CN103232075B - Preparation method for cobalt oxyhydroxide - Google Patents
Preparation method for cobalt oxyhydroxide Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- -1 cobalt oxyhydroxide Chemical compound 0.000 title abstract 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 108
- 239000000243 solution Substances 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000003647 oxidation Effects 0.000 claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 14
- 238000007664 blowing Methods 0.000 claims abstract description 9
- 150000001868 cobalt Chemical class 0.000 claims abstract description 8
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 5
- 239000008139 complexing agent Substances 0.000 claims abstract description 5
- 238000001914 filtration Methods 0.000 claims abstract description 3
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 claims description 38
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 12
- 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
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 230000001105 regulatory effect Effects 0.000 claims description 7
- 229910021529 ammonia Inorganic materials 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 230000002829 reductive effect Effects 0.000 claims description 4
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims 1
- 230000001276 controlling effect Effects 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 10
- 239000002002 slurry Substances 0.000 abstract description 8
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract 1
- 239000003638 chemical reducing agent Substances 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- 238000005086 pumping Methods 0.000 abstract 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 32
- 229910017052 cobalt Inorganic materials 0.000 description 31
- 239000010941 cobalt Substances 0.000 description 31
- 239000000047 product Substances 0.000 description 22
- 239000000463 material Substances 0.000 description 17
- 239000003513 alkali Substances 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 11
- 229910052744 lithium Inorganic materials 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 230000003252 repetitive effect Effects 0.000 description 10
- 239000013078 crystal Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000001681 protective effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 239000010405 anode material Substances 0.000 description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- KSKLUYZQGNZTOY-UHFFFAOYSA-J O[Co](O)(O)O Chemical compound O[Co](O)(O)O KSKLUYZQGNZTOY-UHFFFAOYSA-J 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 229910002640 NiOOH Inorganic materials 0.000 description 1
- 238000012356 Product development Methods 0.000 description 1
- 241001074085 Scophthalmus aquosus Species 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- RFYUQSQGLHNNOY-UHFFFAOYSA-N cobalt;sulfuric acid Chemical compound [Co].OS(O)(=O)=O RFYUQSQGLHNNOY-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001965 increasing effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000010295 mobile communication Methods 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000007704 wet chemistry method Methods 0.000 description 1
Abstract
The present invention provides a preparation method for large-grained spherical cobalt oxyhydroxide. The specific method is as follows: (1) preparing a 0.5-2.0mol / L cobalt salt solution and a 5-10mol / L sodium hydroxide solution, and adding a complexing agent and a reducing agent in the sodium hydroxide solution; (2) under the protection of nitrogen, simultaneously pumping the cobalt salt solution and the sodium hydroxide solution prepared in the step (1) into a reaction vessel for a continuous reaction, wherein a pH value is controlled to be in a range of 10-12 by adjusting the flow rate of the sodium hydroxide solution, and a slurry particle size is controlled to be in a range of 15-20 microns; (3) obtaining cobalt hydroxide with good sphericity and crystallinity, washing and filtering, controlling a water content in a range of 10-30%, transferring into an oxidation reactor, and blowing air in for oxidation; and (4) placing the oxidized slurry into a blast oven for drying to obtain the large-grained spherical cobalt oxyhydroxide.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic materials, specifically, relate to a kind of preparation method of hydroxy cobalt oxide.
Background technology
Since the eighties, cobalt powder, as the activator of high tension battery discharge and recharge, is applied to rechargeable battery field in large quantities.The early 1990s, sub-cobalt material successfully adds in battery raw material by day, De Deng state scientist, becomes the high value of battery industry research and development, high-tech product.The compound of the cobalt such as cobalt powder and cobalt oxyhydrogen powder, as a kind of battery material additive of excellent property, can improve Ni (OH)
2proton conducting, reduce oxidizing potential, improve oxygen evolution potential, to raising electrode performance have unusual effect.Phase can ensure that electrode fully charges before charging, makes Ni (OH)
2fully be converted into NiOOH, contain the precipitation of oxygen simultaneously, improve charging efficiency, increase electrode specific storage.In recent years, along with the development of lithium ion battery, cobalt/cobalt oxide, as the raw material preparing lithium ion battery electrode material, also makes its consumption constantly increase.The cobalt acid lithium of China is produced fast-developing in recent years, thus to Co
30
4demand also corresponding swift and violent increase.Cell-grade Co
30
4as the main raw material of lithium ion cell anode material lithium cobaltate, also increase with the demand increase of lithium-ion secondary cell.The total amount consumed of global cobalt in 2002 is 8,800 ten thousand pounds, and the brill share be applied in battery industry rises rapidly and reaches 32%.And along with the further growth of small-sized discrete movable power source demand, the picture fast development of mobile communication and the quick growth of notebook computer popularity rate, for lithium ion battery industrial expansion creates better opportunity, accordingly, to anode material for lithium-ion batteries LiCo0
2demand also increase substantially.The application expecting cobalt in 2015 will reach 2.3 hundred million pounds, wherein 56% will be applied in lithium cell industry.
