CN105355911B - A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material - Google Patents
A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material Download PDFInfo
- Publication number
- CN105355911B CN105355911B CN201510844880.5A CN201510844880A CN105355911B CN 105355911 B CN105355911 B CN 105355911B CN 201510844880 A CN201510844880 A CN 201510844880A CN 105355911 B CN105355911 B CN 105355911B
- Authority
- CN
- China
- Prior art keywords
- lithium manganate
- cobalt lithium
- nickel
- sintering
- preparation
- 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.)
- Active
Links
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 title claims abstract description 33
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000010406 cathode material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000005245 sintering Methods 0.000 claims abstract description 75
- 239000000463 material Substances 0.000 claims abstract description 42
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000000203 mixture Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 21
- 238000012545 processing Methods 0.000 claims abstract description 18
- 229920002635 polyurethane Polymers 0.000 claims abstract description 17
- 239000004814 polyurethane Substances 0.000 claims abstract description 17
- 235000020985 whole grains Nutrition 0.000 claims abstract description 17
- 238000005253 cladding Methods 0.000 claims abstract description 12
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 12
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 12
- 239000002243 precursor Substances 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims abstract description 11
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 4
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 48
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052593 corundum Inorganic materials 0.000 claims description 11
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium chloride Substances Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- MOLYXOOGDFTUJT-UHFFFAOYSA-L [Li].[Mn](=O)(=O)(O)O.[Co] Chemical compound [Li].[Mn](=O)(=O)(O)O.[Co] MOLYXOOGDFTUJT-UHFFFAOYSA-L 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 239000011343 solid material Substances 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 239000002077 nanosphere Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 7
- 238000000227 grinding Methods 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- 239000010941 cobalt Substances 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229940116007 ferrous phosphate Drugs 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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
-
- 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
-
- 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
-
- 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
Abstract
The invention belongs to battery material technical field, disclose a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, it includes raw material mixing, once sintered, doping, double sintering, cladding and whole grain processing step, wherein raw material, which is mixed into, uses three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor and polyethylene glycol are disperseed, mixed and crushed, forms uniform intermediate mixture；The present invention alumina-coated nickel-cobalt lithium manganate cathode material the once sintered temperature of preparation method it is low, sintering time is short, technique is simple, specific capacity is big, good cycle.The preparation method, which also has, invests the advantages such as less, technically reliable, operating cost be low, has good economic benefit and market popularization value.
Description
Technical field
The invention belongs to battery material technical field, is related to a kind of preparation method of nickel-cobalt lithium manganate cathode material, especially
It is related to a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material.
Background technology
Lithium-ion-power cell is generally acknowledged most potential on-vehicle battery both at home and abroad at present, mainly by positive electrode, negative
The part such as pole material, barrier film, electrolyte forms；Wherein, positive electrode is the important component of lithium ion battery, and is determined
The key factor of performance of lithium ion battery；Therefore, from the aspect of resource, environmental protection and security performance, lithium ion battery is found
Ideal electrode active material is still international energy material worker primary problem to be solved.
Anode material for lithium-ion batteries mainly has cobalt acid lithium, LiMn2O4, cobalt nickel lithium manganate ternary material, ferrous phosphate at present
Lithium etc..Lithium ion battery wherein using cobalt acid lithium as positive electrode have in light weight, capacity is big, higher than energy, operating voltage is high,
Electric discharge is steady, is adapted to the features such as heavy-current discharge, good cycle, long lifespan, there is the advantage that can not substitute on compact battery,
It is the maximum anode material for lithium-ion batteries of current production rate.But cobalt acid lithium is expensive, toxicity is larger, and exists certain
Safety issue.LiMn2O4 cost is low, and security is good, but cycle performance, especially high temperature cyclic performance are poor, in electrolyte
In have certain dissolubility, storge quality is poor.LiFePO 4 because the uniformity of material is poor, preparation technology complexity hinder its
Popularization and application on lithium battery, at present also in the concern of people.Therefore, research and develop that electrical property is close with cobalt acid lithium and price
Cheap anode material of lithium battery has turned into the important directions of lithium battery development.
