CN105355904A - Preparing method for aluminum-coated lithium nickel manganese oxide - Google Patents
Preparing method for aluminum-coated lithium nickel manganese oxide Download PDFInfo
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- CN105355904A CN105355904A CN201510843921.9A CN201510843921A CN105355904A CN 105355904 A CN105355904 A CN 105355904A CN 201510843921 A CN201510843921 A CN 201510843921A CN 105355904 A CN105355904 A CN 105355904A
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- ion doped
- aluminum
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- 238000000034 method Methods 0.000 title claims abstract description 42
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 38
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 38
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title abstract 5
- 239000000463 material Substances 0.000 claims abstract description 76
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002156 mixing Methods 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 9
- 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
- 239000011248 coating agent Substances 0.000 claims abstract description 6
- 238000000576 coating method Methods 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 63
- 238000005245 sintering Methods 0.000 claims description 56
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 229910001453 nickel ion Inorganic materials 0.000 claims description 26
- 239000004411 aluminium Substances 0.000 claims description 23
- 238000002360 preparation method Methods 0.000 claims description 22
- 239000000203 mixture Substances 0.000 claims description 19
- 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 15
- 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
- 239000011572 manganese Substances 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 238000012958 reprocessing Methods 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
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 6
- 239000008118 PEG 6000 Substances 0.000 claims description 6
- 229920002584 Polyethylene Glycol 6000 Polymers 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
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 6
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 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
- 238000005253 cladding Methods 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
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- -1 Polyethylene Polymers 0.000 claims description 3
- 239000004698 Polyethylene Substances 0.000 claims description 3
- 229920001030 Polyethylene Glycol 4000 Polymers 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- 229920000573 polyethylene Polymers 0.000 claims description 3
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000010298 pulverizing process Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 229910001416 lithium ion Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 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
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- 229910015645 LiMn Inorganic materials 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910012820 LiCoO Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000011247 coating layer 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
- 238000007599 discharging Methods 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
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- MMIPFLVOWGHZQD-UHFFFAOYSA-N manganese(3+) Chemical compound [Mn+3] MMIPFLVOWGHZQD-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000002441 reversible effect Effects 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 a preparing method for aluminum-coated lithium nickel manganese oxide. Manganese salt and nickel salt materials are mixed and prepared into a nickel manganese precursor through a sol-gel method, the nickel manganese precursor and lithium salt are mixed through a three-dimensional inclined mixing machine, presintered and sintered at high temperature, then aluminum hydroxide is selected for carrying out wet method coating, and finally low-temperature sintering, airflow pulverizing and grading are carried out to obtain a finished lithium nickel manganese oxide product. Aluminum is adopted for coating the surface of a lithium nickel manganese oxide material by means of a special wet method coating technology, coating is uniform, product uniformity is good, and cycle performance and high-temperature performance of lithium nickel manganese oxide are improved.
Description
Technical field
The present invention relates to battery material technical field, particularly the preparation method of the coated nickel ion doped of a kind of aluminium.
Background technology
Lithium-ion-power cell is the most potential on-vehicle battery of generally acknowledging both at home and abroad at present, primarily of part compositions such as positive electrode, negative material, barrier film, electrolyte; Wherein, positive electrode is the important component part of lithium ion battery, is also the key factor determining performance of lithium ion battery; Therefore, from the viewpoint of resource, environmental protection and security performance, the ideal electrode active material finding lithium ion battery is still an international energy material supplier author primary difficult problem to be solved.
Business-like anode material for lithium-ion batteries mainly contains cobalt acid lithium (LiCoO at present
2), LiMn2O4 (LiMn
2o
4) and LiFePO4 (LiFePO
4); Cobalt acid lithium is the positive electrode being widely used in small-scale lithium ion cell at present, but because cobalt is poisonous, resource reserve is limited expensive, and the battery security assembled as positive electrode of cobalt acid lithium material and thermal stability bad, at high temperature can produce oxygen, can not meet the technical requirement of electrokinetic cell; Although LiMn2O4 is cheap, environmental protection, safety, high rate performance and security performance good, but its theoretical capacity is not high, recycle performance, thermal stability and high-temperature behavior poor, greatest problem is in the application that cycle performance is bad, particularly under high temperature, at the divalent manganesetion that particle surface is formed when the Manganic ion in material and large multiplying power discharging, make material dissolving in the electrolytic solution obvious, finally destroy the structure of LiMn2O4, also reduce the cycle performance of material; The lithium manganate material that commercially really can use at present is all obtained by modified measures, this modified measures needs the synthesis device of high standard on the one hand, also need to be reduce the reversible capacity of material for cost on the other hand, so these materials are to being difficult to realize substituting of cobalt acid lithium so far; LiFePO4 is the Olivine-type Cathode Material in Li-ion Batteries causing extensive concern in recent years, it has superior security performance and good recycles performance, there is good application prospect, but the tap density of this material is little and voltage platform is lower, therefore specific energy is low after being made into battery, it is made to be not suitable for being applied to the occasion of high-energy-density requirement.
