CN105355904B - A kind of preparation method of aluminium cladding nickel ion doped - Google Patents
A kind of preparation method of aluminium cladding nickel ion doped Download PDFInfo
- Publication number
- CN105355904B CN105355904B CN201510843921.9A CN201510843921A CN105355904B CN 105355904 B CN105355904 B CN 105355904B CN 201510843921 A CN201510843921 A CN 201510843921A CN 105355904 B CN105355904 B CN 105355904B
- Authority
- CN
- China
- Prior art keywords
- nickel
- sintering
- aluminium
- cladding
- manganese
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 238000005253 cladding Methods 0.000 title claims abstract description 37
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 34
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 239000004411 aluminium Substances 0.000 title claims abstract description 30
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 80
- 238000000034 method Methods 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 47
- 238000002156 mixing Methods 0.000 claims abstract description 27
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 150000002696 manganese Chemical class 0.000 claims abstract description 11
- 150000002815 nickel Chemical class 0.000 claims abstract description 11
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 7
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 7
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 7
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract 2
- 239000011572 manganese Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 33
- 239000002184 metal Substances 0.000 claims description 33
- 239000000203 mixture Substances 0.000 claims description 22
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 18
- 239000002738 chelating agent Substances 0.000 claims description 14
- 239000001301 oxygen Substances 0.000 claims description 14
- 229910052760 oxygen Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 238000001035 drying Methods 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- -1 Polyethylene Polymers 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 6
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910052744 lithium Inorganic materials 0.000 claims description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 5
- 229920002635 polyurethane Polymers 0.000 claims description 5
- 239000004814 polyurethane Substances 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 239000011702 manganese sulphate Substances 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 3
- 229940113116 polyethylene glycol 1000 Drugs 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims 1
- 239000000243 solution Substances 0.000 description 22
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 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
- 239000002253 acid Substances 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- XEUCQOBUZPQUMQ-UHFFFAOYSA-N Glycolone Chemical compound COC1=C(CC=C(C)C)C(=O)NC2=C1C=CC=C2OC XEUCQOBUZPQUMQ-UHFFFAOYSA-N 0.000 description 1
- UWIULCYKVGIOPW-UHFFFAOYSA-N Glycolone Natural products CCOC1=C(CC=CC)C(=O)N(C)c2c(O)cccc12 UWIULCYKVGIOPW-UHFFFAOYSA-N 0.000 description 1
- 229910032387 LiCoO2 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AMDUMQZTBRMNMG-UHFFFAOYSA-N nickel nitric acid Chemical compound [Ni].O[N+]([O-])=O AMDUMQZTBRMNMG-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- H01M4/50—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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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 discloses the preparation methods that a kind of aluminium coats nickel ion doped, manganese salt, nickel salt material are mixed, nickel manganese presoma is prepared by sol-gal process, nickel manganese presoma is mixed with lithium salts using three-dimensional inclined mixing machine, by pre-sintering, high temperature sintering, reselection aluminium hydroxide carries out wet method cladding, most obtains nickel ion doped finished product through low-temperature sintering, air-flow crushing and classification afterwards.The present invention coats nickel ion doped material surface by using aluminium and by special wet method cladding process, is evenly coated, good product consistency, improves the cycle performance and high-temperature behavior of nickel ion doped.
Description
Technical field
The present invention relates to battery material technical field, especially a kind of preparation method of aluminium cladding nickel ion doped.
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, diaphragm, 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.
Current commercialized anode material for lithium-ion batteries mainly has cobalt acid lithium (LiCoO2), LiMn2O4 (LiMn2O4)
With LiFePO4 (LiFePO4)；Cobalt acid lithium is to be now widely used for the positive electrode of small-scale lithium ion cell, but since cobalt has
Poison, resource reserve are limited expensive, and the battery security that assembles as positive electrode of cobalt acid lithium material and thermal stability are not
It is good, it will produce oxygen at high temperature, can not meet the technology requirement of power battery；LiMn2O4 is although cheap, environmentally friendly, peace
Entirely, high rate performance and have a safety feature, but its theoretical capacity is not high, recycle performance, thermal stability and high-temperature behavior compared with
Difference, greatest problem in the application is that cycle performance is bad, and especially under high temperature, Manganic ion and big multiplying power in material are put
The divalent manganesetion formed in particle surface when electric so that the dissolving of material in the electrolytic solution is apparent, finally destroys LiMn2O4
Structure, also reduce the cycle performance of material；The lithium manganate material that can really use on the market at present is all to pass through modification
What measure obtained, on the one hand this modified measures need the synthesis device of high standard, be on the other hand also required to be to reduce material
Reversible capacity be cost, so these materials are to the replacement for being difficult to realize cobalt acid lithium so far；LiFePO4 is in recent years
Cause the Olivine-type Cathode Material in Li-ion Batteries of extensive concern, it has superior security performance and good recycling
Can, there is preferable application prospect, but the tap density of the material is small and voltage platform is relatively low, therefore compare energy after being fabricated to battery
It is low so that it is not suitable for the occasion required applied to high-energy density.
