CN106241894B - A kind of preparation method of nanometer spinel type nickle cobalt lithium manganate - Google Patents
A kind of preparation method of nanometer spinel type nickle cobalt lithium manganate Download PDFInfo
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- CN106241894B CN106241894B CN201610576507.0A CN201610576507A CN106241894B CN 106241894 B CN106241894 B CN 106241894B CN 201610576507 A CN201610576507 A CN 201610576507A CN 106241894 B CN106241894 B CN 106241894B
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- spinel type
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- lithium manganate
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- 229910052596 spinel Inorganic materials 0.000 title claims abstract description 42
- 239000011029 spinel Substances 0.000 title claims abstract description 42
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 150000001868 cobalt Chemical class 0.000 claims abstract description 13
- 150000002696 manganese Chemical class 0.000 claims abstract description 13
- 150000002815 nickel Chemical class 0.000 claims abstract description 13
- 238000000137 annealing Methods 0.000 claims abstract description 12
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 12
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 12
- 230000005484 gravity Effects 0.000 claims abstract description 11
- 230000008569 process Effects 0.000 claims abstract description 9
- 239000000843 powder Substances 0.000 claims abstract description 8
- 239000011572 manganese Substances 0.000 claims description 41
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 229910012406 LiNi0.5 Inorganic materials 0.000 claims description 13
- 150000001768 cations Chemical class 0.000 claims description 10
- 229910001416 lithium ion Inorganic materials 0.000 claims description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 6
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005245 sintering Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 238000001035 drying Methods 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
- 239000003513 alkali Substances 0.000 claims description 4
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical group [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 4
- 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 group [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 4
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 4
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 3
- 238000007605 air drying Methods 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 229910001437 manganese ion Inorganic materials 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
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002245 particle Substances 0.000 abstract description 15
- 238000009826 distribution Methods 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000012545 processing Methods 0.000 abstract description 3
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 abstract 1
- 238000010923 batch production Methods 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 229910013716 LiNi Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004519 manufacturing process Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910032387 LiCoO2 Inorganic materials 0.000 description 2
- 229910002993 LiMnO2 Inorganic materials 0.000 description 2
- 229910003005 LiNiO2 Inorganic materials 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910011297 LiCox Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 description 1
- NVJVFAHBMSMYNT-UHFFFAOYSA-M [Mn].[Ni]=O.O[Co] Chemical compound [Mn].[Ni]=O.O[Co] NVJVFAHBMSMYNT-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- NVIVJPRCKQTWLY-UHFFFAOYSA-N cobalt nickel Chemical compound [Co][Ni][Co] NVIVJPRCKQTWLY-UHFFFAOYSA-N 0.000 description 1
- SEVNKUSLDMZOTL-UHFFFAOYSA-H cobalt(2+);manganese(2+);nickel(2+);hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mn+2].[Co+2].[Ni+2] SEVNKUSLDMZOTL-UHFFFAOYSA-H 0.000 description 1
- KTPIHRZQGZDLSN-UHFFFAOYSA-N cobalt;nitric acid Chemical compound [Co].O[N+]([O-])=O KTPIHRZQGZDLSN-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/006—Compounds containing, besides nickel, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The present invention provides a kind of preparation method of nanometer spinel type nickle cobalt lithium manganate, comprises the following steps：The first step, nanoscale precursor of nickel-cobalt-lithium-manganese-oxide is prepared, be specifically：Well mixed be made into after mixed liquor in addition super gravity field reactor of nickel salt, cobalt salt and manganese salt is reacted；Solution after reaction is carried out successively to be filtered, washed and dried processing, nanoscale presoma is produced；Second step, nanoscale presoma obtained by the first step is well mixed with lithium salts after carry out pre-burning, roasting and annealing process successively, produce nanometer spinel type nickle cobalt lithium manganate powder.The present invention has advantages below：Technique is simple, with low cost, easy to operate, can rapid batch production；The nickle cobalt lithium manganate size tunable (average grain diameter is about 200nm) of preparation, particle diameter distribution is narrow, soilless sticking, and crystallinity is high and crystal formation is complete.