With regard to current technology, this several positive electrode of commercialization all at below 4V, thus limits the power of battery relative to the voltage of graphite cathode, therefore, and the LiMn of the Ni doping of exploitation high voltage, high power capacity, safety and good cycle
2o
4there is 5V level LiNi
0.5mn
1.5o
4, the development of high power lithium ion power battery used for electric vehicle is had important practical significance.
Summary of the invention
The invention provides the preparation method of the coated nickel ion doped of a kind of aluminium, obtained nickel ion doped has 5.0V high potential discharge platform, can provide higher operating voltage and energy and power density.
For achieving the above object, technical scheme of the present invention is:
A preparation method for the coated nickel ion doped of aluminium, is characterized in that comprising the following steps:
(1) manganese salt, nickel salt material preparation: by manganese salt, nickel salt material by Mn:Ni mol ratio be 3:1 carry out batching mixing;
(2) sol-gal process prepares nickel manganese presoma: add in chelating agent by the mixture of step (1) gained, regulate pH 8 ~ 10 with ammonium hydrogencarbonate, be stirred to thickness, pure water is added under stirring, be made into the solution that metal M n+Ni ion concentration is 100 ~ 150g/l, add settling agent to precipitating completely, filtering, drying precipitate, obtains nickel manganese presoma;
(3) three-dimensional inclined mixing: adopt three-dimensional inclined mixer the nickel manganese presoma of step (2) gained and lithium salts to be carried out disperseing, mixing 2 ~ 4h under medium, obtain intermediate mixture;
(4) presintering: the intermediate mixture of step (3) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 500 ~ 600 DEG C, and constant temperature time 4 ~ 6h, obtains pre-sintered mass;
(5) high temperature sintering: the pre-sintered mass of step (4) gained is loaded saggar, send into pushed bat kiln to sinter, sintering process is continual is filled with oxygen, sintering temperature 800 ~ 900 DEG C, constant temperature time 9.5 ~ 10.5h, obtains high temperature sintering material;
(6) wet method metallized aluminum: by the high temperature sintering material Surface coating aluminium hydroxide of wet method cladding process in step (5) gained, obtain coated material;
(7) third time low-temperature sintering: the coated material of step (6) gained is carried out wash, press filtration, oven dry, sintering, sintering temperature is 300 ~ 400 DEG C, constant temperature time 4 ~ 6h;
(8) reprocessing: the product that step (7) obtains is carried out air-flow crushing, classification and namely obtain the coated nickel ion doped finished product of aluminium.
Further, in step (3), in nickel manganese presoma, in Mn+Ni and lithium salts, the mol ratio of Li is (0.95 ~ 1.0): 1.
Further, in step (1), described manganese salt material is one or more in manganese sulfate, manganese nitrate, manganese chloride; Described nickel salt material is one or more in nickelous sulfate, nickel chloride, nickelous sulfate; In step (3), described lithium salt material is lithium carbonate.
Further, the medium that inclined mixing adopts in described step (3) is the one in zirconia ball or polyurethane ball.
Further, in described step (6), the detailed step of wet method cladding process is: with the high temperature sintering material of step (5) gained for base-material, take pure water as end liquid, temperature controls at 40 ~ 80 DEG C, and mixing speed is 80 ~ 150r/min, will add containing aluminum solutions, sodium hydroxide solution, ammoniacal liquor stream, control pH, 10.5 ~ 11.5, produces aluminum hydroxide precipitation on base-material surface at 40 ~ 80 DEG C; Further, be aluminum sulfate solution or aluminum nitrate solution containing aluminum solutions; Wherein, metal M n+Ni in base-material, be 1000:(1.5 ~ 0.5 containing the mass ratio of metal A l in aluminum solutions).
Further, in step (2), described chelating agent is one or both in PEG-6000, Polyethylene glycol-2000, PEG-4000 and PEG-6000 0; Further, in step (2), the quality of described chelating agent is 80 ~ 120% of metal M n+Ni quality.
Further, in step (2), described settling agent is CMC, and its quality added is 3 ~ 5% of metal M n+Ni quality.