For current technology, the these types of positive electrode of commercialization relative to graphite cathode voltage 4V with
Under, to limit the power of battery, therefore, develop the Ni doping of high voltage, high power capacity, safety and good cycle
LiMn2O4Have 5V grades of LiNi0.5Mn1.5O4, have to the development of high power lithium ion power battery for electric vehicle important
Realistic meaning.
Invention content
The present invention provides the preparation method that a kind of aluminium coats nickel ion doped, nickel ion doped obtained has 5.0V high potentials
Discharge platform can provide higher operating voltage and energy and power density.
To achieve the above object, the technical scheme is that：
A kind of preparation method of aluminium cladding nickel ion doped, it is characterised in that include the following steps：
(1) preparation of manganese salt, nickel salt material：Manganese salt, nickel salt material are pressed into Mn:Ni molar ratios are 3:1, which carries out dispensing, mixes
It closes；
(2) sol-gal process prepares nickel manganese presoma：Mixture obtained by step (1) is added in chelating agent, carbonic acid is used
Hydrogen ammonia adjusts pH 8~10, and pure water is added under stirring, being fabricated to metal Mn+Ni ion concentrations is to sticky in stirring
Settling agent is added to precipitating completely in the solution of 100~150g/l, and filtering, drying precipitate obtains nickel manganese presoma；
(3) three-dimensional inclined mixing：The nickel manganese presoma obtained by step (2) is being situated between with lithium salts using three-dimensional inclined mixing machine
Disperseed under matter, mix 2~4h, obtains intermediate mixture；
(4) it is pre-sintered：Intermediate mixture obtained by step (3) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 500~600 DEG C of sintering temperature, and 4~6h of constant temperature time obtains pre-sintered mass；
(5) high temperature sintering：Pre-sintered mass obtained by step (4) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 800~900 DEG C of sintering temperature, and 9.5~10.5h of constant temperature time obtains high temperature sintering material；
(6) wet method coats aluminium：As wet method cladding process in step (5) obtained by high temperature sintering surface of material coat hydrogen-oxygen
Change aluminium, obtains cladding material；
(7) third time low-temperature sintering：Cladding material obtained by step (6) is washed, press filtration, drying, sintering, sintering
Temperature is 300~400 DEG C, 4~6h of constant temperature time；
(8) it post-processes：The product that step (7) is obtained carries out air-flow crushing, classification and obtains aluminium cladding nickel ion doped
Finished product.
Further, in step (3), the molar ratio of Li is (0.95~1.0) in Mn+Ni and lithium salts in nickel manganese presoma:
1。
Further, in step (1), the manganese salt material is one or more of manganese sulfate, manganese nitrate, manganese chloride；
The nickel salt material is one or more of nickel sulfate, nickel chloride, nickel sulfate；In step (3), the lithium salt material is carbonic acid
Lithium.
Further, the medium that inclined mixing uses in the step (3) is one kind in zirconia ball or polyurethane ball.
Further, in the step (6), the detailed step of wet method cladding process is：It is burnt with the high temperature obtained by step (5)
Knot material is base-material, and using pure water as bottom liquid, at 40~80 DEG C, mixing speed is 80~150r/min, and it is molten will to contain aluminium for temperature control
Liquid, sodium hydroxide solution, ammonium hydroxide cocurrent are added, and pH is 10.5~11.5 for control, and aluminum hydroxide precipitation is generated at 40~80 DEG C and is existed
Base-material surface；Further, it is aluminum sulfate solution or aluminum nitrate solution to contain aluminum solutions；Wherein, metal Mn+Ni in base-material, contain
The mass ratio of metal Al is 1000 in aluminum solutions:(1.5~0.5).