Recently, cobalt nickel lithium manganate ternary material is increasingly subject to attract attention, by the material property such as volume and capacity ratio, weight
The data test of specific capacity, circulation, safety etc., generally shows nickel-cobalt lithium manganate material as novel lithium battery just
Some excellent properties of pole material, as voltage platform is high, reversible specific capacity is big, Stability Analysis of Structures, have a safety feature the advantages that.Although
Cobalt nickel lithium manganate ternary material is quickly grown, but it also has some defects in actual applications.As coulombic efficiency first is low, times
Rate performance and cycle performance are poor, composition and pattern are unmanageable, tap density is low etc..At present, people are mainly by reducing sun
Ion mixing improves its coulombic efficiency first, by increasing electronic conductivity and ionic conductivity improves its high rate performance,
Increase its tap density by preparing the small particle of pattern rule, specific surface area.
One of method for synthesizing nickle cobalt lithium manganate is high temperature solid-state method, is to grind lithium source, nickel source, cobalt source, manganese source together
Mixing, synthesis is calcined under about 1000 DEG C of high temperature.However, this mode necessarily brings the inhomogeneities of material, so as to cause to burn
Product after knot is difficult to obtain the material of no dephasign so that capacity attenuation is fast, comprehensive electrochemical properties reduce.Another method is colloidal sol
Gel method, but method drying water removal is difficult, have impact on its industrialization.
The content of the invention
The goal of the invention of the present invention is：For above-mentioned problem, there is provided a kind of once sintered temperature is low, sintering when
Between it is short, technique is simple, specific capacity is big, the preparation method of the alumina-coated nickel-cobalt lithium manganate cathode material of good cycle.
The technical solution adopted by the present invention is as follows：
A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, comprises the following steps：
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, by lithium carbonate, receive
Rice spherical nickel cobalt manganese hydroxide precursor and polyethylene glycol are disperseed, mixed and crushed, and form uniform intermediate mixing
Thing；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 650~750 DEG C, and sintering time is 2~
7h；
(3) adulterate：Select nano level ZnO, MgO, Al2O3Or TiO2In one kind, to account for total solid material mass
0.1~0.2% adds in the nickel-cobalt lithium manganate material obtained by step (2), and it is batch mixing medium to add polyurethane ball, is mixed
Material；
(4) double sintering：By through overdoping nickle cobalt lithium manganate be sent into pushed bat kiln carry out double sintering, sintering process not between
Disconnected is filled with air or oxygen；
(5) coat：The Al solions that molar concentration is 0.01~0.06mol/L are prepared, by the nickel after double sintering
Cobalt manganic acid lithium is added in solution and is well mixed, and is passed through ammonia spirit, stirring, cleaning, filtering, drying, obtains by Al2O3Cladding
Nickle cobalt lithium manganate material positive electrode.
(6) whole grain is handled：Whole grain processing, adjustment are carried out to the nickle cobalt lithium manganate product of coated processing using special arrangement
Product crushes, value parameter, that is, obtains nickle cobalt lithium manganate finished product.
Further, the proportion of step (1) the polyurethane ball is >=1.3, ratio of grinding media to material 3:4:3, mixing time be 3~
4h。
Further, step (1) lithium carbonate, the mol ratio of nanometer spherical nickel cobalt manganese hydroxide precursor are 1：
0.53~0.56, the mass ratio that polyethylene glycol accounts for total mixture is 10%~40%.
Further, the sintering temperature of step (4) described double sintering is 900~1000 DEG C, and sintering time is 2~7h.
Further, the temperature of step (5) described stirring is 75~80 DEG C, and the time of stirring is 4~6h.
Further, step (5) the Al solions are Al (NO3)3、Al2(SO4)3Or AlCl3One kind in solution.
Further, step (6) described special arrangement is airslide disintegrating mill and grader, loading frequency control 6~
10Hz, grade frequency are controlled in 15~20Hz.
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
(1) for the present invention using lithium carbonate as lithium source, once sintered temperature is low, and sintering time is short, has saved the energy；Use simultaneously
The heat treating regime of high temperature is advantageous to obtain structurally consummate material after first low temperature, is also beneficial to improve the electrochemistry circulation of material
Performance；
(2) pattern of nickle cobalt lithium manganate finished product and granularity depend primarily on presoma, and the present invention is directly with nanometer spherical nickel
Cobalt manganese hydroxide precursor is raw material, and each element can be made to be mixed in molecular level level so that product component is homogeneous, from
And reduce cation mixing；This programme control point is few, reduces production stage, is readily produced, and technique is simple, and properties of product are stable
Property is good；
(3) finished product is doped using improved jet mill grinding equipment, and coated with aluminum oxide, production
Product granularity is moderate and is evenly distributed, and tap density is big, makes have good processing characteristics in lithium ion battery production process；
(4) spheroidization of positive electrode powder granule can improve material bulk density and volume and capacity ratio, and spherical
Product also has excellent mobility, dispersiveness and processability, is advantageous to make the painting of electrode material slurry and electrode slice
Cover, improve electrode tablet quality；
(5) have and invest the advantages such as less, technically reliable, operating cost be low, there is good economic benefit, has well
Market popularization value.