Along with portable type electronic product development, also new requirement is constantly proposed to its battery used.The smart mobile phone particularly continued to bring out and panel computer higher to battery durable Capability Requirement, especially panel computer, great majority all adopt embedded battery project organization, non-dismountable, battery durable ability become its development weakness.The so-called a kind of high-energy-density positive electrode material of cobalt acid lithium is the main positive electrode material of current smart mobile phone and dull and stereotyped computer battery.
One of basic raw material that hydroxy cobalt oxide is produced as cobalt acid lithium, both the compound preparing various cobalt had been suitable for, also be suitable for preparing highly active lithium ion cell anode material lithium cobaltate, colleague, hydroxy cobalt oxide also can be used as the additive of battery, in the process of charging, be formed into spot net, improve charge-discharge performance and the cycle life of battery, therefore, hydroxy cobalt oxide has higher development prospect.
Patent application 201210016504.3 disclose a kind of hydroxy cobalt oxide preparation method, this method is by adding the direct synthesis of hydroxy cobalt oxide of method of oxygenant in reaction process.Patent application 201110327857.0 discloses the method that hydroxyl trivalent cobalt oxide production cobalt acid lithium is produced in the reaction of a kind of wet chemistry, this method first synthesizes hydroxide cobalt, and then by clorox, hydroxide cobalt oxidation is become hydroxyl trivalent cobalt oxide, finally make cobalt acid lithium by sintering again.Patent application 201010117854.X discloses a kind of method preparing trihydroxy cobalt hydroxide, and this method synthesizes trihydroxy cobalt hydroxide by hydrothermal method.But the pattern of the hydroxy cobalt oxide that above-mentioned disclosed method is produced is not that class is spherical, the uneven of downstream industry batch mixing can be caused, reduce efficiency and the effect of batch mixing, and product stability is poor, in building-up process, add oxygenant can cause the uneven of reaction, be difficult to possess production in enormous quantitiesization.
Summary of the invention
For the defect existed in prior art, the object of this invention is to provide a kind of preparation method of large granular spherical hydroxy cobalt oxide, for producing the raw material that cobalt acid lithium provides stability strong in enormous quantities, increasing effect and the efficiency of batch mixing.
In order to realize object of the present invention, the invention provides a kind of preparation method of hydroxy cobalt oxide, concrete steps are as follows:
(1) prepare the cobalt salt solution of 0.5-2.0mol/L and the sodium hydroxide solution of 5-10mol/L, and in sodium hydroxide solution, add complexing agent and reductive agent;
(2) at pH value 10-12, temperature 40-70 DEG C, rotating speed 300-400 rev/min under condition in nitrogen protection, pump into the obtained cobalt salt solution of step (1) and sodium hydroxide solution in reactor simultaneously, and by regulating the flow control pH value 10-12 of sodium hydroxide solution, successive reaction, obtains slip;
(3) draw the hydroxide cobalt of sphericity, better crystallinity degree, washing and filtering, by water content control between 10-30%, proceed in stills for air blowing, blast air, be oxidized;
(4) slip after oxidation is put into convection oven, dry, to obtain final product.
Particularly, the cobalt salt solution in described step (1) is CoSO
4, CoCl
2or Co
3(NO
3)
2one or more.
As preferably, add complexing agent in described step (1) for adding 0.5-1.5L ammonia content 25% ammoniacal liquor in often liter of sodium hydroxide solution, or 50-100 gram of disodium ethylene diamine tetraacetate.
As preferably, the interpolation reductive agent in described step (1) is the hydrazine hydrate solution adding 20-50 milliliter content 80% in often liter of sodium hydroxide solution.
As preferably, after described step (2) successive reaction, obtain Slurry Granularity and control between 15-20 micron.
As preferably, described step proceeds in stills for air blowing in (3), blasts air, be oxidized at 100-200 DEG C of temperature.
As preferably, the time of described oxidation is 3-6 hour.
As preferably, the slip after oxidation is put into convection oven by described step (4), dries, to obtain final product in 120 DEG C of situations.
Present invention also offers above-mentioned preparation method and produce the hydroxyl oxidize cobalt granule obtained.
