CN107973349A - A kind of nickel manganese binary presoma for mixing aluminium and preparation method thereof - Google Patents
A kind of nickel manganese binary presoma for mixing aluminium and preparation method thereof Download PDFInfo
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- CN107973349A CN107973349A CN201711191649.6A CN201711191649A CN107973349A CN 107973349 A CN107973349 A CN 107973349A CN 201711191649 A CN201711191649 A CN 201711191649A CN 107973349 A CN107973349 A CN 107973349A
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- nickel manganese
- nickel
- preparation
- presoma
- aluminium
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- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 33
- 239000004411 aluminium Substances 0.000 title claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 238000002156 mixing Methods 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 42
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 21
- 239000000908 ammonium hydroxide Substances 0.000 claims description 21
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 17
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 239000000843 powder Substances 0.000 claims description 8
- 239000012266 salt solution Substances 0.000 claims description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 7
- 239000011572 manganese Substances 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 5
- 150000002696 manganese Chemical class 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 compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 4
- 150000002815 nickel Chemical class 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- -1 aluminium nickel manganese Chemical compound 0.000 claims description 2
- 159000000013 aluminium salts Chemical class 0.000 claims description 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 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 2
- 238000010926 purge Methods 0.000 claims description 2
- 238000009938 salting Methods 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 238000000975 co-precipitation Methods 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 abstract 1
- 229910052808 lithium carbonate Inorganic materials 0.000 abstract 1
- 239000000463 material Substances 0.000 description 25
- PMSHDIDZIMFTLH-UHFFFAOYSA-J S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].[Ni+2] Chemical compound S(=O)(=O)([O-])[O-].[Mn+2].S(=O)(=O)([O-])[O-].[Ni+2] PMSHDIDZIMFTLH-UHFFFAOYSA-J 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 8
- 229910052744 lithium Inorganic materials 0.000 description 8
- 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 description 3
- 230000032683 aging Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 239000010941 cobalt Substances 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 229910052748 manganese Inorganic materials 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000005211 surface analysis Methods 0.000 description 2
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013215 result calculation Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 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
-
- 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
-
- 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
- H01M4/502—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese for non-aqueous cells
-
- 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
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
-
- 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 kind of nickel manganese binary presoma for mixing aluminium, the chemical formula of the nickel manganese binary presoma for mixing aluminium is：NixMn3xAly(OH)8x+3y, wherein 0.068 ﹤ y/x ﹤ 0.28, and x ﹥ 0, y ﹥ 0；The nickel manganese binary presoma graininess spherical in shape for mixing aluminium, its particle diameter distribution are：D50=6~8 μm, D10=1~6 μm, D90=10~30 μm.The nickel manganese binary presoma, its particle diameter distribution is relatively narrow, and tap density reaches 1.60 g/cm3, after being sintered with lithium carbonate, obtained lithium ion battery energy density is higher, and voltage platform is high, and cycle performance is good, has a safety feature, and high rate performance is superior.The invention also discloses preparation method, by controlling reaction kettle coprecipitation process, the relatively narrow spheric granules of particle diameter distribution, while stringent control pH value in reaction and temperature is obtained, the problem of avoiding granularity fluctuation greatly, cause properties of product to be deteriorated.
Description
Technical field
The invention belongs to field of lithium, more particularly to a kind of preparation method for the nickel manganese binary presoma for mixing aluminium.
Background technology
Industrialized production lithium battery voltage highest is generally 4.35V at present, and the positive electrode that lithium battery uses is mainly cobalt
Sour lithium, and cobalt acid lithium cost is higher, and it is toxic.And nickel manganese binary positive material and cobalt acid lithium, LiMn2O4, ternary material, phosphorus
The tradition positive electrode such as ferrous silicate lithium is compared, and is had voltage platform high, is had a safety feature, and cycle performance, high rate performance are superior, high
Voltage battery combo easily etc. advantage.