Brief description of the drawings
Fig. 1 is the process route chart of production alumina-coated nickel-cobalt lithium manganate cathode material.
Embodiment
In order that the technical means, the inventive features, the objects and the advantages of the present invention are easy to understand, tie below
Conjunction is specifically illustrating and embodiment, and the present invention is expanded on further.It should be appreciated that specific embodiment described herein is only solving
The present invention is released, is not intended to limit the present invention.
Embodiment 1
A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, comprises the following steps：
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, in molar ratio 1：
0.53 weighs lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor, and accounts for the poly- second two that total mixture mass ratio is 10%
Alcohol is disperseed, mixed and crushed, and forms uniform intermediate mixture, and the wherein proportion of polyurethane ball is 1.3, and ratio of grinding media to material is
3:4:3, mixing time 3h；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 650 DEG C, sintering time 3h；
(3) adulterate：Nano level ZnO is selected, processing is doped to the nickle cobalt lithium manganate obtained by step (2), it is total to account for
The 0.1% of solid matter mass is added in the nickle cobalt lithium manganate obtained by step (2), carries out batch mixing；
(4) double sintering：By through overdoping nickle cobalt lithium manganate be sent into pushed bat kiln carry out double sintering, sintering process not between
Disconnected is filled with air, and sintering temperature is 900 DEG C, sintering time 12h；
(5) coat：Prepare 0.01mol/L Al (NO3)3Solution, the nickle cobalt lithium manganate after two are burnt are added to solution and worked as
In be well mixed, be passed through 1mol/L ammonia spirit, 75 DEG C of stirring 4h；Filtering is cleaned with distilled water, 12h is dried at 500 DEG C, obtains
To by Al2O3The nickle cobalt lithium manganate material positive electrode of cladding；
(6) whole grain is handled：Using elite powder Engineered Equipment Co. of Shandong Weifang City AF series airslide disintegrating mill and point
Level machine carries out whole grain processing to the nickle cobalt lithium manganate product through double sintering, and adjustment product crushes, value parameter, that is, obtains nickel cobalt
LiMn2O4 finished product.
Embodiment 2
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, in molar ratio 1：
0.535 weighs lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor, and accounts for the poly- second two that total mixture mass ratio is 20%
Alcohol is disperseed, mixed and crushed, and forms uniform intermediate mixture, and the wherein proportion of polyurethane ball is 1.5, and ratio of grinding media to material is
3:4:3, mixing time 3h；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 700 DEG C, sintering time 3h；
(3) adulterate：Nano level MgO is selected, processing is doped to the nickle cobalt lithium manganate obtained by step (2), it is total to account for
The 0.1% of solid matter mass is added in the nickle cobalt lithium manganate obtained by step (2), carries out batch mixing；
(4) double sintering：Nickle cobalt lithium manganate through overdoping, cladding is sent into pushed bat kiln and carries out double sintering, it is sintered
Journey is continual to be filled with air, and sintering temperature is 1000 DEG C, sintering time 10h；
(5) coat：Prepare 0.03mol/L Al (NO3)3Solution, the nickle cobalt lithium manganate after two are burnt are added to solution and worked as
In be well mixed, be passed through 2mol/L ammonia spirit, 80 DEG C of stirring 5h；Filtering is cleaned with distilled water, 16h is dried at 500 DEG C, obtains
To by Al2O3The nickle cobalt lithium manganate material positive electrode of cladding；
(6) whole grain is handled：The nickle cobalt lithium manganate product through double sintering is carried out using airslide disintegrating mill and grader whole
Grain processing, loading frequency control is in 6~10Hz, and grade frequency is controlled in 15~20Hz, and adjustment product crushes, value parameter, i.e.,
Obtain nickle cobalt lithium manganate finished product.
