CN104332622A - Spheroidic nickel-cobalt-manganese precursor material with high purity and high crystallinity, and preparation method thereof - Google Patents
Spheroidic nickel-cobalt-manganese precursor material with high purity and high crystallinity, and preparation method thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 56
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 39
- 239000002243 precursor Substances 0.000 title abstract 6
- 238000000034 method Methods 0.000 claims abstract description 36
- 238000000975 co-precipitation Methods 0.000 claims abstract description 29
- 238000003483 aging Methods 0.000 claims abstract description 25
- 230000032683 aging Effects 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 20
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 14
- 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 claims abstract description 6
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 6
- 239000011734 sodium Substances 0.000 claims abstract description 6
- 239000000126 substance Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims description 93
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 42
- 238000001556 precipitation Methods 0.000 claims description 32
- 239000003638 chemical reducing agent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 20
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 16
- 239000012266 salt solution Substances 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 14
- 230000005070 ripening Effects 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- OVAQODDUFGFVPR-UHFFFAOYSA-N lithium cobalt(2+) dioxido(dioxo)manganese Chemical compound [Li+].[Mn](=O)(=O)([O-])[O-].[Co+2] OVAQODDUFGFVPR-UHFFFAOYSA-N 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 150000001868 cobalt Chemical class 0.000 claims description 5
- 150000002696 manganese Chemical class 0.000 claims description 5
- 150000002815 nickel Chemical class 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 4
- 210000005056 cell body Anatomy 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- IOVCWXUNBOPUCH-UHFFFAOYSA-M Nitrite anion Chemical compound [O-]N=O IOVCWXUNBOPUCH-UHFFFAOYSA-M 0.000 claims description 3
- 239000003153 chemical reaction reagent Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000003780 insertion Methods 0.000 claims description 2
- 230000037431 insertion Effects 0.000 claims description 2
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Substances [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 2
- 235000010288 sodium nitrite Nutrition 0.000 claims description 2
- 229910015450 Ni1-x-yCoxMny(OH)2 Inorganic materials 0.000 abstract 1
- 238000010924 continuous production Methods 0.000 abstract 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 239000010405 anode material Substances 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000006392 deoxygenation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- MZZUATUOLXMCEY-UHFFFAOYSA-N cobalt manganese Chemical compound [Mn].[Co] MZZUATUOLXMCEY-UHFFFAOYSA-N 0.000 description 2
- 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 2
- 239000011259 mixed solution Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052493 LiFePO4 Inorganic materials 0.000 description 1
- 229910002097 Lithium manganese(III,IV) oxide Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000035882 stress Effects 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
-
- 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
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a spheroidic nickel-cobalt-manganese precursor material with high purity and high crystallinity. The chemical molecular formula of the precursor material is Ni1-x-yCoxMny(OH)2, wherein x is more than 0 and less than 1, and y is more than 0 and less than 1; and the mass fraction of sodium impurities in the precursor material is not more than 0.012%, the mass fraction of sulfate radical impurities is not less than 0.30%, the precursor material has high crystallinity, and the characteristic peak 001 intensity of an XRD atlas is not less than 1100. The invention also discloses a preparation method of the nickel-cobalt-manganese precursor material. The method comprises the steps of raw material preparation, coprecipitation and ageing treatment, and at least one of the above three steps adopts an anti-oxidation measure. The above product has the advantages of low content of impurities, good crystallinity, simple process flow, realization of continuous production, and stable and excellent quality.
Description
Technical field
The invention belongs to anode material of lithium battery technical field, particularly relate to a kind of anode material of lithium battery nickel cobalt manganese persursor material and preparation method thereof.
Background technology
Lithium ion battery as a kind of novel green secondary cell, have specific capacity large, have extended cycle life, the advantage such as self discharge is little, quality is light, memory-less effect.Be widely used in the field such as various mobile electronic product (as mobile phone, camera, notebook computer etc.), artificial satellite, space flight and aviation at present, also have good application prospect in the field such as electric automobile and battery-operated motor cycle.For adapting to the growing needs of these applications, the demand of the lithium rechargeable battery larger to capacity, weight is lighter, size is less constantly increases, and therefore, proposes more and more higher requirement to the specific capacity performance of anode material for lithium-ion batteries.