As power battery requires higher and higher, the research of high-voltage electrolyte in recent years in addition to the power-performance of material
Making progress, domestic and international enterprise has had appreciated that the development potentiality and its broad mass market of high voltage manganese nickel binary positive material,
Some Enterprises have begun to set about the development to high voltage manganese nickel binary material.The research of high voltage nickel manganese binary material and
Exploitation starts from 2001 or so, is accumulated by laboratory for many years, progressively moves towards the track of commercialized development, the world at present
Duo Jia batteries enterprise is being engaged in the work of practicality manganese nickel binary material battery.But the nickel manganese binary material of domestic-developed
Can be bad, key reason is that nickel manganese binary presoma performance does not reach requirement, if nickel manganese binary presoma is under high-multiplying power discharge
Poor circulation, so the nickel manganese binary positive material to have developed, must be first in the nickel manganese binary presoma developed.
The content of the invention
The technical problems to be solved by the invention are to overcome the shortcomings of to mention in background above technology and defect, there is provided one
The preparation method of kind excellent nickel manganese binary presoma for mixing aluminium of cycle performance under high-multiplying power discharge.
In order to solve the above technical problems, technical solution proposed by the present invention is a kind of nickel manganese binary forerunner for mixing aluminium of offer
Body, the chemical formula of the nickel manganese binary presoma for mixing aluminium are：NixMn3xAly(OH)8x+3y, wherein 0.068 ﹤ y/x ﹤ 0.28, and x
﹥ 0, y ﹥ 0；The nickel manganese binary presoma graininess spherical in shape for mixing aluminium, its particle diameter distribution are：D50=6~8 μm, D10=1~6 μ
M, D90=10~30 μm.
Under the conditions of high-multiplying power discharge, the cycle performance of nickel manganese binary material, stability are poor, and the aluminium of incorporation is in sintering
Substitute the position of part manganese into lattice, rock-steady structure, can improve its cycle performance, stability, and improve electric discharge electricity
Flattening bench.
The above-mentioned nickel manganese binary presoma for mixing aluminium, it is preferred that the specific surface area of the nickel manganese binary presoma for mixing aluminium is
13~21 m2/ g, tap density are 1.10~1.65 g/cm3。
Based on a total technical concept, the present invention also provides a kind of preparation method for the nickel manganese binary presoma for mixing aluminium,
Include the following steps：
（1）Nickel salt and manganese salt are dissolved in pure water, obtain nickel manganese salt solution；
（2）Aluminium salt is dissolved in excess sodium hydroxide solution, obtains sodium aluminate solution；
（3）Initial concentration is added in a kettle as at 0.03~0.05mol/L ammonium hydroxide to overflow port, and is passed through nitrogen purge sky
Gas, starts stirring, and it is 11.10~11.50 to add sodium hydroxide solution control ph, then by step（1）The nickel manganese obtained afterwards
Salting liquid, step（2）The sodium aluminate solution and ammonium hydroxide obtained afterwards, which is added in reaction kettle, to be reacted, and reaction temperature is 55~65
DEG C, treat granularity D50Stop reaction for 6~8 μm and without fine powder and during bulky grain, it is aged, centrifuge, dry, sieving, iron removaling, obtains
Mix the nickel manganese binary presoma of aluminium.
Above-mentioned preparation method, it is preferred that the step（1）In, nickel salt includes nickel sulfate or nickel nitrate, and manganese salt includes sulphur
Sour manganese or manganese nitrate.
Preferably, the step（1）In, Ni in nickel manganese salt solution:Mn molar ratios are 0.2~0.4, nickel manganese salt solution
Concentration be 1.5~2.5mol/L.
Preferably, the step（2）In, the mass fraction of sodium hydroxide solution is 10%~20%.
Preferably, the step（2）In, the concentration of sodium aluminate solution is 0.125~0.5mol/L.