Embodiment 3
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, in molar ratio 1:
0.55 weighs lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor, and accounts for the poly- second two that total mixture mass ratio is 30%
Alcohol is disperseed, mixed and crushed, and forms uniform intermediate mixture, and the wherein proportion of polyurethane ball is 1.4, and ratio of grinding media to material is
3:4:3, mixing time 4h；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 750 DEG C, sintering time 5h；
(3) adulterate：Select nano level Al2O3, processing is doped to the nickle cobalt lithium manganate obtained by step (2), it is total to account for
The 0.2% of solid matter mass is added in the nickle cobalt lithium manganate obtained by step (2), carries out batch mixing；
(4) double sintering：Nickle cobalt lithium manganate through overdoping, cladding is sent into pushed bat kiln and carries out double sintering, it is sintered
Journey is continual to be filled with air, and sintering temperature is 1000 DEG C, sintering time 11h；
(5) coat：Prepare 0.06mol/L Al2(SO4)3Solution, the nickle cobalt lithium manganate after two are burnt are added to solution
It is central well mixed, it is passed through 2mol/L ammonia spirit, 75 DEG C of stirring 6h；Filtering is cleaned with distilled water, 20h is dried at 600 DEG C,
Obtain by Al2O3The nickle cobalt lithium manganate material positive electrode of cladding；
(6) whole grain is handled：The nickle cobalt lithium manganate product through double sintering is carried out using airslide disintegrating mill and grader whole
Grain processing, loading frequency control is in 6~10Hz, and grade frequency is controlled in 15~20Hz, and adjustment product crushes, value parameter, i.e.,
Obtain nickle cobalt lithium manganate finished product.
Embodiment 4
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, in molar ratio 1：
0.56 weighs lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor, and accounts for the poly- second two that total mixture mass ratio is 40%
Alcohol is disperseed, mixed and crushed, and forms uniform intermediate mixture, and the wherein proportion of polyurethane ball is 1.4, and ratio of grinding media to material is
3:4:3, mixing time 4h；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 700 DEG C, sintering time 7h；
(3) adulterate：Select nano level TiO2, processing is doped to the nickle cobalt lithium manganate obtained by step (2), it is total to account for
The 0.2% of solid matter mass is added in the nickle cobalt lithium manganate obtained by step (2), carries out batch mixing；
(4) double sintering：Nickle cobalt lithium manganate through overdoping, cladding is sent into pushed bat kiln and carries out double sintering, it is sintered
Journey is continual to be filled with air, and sintering temperature is 1000 DEG C, sintering time 11h；
(5) coat：Prepare 0.01mol/L Al2(SO4)3Solution, the nickle cobalt lithium manganate after two are burnt are added to solution
It is central well mixed, it is passed through 1mol/L ammonia spirit, 75 DEG C of stirring 5h；Filtering is cleaned with distilled water, 24h is dried at 600 DEG C,
Obtain by Al2O3The nickle cobalt lithium manganate material positive electrode of cladding；
(6) whole grain is handled：The nickle cobalt lithium manganate product through double sintering is carried out using airslide disintegrating mill and grader whole
Grain processing, adjustment product crushes, value parameter, that is, obtains nickle cobalt lithium manganate finished product.
Embodiment 5
A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, comprises the following steps：
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, in molar ratio 1：
0.53 weighs lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor, and accounts for the poly- second two that total mixture mass ratio is 10%
Alcohol is disperseed, mixed and crushed, and forms uniform intermediate mixture, and the wherein proportion of polyurethane ball is 1.3, and ratio of grinding media to material is
3:4:3, mixing time 3h；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 650 DEG C, sintering time 3h；
(3) adulterate：Nano level ZnO is selected, processing is doped to the nickle cobalt lithium manganate obtained by step (2), it is total to account for
The 0.1% of solid matter mass is added in the nickle cobalt lithium manganate obtained by step (2), carries out batch mixing；
(4) double sintering：By through overdoping nickle cobalt lithium manganate be sent into pushed bat kiln carry out double sintering, sintering process not between
Disconnected is filled with air, and sintering temperature is 900 DEG C, sintering time 12h；
(5) coat：Prepare 0.01mol/L AlCl3Solution, the nickle cobalt lithium manganate after two are burnt are added among solution
It is well mixed, it is passed through 1mol/L ammonia spirit, 75 DEG C of stirring 4h；Filtering is cleaned with distilled water, 12h is dried at 500 DEG C, obtains
By Al2O3The nickle cobalt lithium manganate material positive electrode of cladding；
(6) whole grain is handled：Using elite powder Engineered Equipment Co. of Shandong Weifang City AF series airslide disintegrating mill and point
Level machine carries out whole grain processing to the nickle cobalt lithium manganate product through double sintering, and adjustment product crushes, value parameter, that is, obtains nickel cobalt
LiMn2O4 finished product.
