CN105470497B - A kind of preparation method of fluorine-ion-doped nickel ion doped - Google Patents
A kind of preparation method of fluorine-ion-doped nickel ion doped Download PDFInfo
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- CN105470497B CN105470497B CN201510844061.0A CN201510844061A CN105470497B CN 105470497 B CN105470497 B CN 105470497B CN 201510844061 A CN201510844061 A CN 201510844061A CN 105470497 B CN105470497 B CN 105470497B
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- fluorine
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910001453 nickel ion Inorganic materials 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 66
- 238000005245 sintering Methods 0.000 claims abstract description 48
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 238000000034 method Methods 0.000 claims abstract description 29
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 26
- 150000001450 anions Chemical class 0.000 claims abstract description 14
- 150000002696 manganese Chemical class 0.000 claims abstract description 12
- 150000002815 nickel Chemical class 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 8
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 8
- 238000009766 low-temperature sintering Methods 0.000 claims abstract description 7
- 239000011572 manganese Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 28
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 19
- 239000002738 chelating agent Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 229910052744 lithium Inorganic materials 0.000 claims description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 11
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- -1 Polyethylene Polymers 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 239000004698 Polyethylene Substances 0.000 claims description 7
- 229920000573 polyethylene Polymers 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229920003063 hydroxymethyl cellulose Polymers 0.000 claims description 6
- 229940031574 hydroxymethyl cellulose Drugs 0.000 claims description 6
- 238000010348 incorporation Methods 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
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 5
- 239000001099 ammonium carbonate Substances 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229940099596 manganese sulfate Drugs 0.000 claims description 4
- 235000007079 manganese sulphate Nutrition 0.000 claims description 4
- 239000011702 manganese sulphate Substances 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
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 claims description 4
- 229940113116 polyethylene glycol 1000 Drugs 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
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 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
- 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 claims 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 229910052748 manganese Inorganic materials 0.000 claims 1
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims 1
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 11
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 9
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000009792 diffusion process Methods 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 9
- 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
- 239000000243 solution Substances 0.000 description 5
- 239000002253 acid Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 229910052493 LiFePO4 Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000000227 grinding Methods 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
- 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
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-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
- 239000000470 constituent Substances 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 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
- 230000001590 oxidative effect Effects 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
- 238000012805 post-processing Methods 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
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
- 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
- H01M4/52—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
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
-
- 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
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of preparation methods of fluorine-ion-doped 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, then adulterates F‑It is mixed, most obtains nickel ion doped finished product through low-temperature sintering, air-flow crushing and classification afterwards.The present invention passes through Doped anions F‑Battery material nickel ion doped is modified, it is small on the material crystal structure variation influence after doping vario-property, and so that the diffusion velocity of lithium ion in modified material is accelerated, conductivity raising, effectively improve the high-temperature behavior and cycle performance of nickel ion doped.
Description
Technical field
The present invention relates to battery material technical field, especially a kind of preparation method of fluorine-ion-doped 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 a kind of preparation method of fluorine-ion-doped nickel ion doped, nickel ion doped obtained has 5.0V high
Current potential 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 fluorine-ion-doped nickel ion doped, includes 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) doping mixing：Using three-dimensional inclined mixing machine by high temperature sintering material and the anion F obtained by step (5)-
Disperseed under medium, mixed, incorporation time is 3~4h, obtains doping material；
(7) third time low-temperature sintering：By the doping material sintering obtained by step (6), sintering temperature is 300~400 DEG C, permanent
Warm 4~6h of time；
(8) it post-processes：The product that step (7) is obtained is subjected to air-flow crushing, classification obtains fluorine-ion-doped nickel manganese
Sour lithium 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.
Wherein, it is to the quality requirement of lithium carbonate：Based on mass concentration, Li2CO3>=99.5%, Li >=18.7%, Na≤
200ppm、K≤200ppm、Ca≤100ppm、Mg≤100ppm、Fe≤50ppm、Cl-≤ 0.15%, and tap density >=
2.1g/cm3, apparent density >=1.2g/cm3。
Preferably, in step (6), high temperature sintering material and anion F-Mixing, wherein metal Mn+Ni and F-Mass ratio
It is 1000:(1.5~1).
Further, the medium that inclined mixing uses in the step (3) and step (6) is zirconia ball or polyurethane ball
In one kind.
In the step (3), the medium that the mixing of three inclineds uses is zirconia ball or polyurethane ball.
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 the 80~120% of metal 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.
Further, in step (10), product carries out air-flow crushing, classification using jet mill grinding equipment.
The preparation method of above-described fluorine-ion-doped nickel ion doped, has the advantage that：
(1) 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.
(2) excellent product performance：Using three-dimensional inclined mixing machine, pass through Doped anions F-To battery material nickel ion doped
It is modified, F-It is added in nickel ion doped, small on the material crystal structure variation influence after doping vario-property, lithium ion is in lattice
The binding force that is subject to reduces in, to make the migration rate of lithium ion in modified material accelerate, conductivity raising, effectively changes
It has been apt to the high-temperature behavior and cycle performance of nickel ion doped；In addition, also being carried out to finished product using improved jet mill grinding equipment
Post-processing, the product granularity produced is moderate and is evenly distributed, and tap density is big, it is made to have in lithium ion battery production process
There is good processing performance.
(3) 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.
(4) product stability is more preferable：This programme is readily produced since control point is few, and properties of product stability is good.