Further, in step (2), the chelating agent is polyethylene glycol-1000, Polyethylene glycol-2000, polyethylene glycol-
One or both of 4000 and polyethylene glycol-1000 0；Further, in step (2), the quality of the chelating agent is gold
Belong to the 80~120% of Mn+Ni mass.
Further, in step (2), the settling agent is hydroxymethyl cellulose, and the quality being added is metal Mn+Ni matter
The 3~5% of amount.
The preparation method of above-described aluminium cladding nickel ion doped, has the advantage that：
(1) nickel manganese presoma stability is good：Nickel manganese presoma is prepared using sol-gel method, and has selected suitable chela
Mixture enhances the stability of nickel manganese presoma.
(2) batch mixing uniformity is more preferable：Using special three-dimensional inclined mixing procedure, make raw material close to molecular level level
It is uniformly mixed.
(3) excellent product performance：By using special wet method cladding process aluminium has been coated in nickel ion doped material surface
Element makes aluminium element be evenly distributed, and good product consistency, clad is close, not easily to fall off, is effectively improved the cycle of nickel ion doped
Performance and high-temperature behavior；In addition, also being post-processed to finished product using improved jet mill grinding equipment, the product produced
Granularity is moderate and is evenly distributed, and tap density is big, it is made to have good processing performance in lithium ion battery production process.
(4) relatively low to raw material and equipment requirement：This method uses succinct technological process, is allowed to be easier to industrialization；
Raw materials and equipment originate from domestic manufacturer, greatly reduce industrialization cost.
(5) product stability is good：This programme is readily produced since control point is few, and production process is easy control, is obtained
Product stability is good.
(6) have the advantages that the less, technically reliable of investment, operating cost are low etc., have good economic benefit, have good
Market popularization value.
Specific implementation mode
Below in conjunction with specific embodiment, the invention will be further described, but protection scope and application range of the present invention are not
It is limited to following embodiment：
One, the preparation of nickel ion doped
Embodiment 1
(1) preparation of manganese salt, nickel salt material：Manganese sulfate, sulfuric acid nickel material are pressed into Mn:Ni molar ratios are 3:1 is matched
Material mixing；
(2) sol-gal process prepares nickel manganese presoma：Chelating agent polyethylene glycol-is added in mixture obtained by step (1)
In 1000, the quality of chelating agent is the 120% of metal Mn+Ni mass, and pH is adjusted 8~10 with ammonium hydrogencarbonate, stirring to sticky,
Pure water is added under stirring, is fabricated to the solution that metal Mn+Ni ion concentrations are 100g/l, addition quality is metal Mn+
The settling agent hydroxymethyl cellulose of the 3% of Ni mass is complete to precipitating, and filtering, drying precipitate obtains nickel manganese presoma；
(3) three-dimensional inclined mixing：Using three-dimensional inclined mixing machine by the nickel manganese presoma and lithium carbonate obtained by step (2)
Disperseed in the case where polyurethane ball is medium, mix 2h, metal (Mn+Ni):Li molar ratios are 0.95:1, obtain intermediate mixing
Object；
(4) it is pre-sintered：Intermediate mixture obtained by step (3) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 520 DEG C of sintering temperature, and constant temperature time 6h obtains pre-sintered mass；
(5) high temperature sintering：Pre-sintered mass obtained by step (4) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 900 DEG C of sintering temperature, and constant temperature time 9.5h obtains high temperature sintering material；
(6) wet method coats aluminium：Using the high temperature sintering material obtained by step (5) as base-material, using pure water as bottom liquid, temperature control
At 40 DEG C, aluminum sulfate solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added for 80r/min stirrings, and pH is 11.0 for control, at 40 DEG C
Aluminum hydroxide precipitation is generated on base-material surface, obtains cladding material；Wherein, metal Al in metal Mn+Ni, aluminum sulfate solution in base-material
Mass ratio be 1000:1.0；
(7) third time low-temperature sintering：Cladding material obtained by step (6) is washed, press filtration, drying, sintering, sintering
Temperature is 400 DEG C, constant temperature time 4h；
(8) it post-processes：The product that step (7) is obtained carries out air-flow crushing, classification and obtains aluminium cladding nickel ion doped
Finished product.