Description
Technical field
The present invention relates to lithium ion battery material preparing technical field, and in particular to a kind of nanometer spinel type nickel cobalt mangaic acid
Lithium LiNi0.5Co0.05Mn1.45O4Preparation method.
Background technology
Anode material for lithium-ion batteries is the key and core technology of lithium ion battery development, is also Study on Li-ion batteries
Main way and focus.Comprehensive LiCoO2、LiNiO2、LiMnO2The advantage of three class materials, forms LiCoO2/LiNiO2/
LiMnO2Eutectic system be combined into containing nickel-cobalt-manganese ternary element the embedding oxidate for lithium composite of novel transition metal, its lead to
Formula is LiCoxMnyNi(1-x-y)O2(0<x<0.5,0<y<0.5), its combination property is better than any single group polymerisable compounds, exists substantially
Trielement synergistic effect：Groundwork interval is located at 2.5~4.6V, with higher specific discharge capacity, and in charge and discharge process
In, the feature of layer structure can be kept.Because it has good chemical property, (such as specific capacity is big, good cycle and work
Make voltage height etc.), thermodynamic stability, security it is good and cheap, therefore, it is most potential to turn into lithium ion two of future generation
The positive electrode of primary cell.
In order to obtain excellent chemical property, it is considered that prepared nickle cobalt lithium manganate should have crystal formation it is complete,
The features such as uniform, the big specific surface area of Stability Analysis of Structures, particle.At present, preparing the main method of nickle cobalt lithium manganate has：
(1) high-temperature solid-phase sintering method, the method is simple to operate, and preparation condition is easily controllable, easily carries out industrialized production,
But energy consumption is big, the product particle of preparation is big, and granule-morphology is difficult to control to, product batches poor repeatability.
(2) spray pyrolysis, the method powder purity is high, pattern is good, even particle size distribution, and technical process is simple, can connect
Continuous metaplasia production, yield are big, but particle is larger.
(3) sol-gel processing etc., the method production cycle is long, is unfavorable for industrialized production.
(4) improved method, Details as Follows：
Chinese invention patent application CN103794778A discloses a kind of using manganese salt, cobalt salt, the preparation of nickel salt coprecipitation
High density spherical nickel-cobalt LiMn2O4, particle is uniform, and bulk density is big, but the reaction time is longer, and particle is larger, not up to nanometer
Level.
Chinese invention patent CN103280575A is using hydroxide nickel cobalt manganese or hydroxy cobalt nickel oxide manganese powder end and lithium carbonate
The method of powder mixing high-temperature calcination, this method prepare nickle cobalt lithium manganate, with volume capacity density it is big, safe, fill
Discharge cycles good endurance, but the method needs high temperature, and easily assemble, particle is larger, is not suitable for industrial production.
Chinese invention patent application CN104319384A prepares nickle cobalt lithium manganate, products therefrom grain using sol-gel processing
Degree is uniform, and soilless sticking, appearance structure is consistent.But particle is larger, and flow is numerous and diverse.
The content of the invention
Present invention aims at providing, a kind of average grain diameter is 150nm, particle diameter distribution is narrow, crystallinity is high and crystal formation is complete
The preparation method of nanometer spinel type nickle cobalt lithium manganate, concrete technical scheme is as follows：
A kind of preparation method of nanometer spinel type nickle cobalt lithium manganate, comprises the following steps：
The first step, prepare nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma, be specifically：
Nickel salt, cobalt salt and manganese salt are well mixed, the mixed liquor that total cation concentration is 0.1-2.0mol/L is made into；Will be mixed
Close liquid and be placed in the super gravity field reactor that stir speed (S.S.) is 400-1500rpm and reacted, hydroxide is added in course of reaction
The mixed ammonium/alkali solutions of sodium and ammoniacal liquor, the pH value for controlling solution after reaction is 10.5-12.0；Solution after reaction was carried out successively
Filter, washing and drying process, produce nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma；
Second step, prepare nanometer spinel type LiNi0.5Co0.05Mn1.45O4, it is specifically：
By nanoscale Ni obtained by the first step0.5Co0.05Mn1.45(OH)2Presoma carries out pre- successively after being well mixed with lithium salts
Burn, be calcined and annealing process, produce nanometer spinel type LiNi0.5Co0.05Mn1.45O4Powder.