Anode material for lithium-ion batteries in the market mainly contains cobalt acid lithium, nickle cobalt lithium manganate, LiMn2O4 and LiFePO4 series four large classes.The ratio of the nickel in nickle cobalt lithium manganate adjustable presoma, cobalt, manganese meets the difference in functionality demand of material, so its application is more and more extensive, in digital product, energy storage and power etc., has use.Nickel cobalt manganese hydroxide, namely nickel cobalt manganese presoma produces the raw material of nickle cobalt lithium manganate, and the particle size of nickel cobalt manganese presoma, pattern, structure have direct impact to the nickle cobalt lithium manganate size of following process, pattern, structure.Therefore the quality of nickel cobalt manganese presoma directly determines the quality of nickle cobalt lithium manganate.
At present, the common method preparing nickel cobalt manganese hydroxide is crystallization control hydroxide coprecipitation step, and the metal salt solution being about to mixing obtains mixed metal hydroxides and precipitates under the effect of complexing agent with sodium hydroxide pellets.But, in the course of reaction of this coprecipitation, due to the problem such as the sealing that there is vigorous stirring in a small amount of oxygen and precipitation process and reactor in solution is not tight, make cobalt manganese in precipitation process, there is oxidation more or less, and then cause nickel cobalt manganese co-precipitation weak effect, obtain tan sediment, and this product impurity content is high, crystallinity is poor, and make homogeneity of product not high, this have impact on the performance of following process battery material further.
Summary of the invention
Technical problem to be solved by this invention is, overcome the deficiency and defect mentioned in above background technology, there is provided that a kind of impurity content is low, the class spherical nickel-cobalt manganese persursor material of high-purity, the high crystalline of good crystallinity, also correspondingly provide that a kind of technological process is simple, automaticity is high, continuous prodution can be realized, the preparation method of the class spherical nickel-cobalt manganese persursor material of product with stable quality excellence.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of class spherical nickel-cobalt manganese persursor material of high-purity, high crystalline, and the chemical molecular formula of described nickel cobalt manganese persursor material is Ni
1-x-yco
xmn
y(OH)
2, wherein 0 < x < 1,0 < y < 1; Mass fraction≤0.012% of the sodium impurity content in described nickel cobalt manganese persursor material, mass fraction≤0.30% of sulfate radical foreign matter content, described nickel cobalt manganese persursor material has high crystalline, and it is characteristic peak 001 intensity>=1100 in XRD collection of illustrative plates characterizes.
As a total technical conceive, the present invention also provides a kind of preparation method of above-mentioned nickel cobalt manganese persursor material, comprise raw material preparation process, co-precipitation step and ripening step, in described raw material preparation process, co-precipitation step and ripening step, have at least a step to have employed anti-oxidation measure.
In above-mentioned preparation method, preferably, anti-oxidation measure in described raw material preparation process comprises: the various raw materials used by subsequent step needs, reagent are purchased with material solution form respectively, forms plurality of raw materials solution, and at least one in plurality of raw materials solution adds reducing agent.Our research shows; owing to there is a small amount of dissolved oxygen in each material solution; although the content of these dissolved oxygens is not high; if but enter into the quality generation material impact of subsequent reactions system meeting to product; and the removal of this dissolved oxygen is not resolved by inert protective gas logical in material solution; because passing into of inert gas can only prevent the oxygen increment in air to be added in material solution, and only have and could remove dissolved oxygen storage in each material solution by adding specific reducing agent.
In above-mentioned preparation method, preferably, described reducing agent is the mixture of one or more in hydrazine hydrate, sodium sulfite, nitrite, and in each material solution, the addition of reducing agent is 0.01% ~ 1% of material solution volume fraction.