Embodiment 2
(1) preparation of manganese salt, nickel salt material：Manganese nitrate, nitric acid nickel material are pressed into Mn:Ni molar ratios are 3:1 is matched
Material mixing；
(2) sol-gal process prepares nickel manganese presoma：Chelating agent polyethylene glycol-is added in mixture obtained by step (1)
In 4000, the quality of chelating agent is the 100% of metal Mn+Ni mass, and pH is adjusted 8~10 with ammonium hydrogencarbonate, stirring to sticky,
Pure water is added under stirring, is fabricated to the solution that metal Mn+Ni ion concentrations are 120g/l, addition quality is metal Mn+
The settling agent hydroxymethyl cellulose of the 5% of Ni mass is complete to precipitating, and filtering, drying precipitate obtains nickel manganese presoma；
(3) three-dimensional inclined mixing：Using three-dimensional inclined mixing machine by the nickel manganese presoma and lithium carbonate obtained by step (2)
Disperseed in the case where zirconia ball is medium, mix 4h, metal (Mn+Ni):Li molar ratios are 0.97:1, obtain intermediate mixing
Object；
(4) it is pre-sintered：Intermediate mixture obtained by step (3) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 550 DEG C of sintering temperature, and constant temperature time 4h obtains pre-sintered mass；
(5) high temperature sintering：Pre-sintered mass obtained by step (4) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 800 DEG C of sintering temperature, and constant temperature time 10.5h obtains high temperature sintering material；
(6) wet method coats aluminium：Using the high temperature sintering material obtained by step (5) as base-material, using pure water as bottom liquid, temperature control
At 80 DEG C, aluminum nitrate solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added for 100r/min stirrings, and pH is 10.5 for control, 80
DEG C generate aluminum hydroxide precipitation on base-material surface, obtain cladding material；Wherein, metal in metal Mn+Ni, aluminum nitrate solution in base-material
The mass ratio of Al is 1000:1.5.
(7) third time low-temperature sintering：Cladding material obtained by step (6) is washed, press filtration, drying, sintering, sintering
Temperature is 300 DEG C, constant temperature time 6h；
(8) it post-processes：The product that step (7) is obtained carries out air-flow crushing, classification and obtains aluminium cladding nickel ion doped
Finished product.
Embodiment 3
(1) preparation of manganese salt, nickel salt material：Manganese chloride, chlorination nickel material are pressed into Mn:Ni molar ratios are 3:1 is matched
Material mixing；
(2) sol-gal process prepares nickel manganese presoma：Chelating agent polyethylene glycol-is added in mixture obtained by step (1)
2000, the quality of chelating agent is the 80% of metal Mn+Ni mass, and pH is adjusted 8~10 with ammonium hydrogencarbonate, and stirring is stirred to sticky
It mixes and pure water is added under state, be fabricated to the solution that metal Mn+Ni ion concentrations are 150g/l, addition quality is metal Mn+Ni
The settling agent hydroxymethyl cellulose of the 4% of quality is complete to precipitating, and filtering, drying precipitate obtains nickel manganese presoma；
(3) three-dimensional inclined mixing：Using three-dimensional inclined mixing machine by the nickel manganese presoma and lithium carbonate obtained by step (2)
Disperseed in the case where polyurethane ball is medium, mix 3h, metal (Mn+Ni):Li molar ratios are 1:1, obtain intermediate mixture；
(4) it is pre-sintered：Intermediate mixture obtained by step (3) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 590 DEG C of sintering temperature, and constant temperature time 5h obtains pre-sintered mass；
(5) high temperature sintering：Pre-sintered mass obtained by step (4) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 850 DEG C of sintering temperature, and constant temperature time 10h obtains high temperature sintering material；
(6) wet method coats aluminium：Using the high temperature sintering material obtained by step (5) as base-material, using pure water as bottom liquid, temperature control
At 60 DEG C, aluminum nitrate solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added for 150r/min stirrings, and pH is 11.5 for control, 60
DEG C generate aluminum hydroxide precipitation on base-material surface, obtain cladding material.Wherein, metal in metal Mn+Ni, aluminum nitrate solution in base-material
The mass ratio of Al is 1000:0.5.
(7) third time low-temperature sintering：Cladding material obtained by step (6) is washed, press filtration, drying, sintering, sintering
Temperature is 350 DEG C, constant temperature time 5h；
(8) it post-processes：The product that step (7) is obtained carries out air-flow crushing, classification and obtains aluminium cladding nickel ion doped
Finished product.