The preparation method of the coated nickel ion doped of above-described aluminium, has following advantage:
(1) nickel manganese presoma good stability: adopt sol-gel process to prepare nickel manganese presoma, and selected suitable chelating agent, enhance the stability of nickel manganese presoma.
(2) batch mixing uniformity is better: adopt special three-dimensional inclined mixing procedure, raw material are mixed close to molecular level level.
(3) excellent product performance: by adopting special wet method cladding process at the coated aluminium element of nickel ion doped material surface, aluminium element is evenly distributed, good product consistency, coating layer is tight, difficult drop-off, effectively improves cycle performance and the high-temperature behavior of nickel ion doped; In addition, also adopt the jet mill grinding equipment of improvement to carry out reprocessing to finished product, the product granularity produced is moderate and be evenly distributed, and tap density is large, makes it in lithium ion battery production process, have good processing characteristics.
(4) to raw material and equipment requirement lower: this method adopts succinct technological process, makes it to be easier to industrialization; Raw materials and equipment all originate from domestic manufacturer, greatly reduce industrialization cost.
(5) product stability is good: this programme is few due to control point, is easy to produce, and production process is easily control, and the product stability obtained is good.
(6) there is the advantages such as investment is less, technically reliable, operating cost are low, there is good economic benefit, there is good market popularization value.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described, but protection scope of the present invention and range of application are not limited to following examples:
One, the preparation of nickel ion doped
Embodiment 1
(1) manganese salt, nickel salt material preparation: by manganese sulfate, nickelous sulfate material by Mn:Ni mol ratio be 3:1 carry out batching mixing;
(2) sol-gal process prepares nickel manganese presoma: add in chelating agent PEG-6000 by the mixture of step (1) gained, the quality of chelating agent is 120% of metal M n+Ni quality, regulate pH 8 ~ 10 with ammonium hydrogencarbonate, be stirred to thickness, pure water is added under stirring, be made into the solution that metal M n+Ni ion concentration is 100g/l, adding quality is that the settling agent CMC of 3% of metal M n+Ni quality is to precipitating completely, filter, drying precipitate, obtains nickel manganese presoma;
(3) three-dimensional inclined mixing: adopt three-dimensional inclined mixer the nickel manganese presoma of step (2) gained and lithium carbonate to be carried out disperseing, mixing 2h under polyurethane ball is medium, metal (Mn+Ni): Li mol ratio is 0.95:1, obtains intermediate mixture;
(4) presintering: the intermediate mixture of step (3) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 520 DEG C, and constant temperature time 6h, obtains pre-sintered mass;
(5) high temperature sintering: the pre-sintered mass of step (4) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 900 DEG C, and constant temperature time 9.5h, obtains high temperature sintering material;
(6) wet method metallized aluminum: with the high temperature sintering material of step (5) gained for base-material, take pure water as end liquid, temperature controls at 40 DEG C, 80r/min stirs, aluminum sulfate solution, sodium hydroxide solution, ammoniacal liquor stream are added, control pH, 11.0, produces aluminum hydroxide precipitation on base-material surface at 40 DEG C, obtains coated material; Wherein, in base-material, in metal M n+Ni, aluminum sulfate solution, the mass ratio of metal A l is 1000:1.0;
(7) third time low-temperature sintering: the coated material of step (6) gained is carried out wash, press filtration, oven dry, sintering, sintering temperature is 400 DEG C, constant temperature time 4h;
(8) reprocessing: the product that step (7) obtains is carried out air-flow crushing, classification and namely obtain the coated nickel ion doped finished product of aluminium.
Embodiment 2
(1) manganese salt, nickel salt material preparation: by manganese nitrate, nickel nitrate material by Mn:Ni mol ratio be 3:1 carry out batching mixing;
(2) sol-gal process prepares nickel manganese presoma: add in chelating agent PEG-4000 by the mixture of step (1) gained, the quality of chelating agent is 100% of metal M n+Ni quality, regulate pH 8 ~ 10 with ammonium hydrogencarbonate, be stirred to thickness, pure water is added under stirring, be made into the solution that metal M n+Ni ion concentration is 120g/l, adding quality is that the settling agent CMC of 5% of metal M n+Ni quality is to precipitating completely, filter, drying precipitate, obtains nickel manganese presoma;
(3) three-dimensional inclined mixing: adopt three-dimensional inclined mixer the nickel manganese presoma of step (2) gained and lithium carbonate to be carried out disperseing, mixing 4h under zirconia ball is medium, metal (Mn+Ni): Li mol ratio is 0.97:1, obtains intermediate mixture;
(4) presintering: the intermediate mixture of step (3) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 550 DEG C, and constant temperature time 4h, obtains pre-sintered mass;
(5) high temperature sintering: the pre-sintered mass of step (4) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 800 DEG C, and constant temperature time 10.5h, obtains high temperature sintering material;
(6) wet method metallized aluminum: with the high temperature sintering material of step (5) gained for base-material, take pure water as end liquid, temperature controls at 80 DEG C, 100r/min stirs, aluminum nitrate solution, sodium hydroxide solution, ammoniacal liquor stream are added, control pH, 10.5, produces aluminum hydroxide precipitation on base-material surface at 80 DEG C, obtains coated material; Wherein, in base-material, in metal M n+Ni, aluminum nitrate solution, the mass ratio of metal A l is 1000:1.5.