Preferred in above technical scheme, the reactor is rotating bed with helix channel or RPB.
Preferred in above technical scheme, the nickel salt, cobalt salt, manganese salt, lithium salts press nickel ion：Cobalt ions：Manganese ion：Lithium
The mol ratio of ion is 0.3-0.8：0.01-0.1：1.0-2.0：1.0-3.0 proportioning carries out dispensing.
It is preferred in above technical scheme, pre-burning, roasting and anneal using microwave heating to enter in the second step
OK, rate temperature change is 2-8 DEG C/min.
Preferred in above technical scheme, calcined temperature is 400 DEG C -700 DEG C in the second step, and burn-in time is 4-
7h；Sintering temperature is 700 DEG C -950 DEG C, and roasting time is 8-24h；Annealing temperature is 500 DEG C -750 DEG C, and annealing time is 7-
15h。
Preferred in above technical scheme, the nickel salt is nickel sulfate or nickel nitrate, and the cobalt salt is cobaltous sulfate or nitric acid
Cobalt, the manganese salt is manganese sulfate or manganese nitrate, and the lithium salts is lithium nitrate or lithium carbonate.
Preferred in above technical scheme, sodium hydroxide and concentration are 25%- in sodium hydroxide solution in the first step
The mol ratio of 28% ammoniacal liquor is 1：4, naoh concentration and the mol ratio of mixed liquor total cation concentration are 1：1.
Preferred in above technical scheme, drying is specifically in the first step：In the condition that temperature is 100 DEG C -200 DEG C
Lower forced air drying 8-14h.
Using nanometer spinel type nickle cobalt lithium manganate LiNi of the present invention0.5Co0.05Mn1.45O4Preparation method, with following
Beneficial effect：
(1) present invention provides a kind of new method for preparing nanometer nickel-cobalt LiMn2O4, and can prepare average grain diameter is
The nanometer spinel type nickle cobalt lithium manganate that 200nm, particle diameter distribution are narrow, crystallinity is high and crystal formation is complete, overcomes prior art system
The particle diameter distribution of standby cobalt nickel ion doped is uneven, easily reunite, the shortcomings of crystalline phase purity is low, crystallinity is not high.
(2) nanoscale Ni of the present invention0.5Co0.05Mn1.45(OH)2Presoma is under Elevated Gravity (preferably with gas-liquid reaction
Or liquid-liquid reactions) prepare, it is ensured that nanoscale Ni0.5Co0.05Mn1.45(OH)2The granularity of presoma is controllable and is evenly distributed.
(3) pre-burning of the present invention, roasting and annealing are carried out using microwave heating, and process is simple and easy to apply, the production cycle
It is short, and product particle size is uniform, crystallinity is high.
(4) the process step of the invention is simplified, and equipment is readily obtained, with short production cycle, is adapted to industrialized production.
In addition to objects, features and advantages described above, the present invention also has other objects, features and advantages.
Below with reference to figure, the present invention is further detailed explanation.
Brief description of the drawings
The accompanying drawing for constituting the part of the application is used for providing a further understanding of the present invention, schematic reality of the invention
Apply example and its illustrate to be used to explain the present invention, do not constitute inappropriate limitation of the present invention.In the accompanying drawings：
Fig. 1 is nanometer spinel type LiNi prepared by the embodiment of the present invention 10.5Co0.05Mn1.45O4XRD；
Fig. 2 is the nanometer spinel type LiNi for preparing in embodiment 10.5Co0.05Mn1.45O4SEM figure；
Fig. 3 is the nanometer spinel type LiNi for preparing in embodiment 10.5Co0.05Mn1.45O4TEM figure；
Fig. 4 is nanometer spinel type LiNi prepared by 1-3 of the embodiment of the present invention0.5Co0.05Mn1.45O4XRD；
Fig. 5 is the nanometer spinel type LiNi prepared in the embodiment of the present invention 1,4,50.5Co0.05Mn1.45O4XRD；
Fig. 6 is nanometer spinel type LiNi prepared by embodiment 60.5Co0.05Mn1.45O4SEM figure；
Fig. 7 is nanometer spinel type LiNi prepared by comparative example 10.5Co0.05Mn1.45O4XRD；
Fig. 8 is nanometer spinel type LiNi prepared by comparative example 20.5Co0.05Mn1.45O4SEM figure.