Embodiment 6
A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, comprises the following steps：
(1) raw material mixes：Use three dimension high efficiency inclined mixer and using polyurethane ball as batch mixing medium, in molar ratio 1：
0.53 weighs lithium carbonate, nanometer spherical nickel cobalt manganese hydroxide precursor, and accounts for the poly- second two that total mixture mass ratio is 10%
Alcohol is disperseed, mixed and crushed, and forms uniform intermediate mixture, and the wherein proportion of polyurethane ball is 1.3, and ratio of grinding media to material is
3:4:3, mixing time 3h；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, it is raw
Nickel-cobalt lithium manganate material is produced, sintering process is continual to be filled with oxygen, and sintering temperature is 650 DEG C, sintering time 3h；
(3) adulterate：Nano level MgO is selected, processing is doped to the nickle cobalt lithium manganate obtained by step (2), it is total to account for
The 0.1% of solid matter mass is added in the nickle cobalt lithium manganate obtained by step (2), carries out batch mixing；
(4) double sintering：By through overdoping nickle cobalt lithium manganate be sent into pushed bat kiln carry out double sintering, sintering process not between
Disconnected is filled with air, and sintering temperature is 900 DEG C, sintering time 12h；
(5) coat：Prepare 0.01mol/L AlCl3Solution, the nickle cobalt lithium manganate after two are burnt are added among solution
It is well mixed, it is passed through 1mol/L ammonia spirit, 75 DEG C of stirring 4h；Filtering is cleaned with distilled water, 12h is dried at 500 DEG C, obtains
By Al2O3The nickle cobalt lithium manganate material positive electrode of cladding；
(6) whole grain is handled：Using elite powder Engineered Equipment Co. of Shandong Weifang City AF series airslide disintegrating mill and point
Level machine carries out whole grain processing to the nickle cobalt lithium manganate product through double sintering, and adjustment product crushes, value parameter, that is, obtains nickel cobalt
LiMn2O4 finished product.
Alumina-coated nickel-cobalt lithium manganate cathode material performance test made from distinct methods
Claims (6)
1. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material, it is characterised in that comprise the following steps：
(1) raw material mixes：Three dimension high efficiency inclined mixer is used and using polyurethane ball as batch mixing medium, by lithium carbonate, nanosphere
Shape nickel cobalt manganese hydroxide precursor and polyethylene glycol are disperseed, mixed and crushed, and form uniform intermediate mixture；
(2) it is once sintered：Intermediate mixture obtained by step (1) is loaded into saggar, pushed bat kiln is sent into and is sintered, produce nickel
Cobalt lithium manganate material, sintering process is continual to be filled with oxygen, and sintering temperature is 650~750 DEG C, and sintering time is 2~7h；
(3) adulterate：Select nano level ZnO, MgO, Al2O3Or TiO2In one kind, with account for the 0.1 of total solid material mass~
0.2% adds in the nickel-cobalt lithium manganate material obtained by step (2), carries out batch mixing；
(4) double sintering：Nickle cobalt lithium manganate through overdoping is sent into pushed bat kiln and carries out double sintering, sintering process is continual
It is filled with air or oxygen；
(5) coat：The Al solions that molar concentration is 0.01~0.06mol/L are prepared, by the nickel cobalt manganese after double sintering
Sour lithium is added in solution and is well mixed, and is passed through ammonia spirit, stirring, cleaning, filtering, drying, obtains by Al2O3The nickel of cladding
Cobalt manganic acid lithium material positive electrode；
(6) whole grain is handled：Whole grain processing is carried out to the nickle cobalt lithium manganate product of coated processing using special arrangement, adjusts product
Crush, value parameter, that is, obtain nickle cobalt lithium manganate finished product.
2. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material according to claim 1, its feature exist
In：Step (1) lithium carbonate, the mol ratio of nanometer spherical nickel cobalt manganese hydroxide precursor are 1：0.53~0.56, poly- second
The mass ratio that glycol accounts for total mixture is 10%~40%.
3. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material according to claim 1, its feature exist
In：The sintering temperature of step (4) described double sintering is 900~1000 DEG C, and sintering time is 2~7h.
4. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material according to claim 1, its feature exist
In：The temperature of step (5) described stirring is 75~80 DEG C, and the time of stirring is 4~6h.
5. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material according to claim 1 or 4, its feature
It is：Step (5) the Al solions are Al (NO3)3、Al2(SO4)3Or AlCl3One kind in solution.
6. a kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material according to claim 1, its feature exist
In：Step (6) described special arrangement is airslide disintegrating mill and grader, and loading frequency control is in 6~10Hz, grade frequency control
In 15~20Hz.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510844880.5A CN105355911B (en) | 2015-11-28 | 2015-11-28 | A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510844880.5A CN105355911B (en) | 2015-11-28 | 2015-11-28 | A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105355911A CN105355911A (en) | 2016-02-24 |
| CN105355911B true CN105355911B (en) | 2018-02-13 |
Family
ID=55331829
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510844880.5A Active CN105355911B (en) | 2015-11-28 | 2015-11-28 | A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105355911B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106784682A (en) * | 2016-12-20 | 2017-05-31 | 复旦大学 | A kind of preparation method of metal oxide coating spinelle type LiMn2O4 |
| CN107302087B (en) * | 2017-07-27 | 2019-10-11 | 格林美（无锡）能源材料有限公司 | A kind of lithium battery nickle cobalt lithium manganate tertiary cathode material and preparation method thereof |
| CN107579244B (en) * | 2017-09-13 | 2021-10-22 | 桑顿新能源科技(长沙)有限公司 | High-crystallinity lithium ion battery positive electrode material synthesis method and positive electrode material |
| CN109962233A (en) * | 2017-12-25 | 2019-07-02 | 格林美（无锡）能源材料有限公司 | A kind of class monocrystalline positive electrode of gradient type and preparation method thereof |
| CN108336327A (en) * | 2017-12-30 | 2018-07-27 | 宁夏科捷锂电池股份有限公司 | A method of doping AL ion coated lithium tetraborates prepare LiMn2O4 |
| CN109037639A (en) * | 2018-08-05 | 2018-12-18 | 南京理工大学 | A kind of preparation method coating nickel element adulterated lithium manganate composite material |
| CN109244407A (en) * | 2018-09-17 | 2019-01-18 | 贵州永合益环保科技有限公司 | A kind of method that cladding nickel-cobalt lithium manganate cathode material is blended in magnesia, aluminium oxide |
| CN109686973A (en) * | 2018-12-12 | 2019-04-26 | 无锡晶石新型能源股份有限公司 | A kind of preparation method of the nickelic positive electrode of low-cost high-quality |
| CN110165178B (en) * | 2019-05-24 | 2022-07-08 | 东莞市安德丰电池有限公司 | Lithium battery positive electrode material, preparation method thereof and lithium battery containing positive electrode material |
| CN112151728B (en) * | 2019-06-28 | 2022-04-15 | 比亚迪股份有限公司 | Lithium ion battery composite diaphragm, preparation method thereof and lithium ion battery |
| CN110767907B (en) * | 2019-11-07 | 2022-07-19 | 河南电池研究院有限公司 | Universal surface coating modification method for lithium ion battery anode material |
| CN112599763A (en) * | 2020-12-15 | 2021-04-02 | 惠州亿纬锂能股份有限公司 | Ternary single crystal positive electrode material and preparation method and application thereof |
| CN114388772A (en) * | 2021-12-09 | 2022-04-22 | 格力钛新能源股份有限公司 | Molybdenum vanadium titanium niobium composite oxide negative electrode material, preparation method thereof and lithium ion battery |
| CN114843488B (en) * | 2022-06-14 | 2024-03-26 | 远景动力技术(江苏)有限公司 | Positive electrode active material, electrochemical device, and electronic device |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102006049098B4 (en) * | 2006-10-13 | 2023-11-09 | Toda Kogyo Corp. | Powdered compounds, process for their production and their use in lithium secondary batteries |
| KR20100139085A (en) * | 2008-03-28 | 2010-12-31 | 비와이디 컴퍼니 리미티드 | A method of preparing a lithium iron phosphate cathode material for lithium secondary batteries |
| CN104577128A (en) * | 2013-10-10 | 2015-04-29 | 无锡星波能源科技有限公司 | Alumina coating method of lithium ion battery positive electrode material |
| CN104183840A (en) * | 2014-08-07 | 2014-12-03 | 青岛乾运高科新材料股份有限公司 | Preparation method of spherical ternary lithium nickel cobalt manganese oxide positive material |