(7) third time low-temperature sintering: the coated material of step (6) gained is carried out wash, press filtration, oven dry, sintering, sintering temperature is 300 DEG C, constant temperature time 6h;
(8) reprocessing: the product that step (7) obtains is carried out air-flow crushing, classification and namely obtain the coated nickel ion doped finished product of aluminium.
Embodiment 3
(1) manganese salt, nickel salt material preparation: by manganese chloride, nickel chloride material by Mn:Ni mol ratio be 3:1 carry out batching mixing;
(2) sol-gal process prepares nickel manganese presoma: the mixture of step (1) gained is added chelating agent Polyethylene glycol-2000, the quality of chelating agent is 80% of metal M n+Ni quality, regulate pH 8 ~ 10 with ammonium hydrogencarbonate, be stirred to thickness, pure water is added under stirring, be made into the solution that metal M n+Ni ion concentration is 150g/l, adding quality is that the settling agent CMC of 4% of metal M n+Ni quality is to precipitating completely, filter, drying precipitate, obtains nickel manganese presoma;
(3) three-dimensional inclined mixing: adopt three-dimensional inclined mixer the nickel manganese presoma of step (2) gained and lithium carbonate to be carried out disperseing, mixing 3h under polyurethane ball is medium, metal (Mn+Ni): Li mol ratio is 1:1, obtains intermediate mixture;
(4) presintering: the intermediate mixture of step (3) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 590 DEG C, and constant temperature time 5h, obtains pre-sintered mass;
(5) high temperature sintering: the pre-sintered mass of step (4) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 850 DEG C, and constant temperature time 10h, obtains high temperature sintering material;
(6) wet method metallized aluminum: with the high temperature sintering material of step (5) gained for base-material, take pure water as end liquid, temperature controls at 60 DEG C, 150r/min stirs, aluminum nitrate solution, sodium hydroxide solution, ammoniacal liquor stream are added, control pH, 11.5, produces aluminum hydroxide precipitation on base-material surface at 60 DEG C, obtains coated material.Wherein, in base-material, in metal M n+Ni, aluminum nitrate solution, the mass ratio of metal A l is 1000:0.5.
(7) third time low-temperature sintering: the coated material of step (6) gained is carried out wash, press filtration, oven dry, sintering, sintering temperature is 350 DEG C, constant temperature time 5h;
(8) reprocessing: the product that step (7) obtains is carried out air-flow crushing, classification and namely obtain the coated nickel ion doped finished product of aluminium.
Embodiment 4
(1) manganese salt, nickel salt material preparation: by manganese sulfate, nickelous sulfate material by Mn:Ni mol ratio be 3:1 carry out batching mixing;
(2) sol-gal process prepares nickel manganese presoma: the mixture of step (1) gained is added chelating agent PEG-6000 0, the quality of chelating agent is 80% of metal M n+Ni quality, regulate pH 8 ~ 10 with ammonium hydrogencarbonate, be stirred to thickness, pure water is added under stirring, be made into the solution that metal M n+Ni ion concentration is 130g/l, adding quality is that the settling agent CMC of 4% of metal M n+Ni quality is to precipitating completely, filter, drying precipitate, obtains nickel manganese presoma;
(3) three-dimensional inclined mixing: adopt three-dimensional inclined mixer the nickel manganese presoma of step (2) gained and lithium carbonate to be carried out disperseing, mixing 3h under polyurethane ball is medium, metal (Mn+Ni): Li mol ratio is 0.96:1, obtains intermediate mixture;
(4) presintering: the intermediate mixture of step (3) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 600 DEG C, and constant temperature time 5h, obtains pre-sintered mass;
(5) high temperature sintering: the pre-sintered mass of step (4) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 850 DEG C, and constant temperature time 10h, obtains high temperature sintering material;
(6) wet method metallized aluminum: with the high temperature sintering material of step (5) gained for base-material, take pure water as end liquid, temperature controls at 70 DEG C, 120r/min stirs, aluminum sulfate solution, sodium hydroxide solution, ammoniacal liquor stream are added, control pH, 11.2, produces aluminum hydroxide precipitation on base-material surface at 70 DEG C, obtains coated material; Wherein, in base-material, in metal M n+Ni, aluminum sulfate solution, the mass ratio of metal A l is 1000:1.2.