In above-mentioned preparation method, preferably, described plurality of raw materials solution comprises precipitant solution, enveloping agent solution and prepares by nickel salt, cobalt salt, manganese salt the mixing salt solution formed, and described mixing salt solution prepares according to the mol ratio of nickel, cobalt, manganese three kinds of elements in standby nickle cobalt lithium manganate of drawing up.Preferred, the addition of reducing agent is 0.02% ~ 0.06% of precipitant solution volume fraction, the addition of reducing agent is 0.02% ~ 0.06% of enveloping agent solution volume fraction, and the addition of reducing agent is 0.02% ~ 0.08% of mixing salt solution volume fraction.
In above-mentioned preparation method, preferably, described nickel salt, cobalt salt, manganese salt are sulfate, and in mixing salt solution, the total concentration of nickel cobalt manganese three kinds of elements controls at 60 ~ 120g/L (more preferably 80 ~ 120g/L); Described precipitant solution is sodium hydrate aqueous solution, and it is 80 ~ 200g/L (more preferably 80 ~ 150g/L) that its concentration controls; Described enveloping agent solution is ammoniacal liquor, and it is 5 ~ 100g/L (more preferably 7 ~ 50g/L) that its concentration controls.
In above-mentioned preparation method, preferred, at the bottom of the reaction in follow-up co-precipitation step, liquid is the mixed solution of NaOH, ammoniacal liquor and reducing agent.At the bottom of described reaction, the initial pH value of liquid preferably controls 10.2 ~ 10.6, and the initial temperature of liquid at the bottom of described reaction is preferably 45 DEG C ~ 55 DEG C, and in reaction end liquid, the initial concentration of ammonia preferably controls at 7g/L ~ 22g/L.
Use some basic seal approach (such as only sealing ring being set) although the precipitation reaction still in other applications existing also has to mention and pass into inert gas shielding; but do not recognize the importance that oxygen barrier seals in existing technique; this often cause seal approach and inert gas shielding measure not comprehensive; also strict not; finally still have influence on the quality of product; therefore in above-mentioned preparation method; preferably, the anti-oxidation measure in described co-precipitation step comprises at least one item in following measures:
(1) thorough seal process is carried out to precipitation reaction still;
(2) continue to pass into inert gas (preferred nitrogen) before coprecipitation reaction and in course of reaction to protect, and in the inner chamber of precipitation reaction still, make inert atmosphere maintain certain normal pressure, to ensure that precipitation environment is in complete anaerobic state.
In above-mentioned preparation method, preferred, the measure of described thorough seal process comprises:
(1) water seal is carried out while mechanical seal being carried out to the shaft of precipitation reaction still;
(2) be connected and sealed by seal washer between the cell body of precipitation reaction still and groove lid;
(3) water seal is carried out by the discharge pipe of precipitation reaction still insertion water.
In above-mentioned preparation method, preferably, in described coprecipitation reaction process, the rotating speed of reactor controls at 160r/min ~ 230r/min, in course of reaction, the temperature of reaction system controls at 45 DEG C ~ 55 DEG C, in reaction system, the concentration of ammonia controls as 10g/L ~ 40g/L, and in reaction system, the overall control of solid matter is 150g/L ~ 250g/L.
In above-mentioned preparation method, preferably, the anti-oxidation measure in described ripening step comprises: the slip after coprecipitation reaction pumps into after washing press carries out ageing reaction, does not carry out Separation of Solid and Liquid and directly pump in pure water drying up after washes clean.
In above-mentioned preparation method, preferably, adopt the alkali lye (preferred sodium hydroxide solution or potassium hydroxide solution) of 5wt% ~ 20wt% (more preferably 10wt% ~ 15wt%) to carry out ageing reaction to slip in described ripening step, ageing reaction temperature is 40 DEG C ~ 80 DEG C (more preferably 40 DEG C ~ 60 DEG C), and the ageing reaction time is 30min ~ 60min; Be adopt deionized water to wash at normal temperatures through the reacted reaction mass of ageing, and washing to pH value is after 7.5 ~ 8.5, carry out after washing drying up, drying, bake out temperature is preferably 90 DEG C ~ 130 DEG C.