Embodiment 4
(1) preparation of manganese salt, nickel salt material：Manganese sulfate, sulfuric acid nickel material are pressed into Mn:Ni molar ratios are 3:1 is matched
Material mixing；
(2) sol-gal process prepares nickel manganese presoma：Chelating agent polyethylene glycol-is added in mixture obtained by step (1)
10000, the quality of chelating agent is the 80% of metal Mn+Ni mass, and pH is adjusted 8~10 with ammonium hydrogencarbonate, and stirring is stirred to sticky
It mixes and pure water is added under state, be fabricated to the solution that metal Mn+Ni ion concentrations are 130g/l, addition quality is metal Mn+Ni
The settling agent hydroxymethyl cellulose of the 4% of quality is complete to precipitating, and filtering, drying precipitate obtains nickel manganese presoma；
(3) three-dimensional inclined mixing：Using three-dimensional inclined mixing machine by the nickel manganese presoma and lithium carbonate obtained by step (2)
Disperseed in the case where polyurethane ball is medium, mix 3h, metal (Mn+Ni):Li molar ratios are 0.96:1, obtain intermediate mixing
Object；
(4) it is pre-sintered：Intermediate mixture obtained by step (3) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 600 DEG C of sintering temperature, and constant temperature time 5h obtains pre-sintered mass；
(5) high temperature sintering：Pre-sintered mass obtained by step (4) is packed into saggar, pushed bat kiln is sent into and is sintered, be sintered
Process is continual to be filled with oxygen, 850 DEG C of sintering temperature, and constant temperature time 10h obtains high temperature sintering material；
(6) wet method coats aluminium：Using the high temperature sintering material obtained by step (5) as base-material, using pure water as bottom liquid, temperature control
At 70 DEG C, aluminum sulfate solution, sodium hydroxide solution, ammonium hydroxide cocurrent are added for 120r/min stirrings, and pH is 11.2 for control, 70
DEG C generate aluminum hydroxide precipitation on base-material surface, obtain cladding material；Wherein, metal in metal Mn+Ni, aluminum sulfate solution in base-material
The mass ratio of Al is 1000:1.2.
(7) third time low-temperature sintering：Cladding material obtained by step (6) is washed, press filtration, drying, sintering, sintering
Temperature is 350 DEG C, constant temperature time 5h；
(8) it post-processes：The product that step (7) is obtained carries out air-flow crushing, classification and obtains aluminium cladding nickel ion doped
Finished product.
Two, nickel ion doped performance test made from distinct methods
Claims (5)
1. a kind of preparation method of the oxide cladding nickel ion doped of aluminium, it is characterised in that include the following steps：
(1) preparation of manganese salt, nickel salt material：Manganese salt, nickel salt material are pressed into Mn:Ni molar ratios are 3:1 carries out dispensing mixing；
(2) sol-gal process prepares nickel manganese presoma：Mixture obtained by step (1) is added in chelating agent, ammonium hydrogencarbonate is used
PH is adjusted 8~10, pure water is added under stirring to sticky in stirring, be fabricated to metal Mn+Ni ion concentrations be 100~
Settling agent is added to precipitating completely in the solution of 150g/l, and filtering, drying precipitate obtains nickel manganese presoma；
(3) three-dimensional inclined mixing：Using three-dimensional inclined mixing machine by nickel manganese presoma and the lithium salts obtained by step (2) under medium
Disperseed, mix 2~4h, obtains intermediate mixture；
(4) it is pre-sintered：Intermediate mixture obtained by step (3) is packed into saggar, pushed bat kiln is sent into and is sintered, sintering process
Continual to be filled with oxygen, 500~600 DEG C of sintering temperature, 4~6h of constant temperature time obtains pre-sintered mass；
(5) high temperature sintering：Pre-sintered mass obtained by step (4) is packed into saggar, pushed bat kiln is sent into and is sintered, sintering process
Continual to be filled with oxygen, 800~900 DEG C of sintering temperature, 9.5~10.5h of constant temperature time obtains high temperature sintering material；
(6) oxide of wet method cladding aluminium：As wet method cladding process in step (5) obtained by high temperature sintering surface of material cladding
Aluminium hydroxide obtains cladding material；
(7) third time low-temperature sintering：Cladding material obtained by step (6) is washed, press filtration, drying, sintering, sintering temperature
It is 300~400 DEG C, 4~6h of constant temperature time；
(8) it post-processes：The product that step (7) is obtained carries out the oxide cladding nickel manganese that air-flow crushing, classification obtain aluminium
Sour lithium finished product；
Wherein, in step (2), the chelating agent is polyethylene glycol-1000, Polyethylene glycol-2000, polyethylene glycol-4000 and gathers
One or both of ethylene glycol -10000；The quality of the chelating agent is the 80~120% of metal Mn+Ni mass；
The medium that step (3) the inclined mixing uses is one kind in zirconia ball or polyurethane ball；
The detailed step of step (6) the wet method cladding process is：Using the high temperature sintering material obtained by step (5) as base-material, with
Pure water is bottom liquid, and at 40~80 DEG C, mixing speed is 80~150r/min for temperature control, will contain aluminum solutions, sodium hydroxide solution,
Ammonium hydroxide cocurrent is added, and pH is 10.5~11.5 for control, and aluminum hydroxide precipitation is generated at 40~80 DEG C on base-material surface；It is described to contain aluminium
Solution is aluminum sulfate solution or aluminum nitrate solution；Wherein, metal Mn+Ni and the mass ratio containing metal Al in aluminum solutions are in base-material
1000:(1.5~0.5).