(7) third time low-temperature sintering: the coated material of step (6) gained is carried out wash, press filtration, oven dry, sintering, sintering temperature is 350 DEG C, constant temperature time 5h;
(8) reprocessing: the product that step (7) obtains is carried out air-flow crushing, classification and namely obtain the coated nickel ion doped finished product of aluminium.
Two, the nickel ion doped performance test that distinct methods is obtained
Claims (10)
1. a preparation method for the coated nickel ion doped of aluminium, is characterized in that comprising the following steps:
(1) manganese salt, nickel salt material preparation: by manganese salt, nickel salt material by Mn:Ni mol ratio be 3:1 carry out batching mixing;
(2) sol-gal process prepares nickel manganese presoma: add in chelating agent by the mixture of step (1) gained, regulate pH 8 ~ 10 with ammonium hydrogencarbonate, be stirred to thickness, pure water is added under stirring, be made into the solution that metal M n+Ni ion concentration is 100 ~ 150g/l, add settling agent to precipitating completely, filtering, drying precipitate, obtains nickel manganese presoma;
(3) three-dimensional inclined mixing: adopt three-dimensional inclined mixer the nickel manganese presoma of step (2) gained and lithium salts to be carried out disperseing, mixing 2 ~ 4h under medium, obtain intermediate mixture;
(4) presintering: the intermediate mixture of step (3) gained is loaded saggar, send into pushed bat kiln and sinter, sintering process is continual is filled with oxygen, sintering temperature 500 ~ 600 DEG C, and constant temperature time 4 ~ 6h, obtains pre-sintered mass;
(5) high temperature sintering: the pre-sintered mass of step (4) gained is loaded saggar, send into pushed bat kiln to sinter, sintering process is continual is filled with oxygen, sintering temperature 800 ~ 900 DEG C, constant temperature time 9.5 ~ 10.5h, obtains high temperature sintering material;
(6) wet method metallized aluminum: by the high temperature sintering material Surface coating aluminium hydroxide of wet method cladding process in step (5) gained, obtain coated material;
(7) third time low-temperature sintering: the coated material of step (6) gained is carried out wash, press filtration, oven dry, sintering, sintering temperature is 300 ~ 400 DEG C, constant temperature time 4 ~ 6h;
(8) reprocessing: the product that step (7) obtains is carried out air-flow crushing, classification and namely obtain the coated nickel ion doped finished product of aluminium.
2. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
In step (3), in nickel manganese presoma, in Mn+Ni and lithium salts, the mol ratio of Li is (0.95 ~ 1.0): 1.
3. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
In step (1), described manganese salt material is one or more in manganese sulfate, manganese nitrate, manganese chloride; Described nickel salt material is one or more in nickelous sulfate, nickel chloride, nickelous sulfate.
4. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
In step (3), described lithium salt material is lithium carbonate.
5. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
The medium that inclined mixing adopts in described step (3) is the one in zirconia ball or polyurethane ball.
6. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
The detailed step of the described wet method cladding process of step (6) is: with the high temperature sintering material of step (5) gained for base-material, take pure water as end liquid, temperature controls at 40 ~ 80 DEG C, mixing speed is 80 ~ 150r/min, to add containing aluminum solutions, sodium hydroxide solution, ammoniacal liquor stream, control pH, 10.5 ~ 11.5, produces aluminum hydroxide precipitation on base-material surface at 40 ~ 80 DEG C.
7. the preparation method of the coated nickel ion doped of aluminium according to claim 6, is characterized in that:
Described is aluminum sulfate solution or aluminum nitrate solution containing aluminum solutions; Wherein, in base-material metal M n+Ni and be 1000:(1.5 ~ 0.5 containing the mass ratio of metal A l in aluminum solutions).
8. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
In step (2), described chelating agent is one or both in PEG-6000, Polyethylene glycol-2000, PEG-4000 and PEG-6000 0.
9. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
In step (2), the quality of described chelating agent is 80 ~ 120% of metal M n+Ni quality.
10. the preparation method of the coated nickel ion doped of aluminium according to claim 1, is characterized in that:
In step (2), described settling agent is CMC, and its quality added is 3 ~ 5% of metal M n+Ni quality.
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