In the technical scheme of the invention described above, links anti-oxidation process in the whole technical process of lay special stress on, because our experiment shows, links carries out tight anti-oxidation measure, for the lifting of properties of product and quality, especially purity and crystalline improvement have very important meaning.Therefore, the most preferred scheme links that yes in technique scheme all strictly processes according to every anti-oxidation measure of the present invention, comprise: each material solution before preparation is all by deoxygenation operation, and in co-precipitation step and ripening step, all take above-mentioned corresponding anti-oxidation measure, and the anti-oxidation measure in co-precipitation step not only comprises and carries out thorough seal process to precipitation reaction still, and continue to pass into inert gas protection before comprising coprecipitation reaction and in course of reaction, and in the inner chamber of precipitation reaction still, make inert atmosphere maintain certain normal pressure and protective layer.By the integrated use of above-mentioned every anti-oxidation measure, can ensure that in course of reaction, reactor environment and outside air are close to completely isolated, stop the oxidation of cobalt manganese, ensure the even co-precipitation of nickel cobalt manganese.Meanwhile, in the ripening process of reaction mass, also take corresponding anti-oxidation measure, ensure that slip does not contact with air before non-washes clean.
Compared with prior art, the advantage of technique scheme of the present invention is:
The present invention adopts continuation mode to carry out coprecipitation reaction; technological process is simple; first solution is carried out deoxygenation process before reaction; encapsulation process is carried out to reactor simultaneously; prevent cobalt, manganese oxidized generation high price compound after entering reaction system; the coprecipitation reaction process of effective control manganese element and nickel, cobalt element; thus enable nickel cobalt manganese carry out coprecipitation reaction equably; in ageing process, slip is protected, thus finally prepare the class spherical nickel-cobalt manganese persursor material that crystallinity is high, impurity content is few.
In general, the present invention is compared with existing dry method or other wet processing, the present invention can make manganese element and nickel, cobalt element form co-precipitation equably, prepare characteristic peak 001 intensity>=1100, sodium impurity content≤0.012% in good crystallinity, XRD sign, sulfate radical foreign matter content≤0.30%, tap density>=2.20g/cm
3nickel cobalt manganese persursor material; Not only technological process is simple for preparation method of the present invention, automaticity is high, and can realize continuous prodution, product with stable quality, excellence.
Accompanying drawing explanation
In order to be illustrated more clearly in the embodiment of the present invention or technical scheme of the prior art, be briefly described to the accompanying drawing used required in embodiment or description of the prior art below, apparently, accompanying drawing in the following describes is some embodiments of the present invention, for those of ordinary skill in the art, under the prerequisite not paying creative work, other accompanying drawing can also be obtained according to these accompanying drawings.
Fig. 1 is the XRD figure of the class spherical nickel-cobalt manganese persursor material that the embodiment of the present invention 1 prepares.
Fig. 2 is the scanning electron microscope (SEM) photograph of the class spherical nickel-cobalt manganese persursor material that the embodiment of the present invention 1 prepares.
Embodiment
The specific embodiment of the present invention is as follows:
A class spherical nickel-cobalt manganese persursor material for high-purity, high crystalline, the chemical molecular formula of nickel cobalt manganese persursor material is Ni
1-x-yco
xmn
y(OH)
2, wherein 0 < x < 1,0 < y < 1; Sodium impurity content≤0.012% in nickel cobalt manganese persursor material, sulfate radical foreign matter content≤0.30%, nickel cobalt manganese persursor material has high crystalline, characteristic peak 001 intensity>=1100 during XRD characterizes.