Embodiment
Embodiments of the invention are described in detail below in conjunction with accompanying drawing, but the present invention can be limited according to claim
Fixed and covering multitude of different ways is implemented.
Embodiment 1：
A kind of nanometer spinel type nickle cobalt lithium manganate (LiNi0.5Co0.05Mn1.45O4) preparation method, comprise the following steps：
The first step, prepare nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma, be specifically：
Nickel salt, cobalt salt, manganese salt is well mixed according to proportioning, it is made into the mixed liquor that total cation concentration is 0.2mol/L；
Super gravity field is produced using rotating bed with helix channel supergravity reactor, and adults power reactor rotor speed is
1000rpm, slurry mixed liquor, which is placed in super gravity field, to be reacted and is circulated, and is added dropwise by matching into super gravity field reactor by hydrogen
Solution after being reacted after the mixed ammonium/alkali solutions of sodium oxide molybdena and ammoniacal liquor composition, fully reaction (pH value is 11.0)；It is molten after reacting
Liquid is filtered, and with distillation water washing and drying, produces nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma, wherein：Dry specific
It is the forced air drying 10h under conditions of temperature is 120 DEG C；
Second step, prepare nanometer spinel type LiNi0.5Co0.05Mn1.45O4, it is specifically：
By nanoscale Ni obtained by the first step0.5Co0.05Mn1.45(OH)2Presoma carries out pre- successively after being well mixed with lithium salts
Burn, be calcined and annealing process, produce nanometer spinel type LiNi0.5Co0.05Mn1.45O4Powder, be specifically：It is placed in microwave Muffle furnace
In, then the pre-burning 6h under the conditions of temperature is 600 DEG C is calcined 12h under the conditions of temperature is 880 DEG C, is finally 700 DEG C in temperature
Under the conditions of anneal 10h.
The nickel salt, cobalt salt, manganese salt, lithium salts are respectively nickel sulfate, cobaltous sulfate, manganese sulfate, lithium carbonate, the nickel sulfate,
Cobaltous sulfate, manganese sulfate, lithium carbonate press nickel ion：Cobalt ions：Manganese ion：The mol ratio of lithium ion is 0.5：0.05：1.45：1.05
Proportioning carry out dispensing.
The concentration of sodium hydroxide and ammoniacal liquor is respectively 0.2mol/L and 0.8mol/L in the mixed ammonium/alkali solutions.
By nanometer spinel type LiNi obtained by the present embodiment0.5Co0.05Mn1.45O4XRD, SEM and TEM detection are carried out, as a result
Fig. 1, Fig. 2 and Fig. 3 are referred to, from Fig. 1-3, prepared nanometer spinel type LiNi0.5Co0.05Mn1.45O4,It is complete with crystal formation
Whole, crystallinity is high, epigranular, soilless sticking the features such as, average grain diameter is in 200nm or so.
Embodiment 2- embodiments 3
The difference from Example 1 of embodiment 2- embodiments 3 is：The temperature and time being calcined in microwave Muffle furnace,
With being：Sintering temperature is 780 DEG C in embodiment 2, and roasting time is 10h；Sintering temperature is 950 DEG C in embodiment 3, during roasting
Between be 14h.
Embodiment 2 and the gained nanometer spinel type LiNi of embodiment 30.5Co0.05Mn1.45O4XRD testing results refer to figure
4,1-3 in conjunction with the embodiments, as can be seen from Figure 4：Under the conditions of 750 DEG C and 950 DEG C of microwave calcinations, the production of other dephasigns is had
Raw, the diffraction maximum of impurity is more apparent.And under 880 DEG C of calcination conditions, crystal formation is good, the presence at free from admixture peak.It follows that calcining
Influence of the temperature to crystalline form is very big, to obtain the good nanometer nickel-cobalt LiMn2O4 of crystalline phase, control sintering temperature 880 DEG C or so compared with
It is good.