2. the preparation method of the oxide cladding nickel ion doped of aluminium according to claim 1, it is characterised in that：
In step (3), the molar ratio of Li is (0.95~1.0) in Mn+Ni and lithium salts in nickel manganese presoma:1.
3. the preparation method of the oxide cladding nickel ion doped of aluminium according to claim 1, it is characterised in that：
In step (1), the manganese salt material is one or more of manganese sulfate, manganese nitrate, manganese chloride；The nickel salt material is
One or more of nickel sulfate, nickel chloride.
4. the preparation method of the oxide cladding nickel ion doped of aluminium according to claim 1, it is characterised in that：
In step (3), the lithium salt material is lithium carbonate.
5. the preparation method of the oxide cladding nickel ion doped of aluminium according to claim 1, it is characterised in that：
In step (2), the settling agent is hydroxymethyl cellulose, and the quality being added is the 3~5% of metal Mn+Ni mass.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510843921.9A CN105355904B (en) | 2015-11-26 | 2015-11-26 | A kind of preparation method of aluminium cladding nickel ion doped |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510843921.9A CN105355904B (en) | 2015-11-26 | 2015-11-26 | A kind of preparation method of aluminium cladding nickel ion doped |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105355904A CN105355904A (en) | 2016-02-24 |
| CN105355904B true CN105355904B (en) | 2018-11-13 |
Family
ID=55331823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510843921.9A Active CN105355904B (en) | 2015-11-26 | 2015-11-26 | A kind of preparation method of aluminium cladding nickel ion doped |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105355904B (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102005563A (en) * | 2010-10-19 | 2011-04-06 | 合肥国轩高科动力能源有限公司 | Lithium ion battery high-voltage anode material preparation and surface coating method |
| CN102195034A (en) * | 2010-03-09 | 2011-09-21 | 深圳市比克电池有限公司 | Preparation method of anode material for lithium ion batteries and prepared battery |
| CN102633300A (en) * | 2011-12-07 | 2012-08-15 | 天津市贝特瑞新能源材料有限责任公司 | Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof |
| CN103117380A (en) * | 2013-01-31 | 2013-05-22 | 中信大锰矿业有限责任公司 | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery |
| CN103441252A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery |
| CN103943844A (en) * | 2014-04-04 | 2014-07-23 | 西安交通大学 | Cobalt-free lithium-rich manganese-based cathode material as well as preparation method and application thereof |
| CN104409730A (en) * | 2014-11-11 | 2015-03-11 | 广西民族师范学院 | Production method capable of reducing energy consumption of lithium iron phosphate preparation through wet method mechanical activation-high temperature solid state |
| CN104766970A (en) * | 2015-04-28 | 2015-07-08 | 湖南瑞翔新材料股份有限公司 | Synthetic method for lithium nickel manganese oxygen covered with lithium titanate |
| CN105047900A (en) * | 2015-07-14 | 2015-11-11 | 北京圣比和科技有限公司 | Preparation method and equipment of nano-flake nickel lithium manganate material |
-
2015
- 2015-11-26 CN CN201510843921.9A patent/CN105355904B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102195034A (en) * | 2010-03-09 | 2011-09-21 | 深圳市比克电池有限公司 | Preparation method of anode material for lithium ion batteries and prepared battery |
| CN102005563A (en) * | 2010-10-19 | 2011-04-06 | 合肥国轩高科动力能源有限公司 | Lithium ion battery high-voltage anode material preparation and surface coating method |
| CN102633300A (en) * | 2011-12-07 | 2012-08-15 | 天津市贝特瑞新能源材料有限责任公司 | Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof |
| CN103117380A (en) * | 2013-01-31 | 2013-05-22 | 中信大锰矿业有限责任公司 | Preparation method of manganese Li-NiCoMn ternary material for lithium ion battery |
| CN103441252A (en) * | 2013-08-12 | 2013-12-11 | 天津巴莫科技股份有限公司 | Method for preparing lithium-enriched manganese-based anode material of nano-oxide-coated lithium ion battery |
