel nitrate and polyacrylamide solution is：0.9~
1.1:1.2~1.9.
4. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（1）Concentration of polyacrylamide in the polyacrylamide solution is 50~120g/L, described poly- third
The molecular weight of acrylamide is 3,000,000 or less.
5. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（2）The precipitating phase, cladding section, lithium source ground section are both provided with charge door, are respectively used to that hydrogen is added
Sodium oxide molybdena, alumine hydroxide colloid, lithium salts；Wherein addition amount of sodium hydroxide is the 3-5% of jelly quality, and alumine hydroxide colloid adds
Enter the 0.5-3% that amount is jelly quality.
6. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（2）The lithium salts is lithium nitrate.
7. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（2）Granularity after the lithium salts grinding is less than 500 μm.
8. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（3）The temperature of the sintering is 800~1250 DEG C.
9. a kind of method preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1,
It is characterized in that, step（2）The three-screw extruder uses three screw rods of flat raft, screw rod to engage in the same direction, realizes high Strong shear
Successive reaction；The three-screw extruder disperses section, precipitating phase, cladding section, ground section and designs conveying screwing element, tooth successively
Shape screwing element, 90 ° of engagement screwing elements, compression screwing element.
10. preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod according to claim 1~9 any one of them is a kind of
The high ni-type nickel cobalt aluminium acid lithium ternary electrode material that the method for material is prepared.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810156231.XA CN108306017A (en) | 2018-02-24 | 2018-02-24 | A method of preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810156231.XA CN108306017A (en) | 2018-02-24 | 2018-02-24 | A method of preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108306017A true CN108306017A (en) | 2018-07-20 |
Family
ID=62848870
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810156231.XA Withdrawn CN108306017A (en) | 2018-02-24 | 2018-02-24 | A method of preparing high ni-type nickel cobalt aluminium acid lithium ternary electrode material using screw rod |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108306017A (en) |
-
2018
- 2018-02-24 CN CN201810156231.XA patent/CN108306017A/en not_active Withdrawn
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Myung et al. | Nanostructured cathode materials for rechargeable lithium batteries | |
| KR101757490B1 (en) | Nickel-cobalt-manganese compound particle powder and method for producing same, lithium composite oxide particle powder and method for producing same, and nonaqueous electrolyte secondary battery | |
| JP5590337B2 (en) | Manganese composite hydroxide particles, positive electrode active material for non-aqueous electrolyte secondary battery, non-aqueous electrolyte secondary battery, and production methods thereof | |
| TWI584520B (en) | Li-Ni composite oxide particles and nonaqueous electrolyte batteries | |
| WO2012164763A1 (en) | Transition metal composite hydroxide capable of serving as precursor of positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing same, positive electrode active material for nonaqueous electrolyte secondary batteries, method for producing positive electrode active material for nonaqueous electrolyte secondary batteries, and nonaqueous electrolyte secondary battery using positive electrode active material | |
| CN103715424A (en) | Core-shell structured cathode material and preparation method thereof | |
| Wang et al. | Effect of surface fluorine substitution on high voltage electrochemical performances of layered LiNi0. 5Co0. 2Mn0. 3O2 cathode materials | |
| JP2015122234A (en) | Positive electrode active material for nonaqueous electrolyte secondary batteries, and method for manufacturing the same | |
| WO2023124357A1 (en) | Nanoscale precursor of sodium-ion battery, composite positive electrode material and preparation method | |
| CN104953109B (en) | A kind of nucleocapsid LiMn2O4 and its synthetic method for promoting high temperature resistance | |
| JP6568333B1 (en) | Positive electrode active material, method for producing the same, positive electrode, and lithium ion battery | |
| Tao et al. | Understanding the Ni-rich layered structure materials for high-energy density lithium-ion batteries | |
| JP2009123400A (en) | Active material for lithium secondary battery, and lithium secondary battery | |
| US9166225B2 (en) | Sodium vanadium oxide anode material for sodium ion secondary battery, preparation method thereof and sodium ion secondary battery having the same | |
| Cheng et al. | Enhanced electrochemical performance of LiNi1/3Co1/3Mn1/3O2 cathode material by Al2O3 surface coating derived via NH2-MIL-53 (Al) MOF | |
| Thirunakaran et al. | Studies on chromium/aluminium-doped manganese spinel as cathode materials for lithium-ion batteries—A novel chelated sol–gel synthesis | |
| JP2020035693A (en) | Transition metal composite hydroxide, manufacturing method thereof, lithium transition metal composite oxide active material, and lithium ion secondary battery | |
| JP2015122235A (en) | Positive electrode active material for nonaqueous electrolyte secondary batteries, and method for manufacturing the same | |
| JP5392035B2 (en) | Nickel-manganese composite hydroxide particles for non-aqueous electrolyte secondary battery positive electrode active material and method for producing the same, positive electrode active material for non-aqueous electrolyte secondary battery and method for producing the same, and non-aqueous electrolyte secondary battery | |
| JP2011219354A (en) | Crystalline manganese complex oxide, lithium manganese complex oxide for lithium secondary battery and method for producing the same | |
| JP2011116582A5 (en) | ||
| CN106654224B (en) | A kind of cobalt acid lithium composite material and preparation method, positive electrode | |
| JP7273260B2 (en) | Positive electrode active material for lithium ion secondary battery, method for producing the same, and lithium ion secondary battery | |
| JP7167491B2 (en) | Method for producing positive electrode active material for lithium ion secondary battery, positive electrode active material for lithium ion secondary battery, and lithium ion secondary battery | |
| JP7473828B2 (en) | Positive electrode for non-aqueous electrolyte secondary battery and method for producing same |
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 | ||
| WW01 | Invention patent application withdrawn after publication |
Application publication date: 20180720 |
|
| WW01 | Invention patent application withdrawn after publication |