| CN104183829A (en) * | 2014-08-08 | 2014-12-03 | 青岛乾运高科新材料股份有限公司 | Preparation method of nickel cobalt lithium manganate |
-
2015
- 2015-11-28 CN CN201510844880.5A patent/CN105355911B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN105355911A (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105355911B (en) | A kind of preparation method of alumina-coated nickel-cobalt lithium manganate cathode material | |
| CN103094558B (en) | A kind of zinc ferrite based nano composite material, preparation method and its usage | |
| CN103794773B (en) | A kind of method of producing high power capacity 523 type tertiary cathode material | |
| CN105789581B (en) | The production method of the type tertiary cathode material of high power capacity long circulating richness lithium 622 | |
| CN109148838B (en) | Anode material of lithium-ion battery and its preparation method and application | |
| CN104466099B (en) | High-voltage lithium cobaltate based composite cathode material of lithium ion battery and preparation method of high-voltage lithium cobaltate based composite cathode material | |
| CN105355905B (en) | A kind of preparation method of high voltage modification lithium-ion battery anode material nickel ion doped | |
| CN101465420B (en) | Method for preparing nickle lithium manganate material for lithium ion power battery anode | |
| Li et al. | Improve first-cycle efficiency and rate performance of layered-layered Li1. 2Mn0. 6Ni0. 2O2 using oxygen stabilizing dopant | |
| CN103647071B (en) | A kind of High-compaction-denslithium-manganese lithium-manganese oxide for lithium ion battery and preparation method thereof | |
| CN103117380A (en) | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery | |
| CN101964416A (en) | Preparation method of lithium ion battery anode material lithium manganate and automobile lithium ion battery | |
| CN105489881A (en) | Method for improving tap density of ternary nickel-cobalt-manganese cathode material for lithium-ion battery | |
| CN104953107A (en) | Preparation method of lithium titanate cathode material with high tap density | |
| CN106450289A (en) | High-voltage lithium cobalt oxide positive electrode material and preparation method therefor | |
| CN105355906A (en) | Preparing method for spherical LiMn1-x-yNixCoyO2 anode material | |
| CN108493435A (en) | Anode material for lithium-ion batteries Li (Ni0.8Co0.1Mn0.1)1-xYxO2And preparation method | |
| CN103762354A (en) | LiNi0.5Mn1.5O4 material, preparation method thereof as well as lithium ion battery | |
| CN105489856A (en) | Preparation method for zinc oxide-coated lithium nickel manganese cobalt positive electrode material | |
| CN108878826A (en) | A kind of sodium manganate/graphene combination electrode material and its preparation method and application | |
| CN102259933A (en) | Preparation method and application of rice-grain alpha-iron trioxide | |
| CN105322150B (en) | A kind of preparation process of modification lithium-ion battery anode material nickel ion doped | |
| CN101841039A (en) | Cathode material ferric phosphate doped with metallic ions for lithium ion battery and preparation method thereof | |
| CN103094544A (en) | Preparation method of cathode material of nanoscale lithium-ion battery | |
| CN103904322B (en) | A kind of three-dimensional porous nano carbon compound LiMn2O4 spherical anode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CP03 | Change of name, title or address |
Address after: 532399 Xialei Town, Daxin County, Chongzuo City, Guangxi Zhuang Autonomous Region Patentee after: Daxin Manganese Mine Branch of Nanfang Manganese Industry Group Co.,Ltd. Address before: 532315 Daxin Manganese Mine, Xialei Town, Chongzuo City, Guangxi Zhuang Autonomous Region Patentee before: DAXIN MANGANESE MINE BRANCH OF CITIC DAMENG MINING INDUSTRIES Ltd. |
|
| CP03 | Change of name, title or address | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20211029 Address after: 532399 Xialei Town, Daxin County, Chongzuo City, Guangxi Zhuang Autonomous Region Patentee after: Daxin Manganese Mine Branch of Nanfang Manganese Industry Group Co.,Ltd. Patentee after: Nanfang Manganese Industry Group Co.,Ltd. Address before: 532399 Xialei Town, Daxin County, Chongzuo City, Guangxi Zhuang Autonomous Region Patentee before: Daxin Manganese Mine Branch of Nanfang Manganese Industry Group Co.,Ltd. |
|
| TR01 | Transfer of patent right |