Preferably, the step（3）In, nitrogen flow is 2~3m3/ h, the time of air-discharging is 1.5~2.5h, stirring
Revolution be 500~700r/min.
Preferably, the step（3）In, the feed rate of nickel manganese salt solution is 5L/h~200L/h, sodium aluminate solution
Charging rate be 1.4~52 L/h, the charging rate of ammonium hydroxide is 0.13~5.1L/h.
Preferably, the step（3）In, reaction temperature is 55~65 DEG C, and digestion time is 3.5~4.5h, drying temperature
For 105~125 DEG C, it is 325 mesh to cross grit number.
Compared with prior art, beneficial effects of the present invention are：
1st, the present invention mixes the nickel manganese binary presoma of aluminium, its particle diameter distribution is relatively narrow, and tap density reaches 1.60 g/cm3, with carbonic acid
After lithium sintering, obtained lithium ion battery energy density is higher, and voltage platform is high, and cycle performance is good, has a safety feature, times
Rate superior performance.
2nd, preparation method of the invention is by controlling reaction kettle coprecipitation process, obtains relatively narrow spherical of particle diameter distribution
Grain, while stringent control pH value in reaction and temperature, the problem of avoiding granularity fluctuation greatly, cause properties of product to be deteriorated.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is attached drawing needed in technology description to be briefly described, it should be apparent that, drawings in the following description are the present invention
Some embodiments, for those of ordinary skill in the art, without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the nickel manganese binary presoma electron microscope that the present invention mixes aluminium.
Fig. 2 is the presoma grading curve figure of the present invention.
Embodiment
For the ease of understanding the present invention, the present invention is done below in conjunction with Figure of description and preferred embodiment more complete
Face, meticulously describe, but protection scope of the present invention is not limited to specific examples below.
Unless otherwise defined, all technical terms used hereinafter are generally understood that implication phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, is not intended to the limitation present invention's
Protection domain.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1：
A kind of nickel manganese binary presoma for mixing aluminium of the invention, the nickel manganese binary presoma graininess spherical in shape for mixing aluminium（Such as
Fig. 1）, its chemical formula is：NiMn3Al0.2(OH)8.6, its preparation method includes the following steps：
（1）Nickel sulfate and manganese sulfate are dissolved in 45 DEG C or so of pure water, obtain Ni:Mn molar ratios are 1:3, concentration is
The nickel sulfate manganese solution of 2mol/L；
（2）Aluminum nitrate is dissolved in the sodium hydroxide solution that excessive mass fraction is 15%, stirs 2h, obtaining concentration is
The sodium aluminate solution of 0.375 mol/L；
（3）After reaction kettle is cleaned up with pure water, add pure water and reach at overflow port, open reaction kettle stirring motor, adjust
Frequency, makes revolution in 600r/min or so, adds the ammonium hydroxide that mass fraction is 15%, the concentration of ammonium hydroxide is reached 0.05mol/
L, stops adding ammonium hydroxide, and reaction kettle lid lid is real, is passed through nitrogen（Nitrogen flow 2.5m3/h）, evacuation of air 2h, raises simultaneously temperature
For degree to 60 DEG C, it is 11.10~11.50 to add sodium hydroxide solution control ph（Adjusted according to the growth rate of Control granularity
pH）, then by step（1）The nickel sulfate manganese solution that obtains afterwards, step（2）The sodium aluminate solution and ammonium hydroxide obtained afterwards passed through
Add in reaction kettle and reacted after filter filtering, nickel sulfate manganese solution feed rate is 9L/h, and sodium aluminate solution charging is fast
Spend for 2.4 L/h, the charging rate of ammonium hydroxide is 0.23L/h, treats granularity D50Stop for 7.6 μm and without fine powder and during bulky grain anti-
Should；
（4）Reaction kettle material is extracted into ageing tank, stirring hydrogenation sodium hydroxide solution adjusts pH to 11.5~12.5, after being aged 4h,
Centrifugation is pumped, after centrifuge, then material pure water 30min or so, material is taken out, moves to tray drier and do
Dry, tray drying machine host frequency 14Hz, feeding frequency 13Hz, upper disk temperature are 120 DEG C, and lower wall temperature is 95 DEG C or so, will
Dried material, is added in the mixed machine of cone, frequency 40Hz, after mixing 30min, then material is crossed 325 mesh sieves, uses
12000GS electric magnetic iron removers carry out iron removaling, and excitation gear gets to 75%, and temperature control is within 60 DEG C, 24 ± 2A of electric current, from except
Ironware mouth is fed, and outlet collects and removes magnetic material, obtains the nickel manganese binary presoma for mixing aluminium.