The preparation method of class spherical nickel-cobalt manganese persursor material of the present invention, comprises the following steps:
(1) raw material prepares: first nickel salt, cobalt salt, the preparation of manganese salt are formed mixing salt solution, in mixing salt solution, the total concentration of nickel cobalt manganese three kinds of elements controls at 80 ~ 120g/L; Then nickel cobalt-manganese salt solution is mixed to obtain mixed liquor A (addition of reducing agent is 0.02% ~ 0.08% of mixing salt solution volume fraction) with reducing agent; Again the sodium hydroxide solution of 80 ~ 150g/L and reducing agent are mixed to obtain mixed liquid B (addition of reducing agent is 0.02% ~ 0.06% of sodium hydroxide solution volume fraction); The ammoniacal liquor of 7 ~ 50g/L and reducing agent are mixed to obtain mixed liquor C (addition of reducing agent is 0.02% ~ 0.06% of sodium hydroxide solution volume fraction); Reducing agent is the mixture of one or more in hydrazine water, sodium sulfite, nitrite;
(2) co-precipitation: by the mixed liquor A of above-mentioned preparation, mixed liquid B together with mixed liquor C and stream joins reaction end liquid is housed and carries out the coprecipitation reaction of continous way in the precipitation reaction still of thorough seal process (seal is good), reaction end liquid is the mixed solution of NaOH, ammoniacal liquor and reducing agent, the initial pH value of reaction end liquid controls 10.2 ~ 10.6, the initial temperature of reaction end liquid is 45 DEG C ~ 55 DEG C, and in reaction end liquid, the initial concentration of ammonia controls at 7g/L ~ 22g/L; Constantly pass into nitrogen protection in course of reaction, and in the inner chamber of precipitation reaction still, make inert atmosphere maintain certain normal pressure, to ensure that precipitation environment is in complete anaerobic state; PH value in course of reaction controls 10.5 ~ 11.5, the rotating speed of reactor controls at 160r/min ~ 230r/min, the temperature of reaction system controls at 45 DEG C ~ 55 DEG C, in reaction system, the concentration of ammonia controls as 10g/L ~ 40g/L, in reaction system, the overall control of solid matter is 150g/L ~ 250g/L, reacts completely until raw material is stable;
The measure of thorough seal process comprises: carry out water seal while carrying out mechanical seal to the shaft of precipitation reaction still; Be connected and sealed by seal washer between the cell body of precipitation reaction still and groove lid; The discharge pipe of precipitation reaction still is inserted in water and carries out water seal;
(3) ageing: after stable reaction, ageing reaction is carried out to the slurry overflowed continuously from precipitation reaction still, adopt the alkali lye (sodium hydroxide solution or potassium hydroxide solution) of 10wt% ~ 15wt% to carry out ageing reaction to slip in ripening step, ageing reaction temperature is 40 DEG C ~ 60 DEG C, the ageing reaction time is 30min ~ 60min, do not carry out Separation of Solid and Liquid at normal temperatures and directly pump in deionized water washing through the reacted reaction mass of ageing, and washing to pH value is after 7.5 ~ 8.5, dry up after washes clean in pure water, dry, bake out temperature is 90 DEG C ~ 130 DEG C, the impurity content obtaining anode material for lithium-ion batteries after oven dry is low, the class spherical nickel-cobalt manganese persursor material that crystallinity is high.
For the ease of understanding the present invention, hereafter will do to describe more comprehensively, meticulously to the present invention in conjunction with Figure of description and preferred embodiment, but protection scope of the present invention is not limited to following specific embodiment.
Unless otherwise defined, hereinafter used all technical terms are identical with the implication that those skilled in the art understand usually.The object of technical term used herein just in order to describe specific embodiment is not be intended to limit the scope of the invention.
Unless otherwise specified, the various raw material, reagent, instrument and equipment etc. used in the present invention are all bought by market and are obtained or prepare by existing method.
Embodiment 1:
A class spherical nickel-cobalt manganese persursor material for high-purity, high crystalline of the present invention as shown in Figure 1 and Figure 2, the chemical molecular formula of nickel cobalt manganese persursor material is Ni
1-x-yco
xmn
y(OH)
2, wherein 0 < x < 1,0 < y < 1; Sodium impurity content in nickel cobalt manganese persursor material is 0.006%, and sulfate radical content is 0.12%, and nickel cobalt manganese persursor material has high crystalline, and during XRD characterizes, characteristic peak 001 intensity is 1256.