(5) 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, 500 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) doping mixing：Using three-dimensional inclined mixing machine by high temperature sintering material and the anion F obtained by step (5)-
Disperseed under medium polyurethane ball, mixed, wherein anion F-The preferred LiF in source, F in LiF-Quality be metal Mn+
The 0.1% of Ni mass, incorporation time 3h obtain doping material；
(7) third time low-temperature sintering：By the doping material sintering obtained by step (6), sintering temperature is 400 DEG C, when constant temperature
Between 4.5h；
(8) it post-processes：The product that step (7) is obtained is subjected to air-flow crushing, classification obtains fluorine-ion-doped nickel manganese
Sour lithium 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 0.98:1；
(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 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) doping mixing：Using three-dimensional inclined mixing machine by high temperature sintering material and the anion F obtained by step (5)-
Disperseed under medium oxidizing zirconium ball, mixed, wherein anion F-The preferred LiF in source, F in LiF-Quality be metal Mn+
The 0.12% of Ni mass, incorporation time 3.5h obtain doping material；
(7) third time low-temperature sintering：By the doping material sintering obtained by step (6), sintering temperature is 300 DEG C, when constant temperature
Between 5.5h；
(8) it post-processes：The product that step (7) is obtained is subjected to air-flow crushing, classification obtains fluorine-ion-doped nickel manganese
Sour lithium 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, 550 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) doping mixing：Using three-dimensional inclined mixing machine by high temperature sintering material and the anion F obtained by step (5)-
Disperseed under medium polyurethane ball, mixed, wherein anion F-The preferred LiF in source, F in LiF-Quality be metal Mn+
The 0.13% of Ni mass, incorporation time 3h obtain doping material；
(7) third time low-temperature sintering：By the doping material sintering obtained by step (6), sintering temperature is 350 DEG C, when constant temperature
Between 5h；
(8) it post-processes：The product that step (7) is obtained is subjected to air-flow crushing, classification obtains fluorine-ion-doped nickel manganese
Sour lithium 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 140g/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 0.99:1, 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, 560 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, 860 DEG C of sintering temperature, and constant temperature time 10h obtains high temperature sintering material；
(6) doping mixing：The high temperature sintering material obtained by step (5) is existed with anion F- using three-dimensional inclined mixing machine
Disperseed under medium polyurethane ball, mixed, wherein F in the preferred LiF in source of anion F-, LiF-Quality be metal Mn+
The 0.15% of Ni mass, incorporation time 4h obtain doping material；
(7) third time low-temperature sintering：By the doping material sintering obtained by step (6), sintering temperature is 360 DEG C, when constant temperature
Between 5h；
(8) it post-processes：The product that step (7) is obtained is subjected to air-flow crushing, classification obtains fluorine-ion-doped nickel manganese
Sour lithium finished product.
In above-described embodiment 1~4, to improve the product quality of nickel ion doped, raw material should select Fe, Na, Ca, S etc. miscellaneous
The lower manganese salt of will constituent content, nickel salt and lithium salts, wherein the quality requirement to lithium carbonate is：Li2CO3>=99.5%, Li >=
18.7%, Na≤200ppm, K≤200ppm, Ca≤100ppm, Mg≤100ppm, Fe≤50ppm, and tap density >=2.1g/
cm3, apparent density >=1.2g/cm3。
Two, nickel ion doped performance test made from distinct methods
Claims (7)
1. a kind of preparation method of fluorine-ion-doped 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 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) doping mixing：Using three-dimensional inclined mixing machine by high temperature sintering material and the anion F obtained by step (5)-In medium
Under disperseed, mixed, incorporation time is 3~4h, obtains doping material；
(7) third time low-temperature sintering：By the doping material sintering obtained by step (6), sintering temperature is 300~400 DEG C, when constant temperature
Between 4.5~5.5h；
(8) it post-processes：The product that step (7) is obtained is subjected to air-flow crushing, classification obtains fluorine-ion-doped nickel ion doped
Finished product；
In step (3), the lithium salt material is lithium carbonate；The quality requirement of lithium carbonate is：By mass percentage, Li2CO3≥
99.5%, Li >=18.7%, Na≤200ppm, K≤200ppm, Ca≤100ppm, Mg≤100ppm, Fe≤50ppm, Cl-≤
0.15%, and tap density >=2.1g/cm3, apparent density >=1.2g/cm3；In step (6), high temperature sintering material and anion
F-Mixing, wherein metal Mn+Ni and F-Mass ratio be 1000：(1.5~1).
2. the preparation method of fluorine-ion-doped nickel ion doped according to claim 1, it is characterised in that：In step (3), nickel
The molar ratio of Li is (0.95~1.0) in Mn+Ni and lithium salts in manganese presoma：1.
3. the preparation method of fluorine-ion-doped nickel ion doped according to claim 1, it is characterised in that：In step (1), institute
It is one or more of manganese sulfate, manganese nitrate, manganese chloride to state manganese salt material；The nickel salt material is nickel sulfate, nickel chloride, sulphur
One or more of sour nickel.
4. the preparation method of fluorine-ion-doped nickel ion doped according to claim 1, it is characterised in that：The step (3)
The medium used is mixed as one kind in zirconia ball or polyurethane ball with inclined in step (6).
5. the preparation method of fluorine-ion-doped nickel ion doped according to claim 1, it is characterised in that：In step (2), institute
State chelating agent be polyethylene glycol-1000, Polyethylene glycol-2000, polyethylene glycol-4000 and one kind in polyethylene glycol-1000 0 or
Two kinds.
6. the preparation method of fluorine-ion-doped nickel ion doped according to claim 1, it is characterised in that：In step (2), institute
The quality for stating chelating agent is the 80~120% of metal Mn+Ni mass.
7. the preparation method of fluorine-ion-doped nickel ion doped according to claim 1, it is characterised in that：In step (2), institute
It is hydroxymethyl cellulose to state settling agent, and the quality being added is the 3~5% of metal Mn+Ni mass.
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