After testing, in the nickel manganese binary presoma that this method is prepared, Al content 1.4%, tap density 1.66g/
cm3, specific surface area 13.97m2/g, its particle diameter distribution is as shown in Figure 2.As shown in Figure 2：Size distribution compares concentration, no fine powder
And coarse granule.
Al content：Detected with ICP~OESC.
Tap density detection method：
1st, 50g samples are weighed into 100mL graduated cylinders, are recorded data in tap density test recording table；
2nd, graduated cylinder is put into instrument designated position, fixed, tested according to tap density meter operational procedure；
3rd, vibration terminates, and removes graduated cylinder, volume after reading is shaken:30.12ml, is recorded in tap density test recording table；
4th, Analysis result calculation, by the quality divided by tap volume of powder, obtains the tap density of powder, and result is filled in
In tap density test recording table.
Method for detecting specific area：
1st, sample cell, filler rod are cleaned；
2nd, sample pretreatment, sample should be placed in high temperature oven, and when drying 2 is small at least under 110 degree, sample is naturally cold
But to room temperature, and preserved in dry vessel；
3rd, with spoon spoon from sample sack all around in 5 points respectively take sample to be sequentially loaded into sample cell, add to sample cell ball
At shape bottom about 50%；
4th, toward liquid feeding nitrogen in Dewar bottle to from 5 centimeters of upper end, place about two minutes, the cross of inspection liquid nitrogen liquid level is put
Into Dewar bottle, control hole is not exceeded；
5th, it is de-gassed and tests according to 3020 surface analysis instrument operational procedures of Tristar；
6th, analysis result is expressed, and reads analysis result from 3020 surface analysis instrument test report interfaces of Tristar, and remember
Record is in specific surface area test recording table.
Example below, aluminium content, jolt ramming, be same as above than table detection method.
Embodiment 2：
A kind of nickel manganese binary presoma for mixing aluminium of the invention, the nickel manganese binary presoma graininess spherical in shape for mixing aluminium, its
Chemical formula is：NiMn3Al0.125(OH)8.375, its preparation method includes the following steps：
（1）Nickel sulfate and manganese sulfate are dissolved in 45 DEG C or so of water, obtain Ni:Mn molar ratios are 1:3, concentration is
The nickel sulfate manganese solution of 2mol/L；
（2）Aluminum nitrate is dissolved in the sodium hydroxide solution that excessive mass fraction is 15%, stirs 2h, obtaining concentration is
The sodium aluminate solution of 0.375 mol/L；
（3）After reaction kettle is cleaned up with pure water, add pure water and reach at overflow port, open reaction kettle stirring motor, adjust
Frequency, makes revolution in 600r/min or so, adds the ammonium hydroxide that mass fraction is 15%, the concentration of ammonium hydroxide is reached 0.05mol/
L, stops adding ammonium hydroxide, and reaction kettle lid lid is real, is passed through nitrogen（Nitrogen flow 2.5m3/h）, evacuation of air 2h, raises simultaneously temperature
For degree to 60 DEG C, it is 11.10~11.50 to add sodium hydroxide solution control ph（Adjusted according to the growth rate of Control granularity
pH）, then by step（1）The nickel sulfate manganese solution that obtains afterwards, step（2）The sodium aluminate solution and ammonium hydroxide obtained afterwards passed through
Add in reaction kettle and reacted after filter filtering, nickel sulfate manganese solution feed rate is 9L/h, and sodium aluminate solution charging is fast
Spend for 1.5 L/h, the charging rate of ammonium hydroxide is 0.23L/h, treats granularity D50Stop for 7.1 μm and without fine powder and during bulky grain anti-
Should；