The preparation method of the class spherical nickel-cobalt manganese persursor material of the present embodiment, comprises the following steps:
(1) first nickelous sulfate, manganese sulfate and cobaltous sulfate are prepared formation mixing salt solution with after water-soluble solution respectively, in mixing salt solution, the total concentration of nickel cobalt manganese three kinds of elements controls at 115g/L, and wherein the mol ratio of nickel, cobalt, manganese metal ion is 5: 2: 3; Then nickel cobalt-manganese salt solution is mixed to obtain mixed liquor A (hydrazine hydrate addition is 0.05% of mixing salt solution volume fraction) with reducing agent hydrazine hydrate; Again the sodium hydroxide solution of 80g/L and reducing agent are mixed to obtain mixed liquid B (hydrazine hydrate addition is 0.04% of sodium hydroxide solution volume fraction); The ammoniacal liquor of 20g/L and reducing agent hydrazine hydrate are mixed to obtain mixed liquor C (addition of hydrazine hydrate is 0.04% of sodium hydroxide solution volume fraction);
(2) prepare before reaction: in precipitation reaction still, add pure water, carry out thorough seal process to precipitation reaction still, the measure of thorough seal process comprises: carry out water seal while carrying out mechanical seal to the shaft of precipitation reaction still; Be connected and sealed by seal washer between the cell body of precipitation reaction still and groove lid; The discharge pipe of precipitation reaction still is imbedded in water; Then nitrogen is passed into, add sodium hydroxide solution adjust ph to 10.5 again, add ammoniacal liquor simultaneously and regulate ammonia ion concentration to 15g/L, the reducing agent simultaneously adding 0.05% obtains reaction end liquid, the initial temperature controlling reaction end liquid, at 50 ± 1 DEG C, ensures to form nitrogen blanket in reactor;
(3) co-precipitation: the mixed liquor A of above-mentioned preparation, mixed liquid B are flowed through measuring pump and join and above-mentioned reaction end liquid and in the precipitation reaction still of thorough seal process (seal is good) is housed together with mixed liquor C, start the coprecipitation reaction carrying out continous way, constantly nitrogen protection is passed in course of reaction, and in the inner chamber of precipitation reaction still, make inert atmosphere maintain certain normal pressure, to ensure that precipitation environment is in complete anaerobic state; PH value in course of reaction controls 10.6 ~ 11.1, the rotating speed of reactor controls at 220r/min, the temperature of reaction system controls at 50 ± 1 DEG C, in reaction system, the concentration of ammonia controls as 15g/L, in reaction system, the overall control of solid matter is 150g/L ~ 250g/L, continous-stable reaction 20h ~ 24h, reacts completely until raw material is stable;
(4) ripening: after stable reaction, ageing reaction is carried out to the slurry overflowed continuously from precipitation reaction still, adopt the alkali lye (sodium hydroxide solution or potassium hydroxide solution) of 15wt% to carry out ageing reaction to slip in ripening step, ageing reaction temperature is 60 DEG C, the ageing reaction time is 45min ~ 60min, do not carry out Separation of Solid and Liquid at normal temperatures and directly pump in deionized water washing through the reacted reaction mass of ageing, and washing to pH value is after 8.0, dry up after washes clean in pure water, dry, bake out temperature is 125 DEG C, the impurity content obtaining anode material for lithium-ion batteries after oven dry is low, the class spherical nickel-cobalt manganese persursor material A that crystallinity is high.
Comparative example 2:
In the present embodiment, reactor does not do thorough seal process, and all the other conditions, with embodiment 1, are settled out yellowish-brown slip, obtained nickel cobalt manganese persursor material B.
Comparative example 3:
Do not add reducing agent in each material solution in the present embodiment, all the other conditions, with embodiment 1, are settled out yellowish-brown slip, obtained nickel cobalt manganese persursor material C.
Comparative example 4:
In the present embodiment, slip first filters and dries up ageing again, and all the other conditions, with embodiment 1, are settled out greyish white slip, obtained nickel cobalt manganese persursor material D.