Embodiment 4- embodiments 5
The difference from Example 1 of embodiment 4- embodiments 5 is only that the concentration of total cation, is specifically：In embodiment 4
The concentration of total cation is that the concentration of total cation in 0.1mol/L, embodiment 5 is 0.25mol/L.
The gained nanometer spinel type LiNi of embodiment 4- embodiments 50.5Co0.05Mn1.45O4XRD testing results refer to Fig. 5.
1, embodiment 4 and embodiment 5 (see Fig. 5) are understood in conjunction with the embodiments：The concentration of total cation is prepared in 0.20mol/L or so
Sample crystallinity it is high, free from admixture is produced.
Embodiment 6
The difference of embodiment 6 and embodiment 1 is：
Pre-burning, roasting and annealing process are carried out in conventional Muffle furnace.
The gained nanometer spinel type LiNi of embodiment 60.5Co0.05Mn1.45O4SEM testing results refer to Fig. 6.With reference to implementation
Example 1 and embodiment 6 are understood：Conventional Muffle furnace calcines (embodiment 6), and product slightly has reunion；And use microwave calcination (embodiment 1)
The product of acquisition, particle diameter distribution is uniform, reunites few, crystallinity is high.Therefore, the properties of product obtained using microwave calcination are better than normal
Rule mode is calcined.
6 (referring to Fig. 6) and comparative example 2 (referring to Fig. 8) in conjunction with the embodiments, the products obtained therefrom of embodiment 6 are implemented with contrast
The product of example 2 compares, and particle diameter distribution is uniform, reunites few, crystallinity is high.
Comparative example 1
A kind of nanometer spinel type nickle cobalt lithium manganate LiNi0.5Co0.05Mn1.45O4Preparation method, comprise the following steps：
The first step, prepare nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma, be specifically：
Nickel salt, cobalt salt, manganese salt, lithium salts are made into mixed liquor according to proportioning is well mixed；Use rotating bed with helix channel
Supergravity reactor produces super gravity field, and adults power reactor rotor speed is 1000rpm, and slurry mixed liquor is placed in overweight
Reacted and circulated in the field of force, by proportioning toward sal volatile is added dropwise in super gravity field reactor, by total cation concentration with
The mol ratio of sal volatile is 1：1, solution after fully being reacted after reaction (pH value is 11.0)；By solution after reaction successively
Progress is filtered, washed and dried processing, produces presoma, wherein：It is dry that air blast is done specifically under conditions of temperature is 120 DEG C
Dry 10h；
Second step, prepare nanometer spinel type LiNi0.5Co0.05Mn1.45O4, it is specifically：
Presoma obtained by the first step is subjected to pre-burning, roasting and annealing process successively, nanometer spinel type is produced
LiNi0.5Co0.05Mn1.45O4Powder, be specifically：It is placed in microwave Muffle furnace, the pre-burning 6h under the conditions of temperature is 600 DEG C, then
12h is calcined under the conditions of temperature is 880 DEG C, finally anneal 10h under the conditions of temperature is 700 DEG C.
The nickel salt, cobalt salt, manganese salt, lithium salts are respectively nickel nitrate, cobalt nitrate, manganese nitrate and lithium nitrate.
Other procedure of processings and technological parameter be the same as Example 1.
The gained nanometer spinel type LiNi of comparative example 10.5Co0.05Mn1.45O4XRD testing results refer to Fig. 7.
In conjunction with the embodiments 1 and comparative example 1 understand：Embodiment 1 can prepare the nanometer point crystalline substance of crystallinity height, free from admixture
Stone-type LiNi0.5Co0.05Mn1.45O4, and the product obtained by comparative example 1 easily produces the oxidation of the oxide of manganese nickel, lithium
The impurity such as thing, therefore, the influence of the order of addition of raw material (nickel salt, cobalt salt, manganese salt, lithium salts) to properties of product are very big, only
High performance product could be obtained using the addition manner of the present invention.