（4）Reaction kettle material is extracted into ageing tank, stirring hydrogenation sodium hydroxide solution adjusts pH to 11.5~12.5, is aged 4.5h
Afterwards, centrifugation is pumped, after centrifuge, then material pure water 20min or so, material is taken out, moves to tray drying
Machine is dried, tray drying machine host frequency 14Hz, feeding frequency 13Hz, and upper disk temperature is 125 DEG C, and lower wall temperature is 102 DEG C of left sides
The right side, dried material is added in the mixed machine of cone, frequency 40Hz, after mixing 20min, then material is crossed 325 mesh sieves, is used
12000GS electric magnetic iron removers carry out iron removaling, and excitation gear gets to 75%, and temperature control is within 60 DEG C, 24 ± 2A of electric current, from except
Ironware mouth is fed, and outlet collects and removes magnetic material, obtains the nickel manganese binary presoma for mixing aluminium.
After testing, in the nickel manganese binary presoma that this method is prepared, Al content 0.9%, tap density 1.47g/
Cm3, specific surface area 16.33m2/ g, its particle diameter distribution are：D50=6~8 μm, D10=1~6 μm, D90=10~30 μm.
Embodiment 3：
A kind of nickel manganese binary presoma for mixing aluminium of the invention, the nickel manganese binary presoma graininess spherical in shape for mixing aluminium, its
Chemical formula is：NiMn3Al0.25(OH)8.75, its preparation method includes the following steps：
（1）Nickel sulfate and manganese sulfate are dissolved in 45 DEG C or so of water, obtain Ni:Mn molar ratios are 1:3, concentration is
The nickel sulfate manganese solution of 2mol/L；
（2）Aluminum nitrate is dissolved in the sodium hydroxide solution that excessive mass fraction is 15%, stirs 2h, obtaining concentration is
The sodium aluminate solution of 0.375 mol/L；
（3）After reaction kettle is cleaned up with pure water, add pure water and reach at overflow port, open reaction kettle stirring motor, adjust
Frequency, makes revolution in 600r/min or so, adds the ammonium hydroxide that mass fraction is 15%, the concentration of ammonium hydroxide is reached 0.05mol/
L, stops adding ammonium hydroxide, and reaction kettle lid lid is real, is passed through nitrogen（Nitrogen flow 2.5m3/h）, evacuation of air 2h, raises simultaneously temperature
For degree to 60 DEG C, it is 11.10~11.50 to add sodium hydroxide solution control ph（Adjusted according to the growth rate of Control granularity
pH）, then by step（1）The nickel sulfate manganese solution that obtains afterwards, step（2）The sodium aluminate solution and ammonium hydroxide obtained afterwards passed through
Add in reaction kettle and reacted after filter filtering, nickel sulfate manganese solution feed rate is 9L/h, and sodium aluminate solution charging is fast
Spend for 3 L/h, the charging rate of ammonium hydroxide is 0.23L/h, treats granularity D50Stop reaction for 6.8 μm and without fine powder and during bulky grain；
（4）Reaction kettle material is extracted into ageing tank, stirring hydrogenation sodium hydroxide solution adjusts pH to 11.5~12.5, is aged 3.5h
Afterwards, centrifugation is pumped, after centrifuge, then material pure water 40min or so, material is taken out, moves to tray drying
Machine is dried, tray drying machine host frequency 14Hz, feeding frequency 13Hz, and upper disk temperature is 114 DEG C, and lower wall temperature is 90 DEG C of left sides
The right side, dried material is added in the mixed machine of cone, frequency 40Hz, after mixing 40min, then material is crossed 325 mesh sieves, is used
12000GS electric magnetic iron removers carry out iron removaling, and excitation gear gets to 75%, and temperature control is within 60 DEG C, 24 ± 2A of electric current, from except
Ironware mouth is fed, and outlet collects and removes magnetic material, obtains the nickel manganese binary presoma for mixing aluminium.