To nickel cobalt manganese persursor material A, B, C and D prepared by four examples above, detect, concrete outcome sees the following form 1:
Table 1: the performance test of nickel cobalt manganese persursor material
As can be seen from the data of upper table 1, by carrying out anti-oxidation process to solution deoxygenation, coprecipitation process and ageing process, produce the presoma good crystallinity obtained, impurity content is low.
Claims (10)
1. a class spherical nickel-cobalt manganese persursor material for high-purity, high crystalline, the chemical molecular formula of described nickel cobalt manganese persursor material is Ni
1-x-yco
xmn
y(OH)
2, wherein 0 < x < 1,0 < y < 1; It is characterized in that: mass fraction≤0.012% of the sodium impurity content in described nickel cobalt manganese persursor material, mass fraction≤0.30% of sulfate radical foreign matter content, described nickel cobalt manganese persursor material has high crystalline, and it is characteristic peak 001 intensity>=1100 in XRD collection of illustrative plates characterizes.
2. the preparation method of a nickel cobalt manganese persursor material as claimed in claim 1, comprise raw material preparation process, co-precipitation step and ripening step, it is characterized in that: in described raw material preparation process, co-precipitation step and ripening step, have at least a step to have employed anti-oxidation measure.
3. preparation method according to claim 2, it is characterized in that, anti-oxidation measure in described raw material preparation process comprises: the various raw materials used by subsequent step needs, reagent are purchased with material solution form respectively, form plurality of raw materials solution, and at least one in plurality of raw materials solution adds reducing agent.
4. preparation method according to claim 3, it is characterized in that, described reducing agent is the mixture of one or more in hydrazine hydrate, sodium sulfite, nitrite, and in each material solution, the addition of reducing agent is 0.01% ~ 1% of material solution volume fraction.
5. the preparation method according to claim 3 or 4, it is characterized in that, described plurality of raw materials solution comprises precipitant solution, enveloping agent solution and prepares by nickel salt, cobalt salt, manganese salt the mixing salt solution formed, and described mixing salt solution prepares according to the mol ratio of nickel, cobalt, manganese three kinds of elements in standby nickle cobalt lithium manganate of drawing up.
6. preparation method according to claim 5, is characterized in that, described nickel salt, cobalt salt, manganese salt are sulfate, and in mixing salt solution, the total concentration of nickel cobalt manganese three kinds of elements controls at 60 ~ 120g/L; Described precipitant solution is sodium hydrate aqueous solution, and it is 80 ~ 200g/L that its concentration controls; Described enveloping agent solution is ammoniacal liquor, and it is 5 ~ 100g/L that its concentration controls.
7. the preparation method according to any one of claim 2 ~ 6, is characterized in that, the anti-oxidation measure in described co-precipitation step comprises at least one item in following measures:
(1) thorough seal process is carried out to precipitation reaction still;
(2) continue to pass into inert gas protection before coprecipitation reaction and in course of reaction, and in the inner chamber of precipitation reaction still, make inert atmosphere maintain certain normal pressure.
8. preparation method according to claim 7, is characterized in that, the measure of described thorough seal process comprises:
(1) water seal is carried out while mechanical seal being carried out to the shaft of precipitation reaction still;
(2) be connected and sealed by seal washer between the cell body of precipitation reaction still and groove lid;
(3) water seal is carried out by the discharge pipe of precipitation reaction still insertion water.
9. the preparation method according to any one of claim 2 ~ 8, it is characterized in that, anti-oxidation measure in described ripening step comprises: the slip after coprecipitation reaction pumps into after washing press carries out ageing reaction, does not carry out Separation of Solid and Liquid and directly pump in pure water drying up after washes clean.
10. preparation method according to claim 9, is characterized in that, is to adopt the alkali lye of 5wt% ~ 20wt% to carry out ageing reaction to slip in described ripening step, and ageing reaction temperature is 40 DEG C ~ 80 DEG C, and the ageing reaction time is 30min ~ 60min; Be adopt deionized water to wash at normal temperatures through the reacted reaction mass of ageing, and washing to pH value is after 7.5 ~ 8.5, carries out drying up, drying after washing.
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