Comparative example 2
The difference of comparative example 2 and embodiment 1 is：
Presoma is prepared in three-necked flask (under i.e. normal gravity environment).
The gained nanometer spinel type LiNi of comparative example 20.5Co0.05Mn1.45O4SEM testing results refer to Fig. 8.
In conjunction with the embodiments 1 and comparative example 2 understand：Under normal gravity environment (comparative example 2), the product of preparation
Grain is big, and granule-morphology is difficult to control to, and under hypergravity effect (embodiment 1), can prepare nanoscale, the sample being evenly distributed
Product.It can be seen that to prepare presoma very big to the performance impact of product for use supergravity reactor.
The preferred embodiments of the present invention are the foregoing is only, are not intended to limit the invention, for the skill of this area
For art personnel, the present invention can have various modifications and variations.Within the spirit and principles of the invention, that is made any repaiies
Change, equivalent substitution, improvement etc., should be included in the scope of the protection.
Claims (8)
1. a kind of preparation method of nanometer spinel type nickle cobalt lithium manganate, it is characterised in that comprise the following steps：
The first step, prepare nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma, be specifically：
Nickel salt, cobalt salt and manganese salt are well mixed, the mixed liquor that total cation concentration is 0.1-2.0mol/L is made into；By mixed liquor
Be placed in stir speed (S.S.) be 400-1500rpm super gravity field reactor in reacted, in course of reaction add sodium hydroxide with
The mixed ammonium/alkali solutions of ammoniacal liquor, the pH value for controlling solution after reaction is 10.5-12.0；Solution after reaction is filtered successively, washed
Wash and drying process, produce nanoscale Ni0.5Co0.05Mn1.45(OH)2Presoma；
Second step, prepare nanometer spinel type LiNi0.5Co0.05Mn1.45O4, it is specifically：
By nanoscale Ni obtained by the first step0.5Co0.05Mn1.45(OH)2Presoma carries out pre-burning, roasting successively after being well mixed with lithium salts
Burn and annealing process, produce nanometer spinel type LiNi0.5Co0.05Mn1.45O4Powder.
2. the preparation method of nanometer spinel type nickle cobalt lithium manganate according to claim 1, it is characterised in that the reaction
Device is rotating bed with helix channel or RPB.
3. the preparation method of nanometer spinel type nickle cobalt lithium manganate according to claim 2, it is characterised in that the nickel
Salt, cobalt salt, manganese salt, lithium salts press nickel ion：Cobalt ions：Manganese ion：The mol ratio of lithium ion is 0.3-0.8：0.01-0.1：1.0-
2.0：1.0-3.0 proportioning carries out dispensing.
4. the preparation method of the nanometer spinel type nickle cobalt lithium manganate according to claim 1-3 any one, its feature exists
In pre-burning, roasting and annealing are carried out using microwave heating in the second step, and rate temperature change is 2-8 DEG C/min.
5. the preparation method of nanometer spinel type nickle cobalt lithium manganate according to claim 4, it is characterised in that described second
Calcined temperature is 400 DEG C -700 DEG C in step, and burn-in time is 4-7h；Sintering temperature is 700 DEG C -950 DEG C, and roasting time is 8-
24h；Annealing temperature is 500 DEG C -750 DEG C, and annealing time is 7-15h.
6. the preparation method of nanometer spinel type nickle cobalt lithium manganate according to claim 4, it is characterised in that the nickel salt
For nickel sulfate or nickel nitrate, the cobalt salt is cobaltous sulfate or cobalt nitrate, and the manganese salt is manganese sulfate or manganese nitrate, and the lithium salts is
Lithium nitrate or lithium carbonate.
7. the preparation method of nanometer spinel type nickle cobalt lithium manganate according to claim 4, it is characterised in that the mixing
In aqueous slkali：The mol ratio of sodium hydroxide and ammonium ion is 1：4, the mol ratio of sodium hydroxide and total cation in mixed liquor is
1：1.
8. the preparation method of nanometer spinel type nickle cobalt lithium manganate according to claim 4, it is characterised in that described first
Drying is specifically in step：The forced air drying 8-14h under conditions of temperature is 100 DEG C -200 DEG C.
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