| CN103943844A (en) * | 2014-04-04 | 2014-07-23 | 西安交通大学 | Cobalt-free lithium-rich manganese-based cathode material as well as preparation method and application thereof |
| CN104409730A (en) * | 2014-11-11 | 2015-03-11 | 广西民族师范学院 | Production method capable of reducing energy consumption of lithium iron phosphate preparation through wet method mechanical activation-high temperature solid state |
| CN104766970A (en) * | 2015-04-28 | 2015-07-08 | 湖南瑞翔新材料股份有限公司 | Synthetic method for lithium nickel manganese oxygen covered with lithium titanate |
| CN105047900A (en) * | 2015-07-14 | 2015-11-11 | 北京圣比和科技有限公司 | Preparation method and equipment of nano-flake nickel lithium manganate material |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105355904A (en) | 2016-02-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105355905B (en) | A kind of preparation method of high voltage modification lithium-ion battery anode material nickel ion doped | |
| CN105280912B (en) | A kind of preparation method of oxide coated lithium ion battery positive electrode nickel ion doped | |
| CN103490051B (en) | One is applicable to high-tension multielement cathode lithium electric material and preparation method thereof | |
| CN102983326B (en) | Spherical lithium-nickel-cobalt composite oxide positive electrode material preparation method | |
| CN104393285B (en) | Nickel-cobalt-aluminum ternary positive electrode material and its preparation method | |
| CN109273701A (en) | High nickel core-shell structure gradient nickel-cobalt-manganternary ternary anode material and preparation method thereof | |
| CN105810934B (en) | A kind of stabilizing lithium rich layered oxide material crystalline domain structure method | |
| CN107078293A (en) | Positive active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery | |
| CN109256533A (en) | Ni-base cathode material for rechargable lithium ion battery | |
| CN106784790B (en) | A kind of preparation method of nickle cobalt lithium manganate tertiary cathode material | |
| CN105576233A (en) | Nickel base trinary positive electrode material and preparation method thereof | |
| CN103928660B (en) | A kind of preparation method of the polynary positive pole material with multilevel hierarchy | |
| CN103794782B (en) | A kind of lithium-rich manganese base material, its preparation method and lithium ion battery | |
| CN105322150B (en) | A kind of preparation process of modification lithium-ion battery anode material nickel ion doped | |
| CN109643798A (en) | Positive active material for lithium secondary battery, positive electrode for lithium secondary battery and lithium secondary battery | |
| CN106207158B (en) | The preparation method of rich lithium manganate cathode material for lithium | |
| CN105322151B (en) | A kind of preparation method of modification lithium-ion battery anode material nickel ion doped | |
| CN103280570A (en) | Preparation method of micron-order single-crystal nickel lithium manganate anode material | |
| CN103441238A (en) | Mg-doped Li-rich anode material and preparation method for same | |
| CN104466139A (en) | Preparation method of polyaniline-clad germanium-doped lithium manganate composite cathode material | |
| CN103956456A (en) | Halogen anion doped lithium-rich positive electrode material as well as preparation method and application of positive electrode material | |
| CN103413935A (en) | Mo-doped lithium-rich positive electrode material and preparation method thereof | |
| CN107204424B (en) | Preparation method of lithium-rich manganese-based layered lithium battery positive electrode material | |
| Hou et al. | A novel double-shelled LiNi0. 5Co0. 2Mn0. 3O2 cathode material for Li-ion batteries | |
| CN105655572A (en) | Spherical lithium nickel manganese positive electrode material preparation method |
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 |