After testing, in the nickel manganese binary presoma that this method is prepared, Al content 1.7%, tap density 1.59g/
Cm3, specific surface area 15.24m2/ g, its particle diameter distribution are：D50=6~8 μm, D10=1~6 μm, D90=10~30 μm.
Claims (10)
1. a kind of nickel manganese binary presoma for mixing aluminium, it is characterised in that the chemical formula of the nickel manganese binary presoma for mixing aluminium is：
NixMn3xAly(OH)8x+3y, wherein 0.068 ﹤ y/x ﹤ 0.28, and x ﹥ 0, y ﹥ 0；It is described mix aluminium nickel manganese binary presoma it is spherical in shape
Graininess, its particle diameter distribution are：D50=6~8 μm, D10=1~6 μm, D90=10~30 μm.
2. the nickel manganese binary presoma according to claim 1 for mixing aluminium, it is characterised in that the nickel manganese binary for mixing aluminium
The specific surface area of presoma is 13~21 m2/ g, tap density are 1.10~1.65 g/cm3。
3. a kind of preparation method for the nickel manganese binary presoma for mixing aluminium, includes the following steps：
（1）Nickel salt and manganese salt are dissolved in pure water, obtain nickel manganese salt solution；
（2）Aluminium salt is dissolved in excess sodium hydroxide solution, obtains sodium aluminate solution；
（3）Initial concentration is added in a kettle as at 0.03~0.05mol/L ammonium hydroxide to overflow port, and is passed through nitrogen purge sky
Gas, starts stirring, and it is 11.10~11.50 to add sodium hydroxide solution control ph, then by step（1）The nickel manganese obtained afterwards
Salting liquid, step（2）The sodium aluminate solution and ammonium hydroxide obtained afterwards, which is added in reaction kettle, to be reacted, and reaction temperature is 55~65
DEG C, treat granularity D50Stop reaction for 6~8 μm and without fine powder and during bulky grain, it is aged, centrifuge, dry, sieving, iron removaling, obtains
Mix the nickel manganese binary presoma of aluminium.
4. preparation method according to claim 3, it is characterised in that the step（1）In, nickel salt includes nickel sulfate or nitre
Sour nickel, manganese salt include manganese sulfate or manganese nitrate.
5. the preparation method according to claim 3 or 4, it is characterised in that the step（1）In, Ni in nickel manganese salt solution
:Mn molar ratios are 0.2~0.4, and the concentration of nickel manganese salt solution is 1.5~2.5mol/L.
6. preparation method according to claim 3, it is characterised in that the step（2）In, the quality of sodium hydroxide solution
Fraction is 10%~20%.
7. the preparation method according to claim 3 or 6, it is characterised in that the step（2）In, sodium aluminate solution
Concentration is 0.125~0.5mol/L.
8. preparation method according to claim 3, it is characterised in that the step（3）In, nitrogen flow is 2~3m3/ h,
The time of air-discharging is 1.5~2.5h, and the revolution of stirring is 500~700r/min.
9. preparation method according to claim 3, it is characterised in that the step（3）In, the charging of nickel manganese salt solution
Flow is 5L/h~200L/h, and the charging rate of sodium aluminate solution is 1.4~52 L/h, and the charging rate of ammonium hydroxide is 0.13
~5.1L/h.
10. preparation method according to claim 3, it is characterised in that the step（3）In, digestion time for 3.5~
4.5h, drying temperature are 105~125 DEG C, and it is 325 mesh to cross grit number.
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