Present invention also offers above-mentioned preparation method and produce the application in hydroxy cobalt oxide.
The preparation method of a kind of large granular spherical hydroxy cobalt oxide provided by the invention, producing the hydroxy cobalt oxide obtained is that class is spherical, and downstream industry batch mixing can be made even, and product stability is strong, can be the raw material produced cobalt acid lithium in enormous quantities and provide stability strong, increase effect and the efficiency of batch mixing.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the hydroxy cobalt oxide that the preparation method of a kind of hydroxy cobalt oxide of the present invention obtains;
Fig. 2 is the SEM figure of the hydroxy cobalt oxide that the preparation method of a kind of hydroxy cobalt oxide of the present invention obtains;
The SEM figure of the hydroxy cobalt oxide that Fig. 3 obtains for the preparation method of hydroxy cobalt oxide disclosed in patent application 201210016504.3.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.
Embodiment 1
1, cobalt liquid configuration: weigh 1.5 kilograms of cobalt chloride crystal, and add deionized water and dissolve, be settled to 5 liters, for configuring enough cobalt liquid, above step can repetitive operation;
2, alkali lye configuration: weigh 1 kilogram sodium hydroxide crystal, add deionized water and dissolve, be settled to 3 liters, and then add the hydrazine hydrate solution of 0.7L ammonia content 25% ammoniacal liquor and 20 milliliters of content 80%, finally be settled to 5L, for configuring enough alkali lye, above step can repetitive operation;
3, cleaning reaction still, at pH value 11.1, temperature 65 DEG C, rotating speed (300-rev/min) under keeping the protective condition of nitrogen, pump into the cobalt liquid of step 1 and the alkali lye of step 2 simultaneously, and by regulating sodium hydroxide stability of flow to control pH value 11.1, successive reaction, after charging in 12 hours, detecting Slurry Granularity between 15-20 micron, is now qualified product;
4, slip granularity being reached 15-20 micron takes out, after centrifugation, washing 3 times, obtain the pink material of water content 12%, proceed to again in stills for air blowing, open stirring to heat up, temperature controls, at 150 DEG C, to blast air, after oxidation in 4 hours, obtain the hydroxy cobalt oxide material of black.
5, convection oven is put in the sabot of black material, after 120 DEG C dry, obtain black powder product, be product hydroxy cobalt oxide.As shown in Figure 1, SEM figure is similar with Fig. 2 for the hydroxy cobalt oxide XRD figure obtained.
Embodiment 2.
1, cobalt liquid configuration: weigh 2.2 kilograms of cobalt chloride crystal, and add deionized water and dissolve, be settled to 5 liters, for configuring enough cobalt liquid, above step can repetitive operation;
2, alkali lye configuration: weigh 1 kilogram sodium hydroxide crystal, add deionized water and dissolve, be settled to 3 liters, and then add the hydrazine hydrate solution of 0.9L ammonia content 25% ammoniacal liquor and 20 milliliters of content 80%, finally be settled to 5L, for configuring enough alkali lye, above step can repetitive operation;
3, cleaning reaction still, at pH value 10.9, temperature 50 C, rotating speed (350-rev/min) under keeping the protective condition of nitrogen, pump into the cobalt liquid of step 1 and the alkali lye of step 2 simultaneously, and by regulating sodium hydroxide stability of flow to control pH value 10.9, successive reaction, after charging in 12 hours, detecting Slurry Granularity between 15-20 micron, is now qualified product;
4, slip granularity being reached 15-20 micron takes out, after centrifugation, washing 3 times, obtain the pink material of water content 12%, proceed to again in stills for air blowing, open stirring to heat up, temperature controls, at 100 DEG C, to blast air, after oxidation in 3 hours, obtain the hydroxy cobalt oxide material of black.
5, convection oven is put in the sabot of black material, after 120 DEG C dry, obtain black powder product, be product hydroxy cobalt oxide.The hydroxy cobalt oxide XRD figure obtained and Fig. 1 similar, SEM figure as Fig. 2.
Embodiment 3
1, cobalt liquid configuration: weigh 1.9 kilo sulfuric acid cobalt crystal, and add deionized water and dissolve, be settled to 5 liters, for configuring enough cobalt liquid, above step can repetitive operation;
2, alkali lye configuration: weigh 1 kilogram sodium hydroxide crystal, add deionized water and dissolve, be settled to 3 liters, and then add the hydrazine hydrate solution of 0.9L ammonia content 25% ammoniacal liquor and 20 milliliters of content 80%, finally be settled to 5L, for configuring enough alkali lye, above step can repetitive operation;
3, cleaning reaction still, at pH value 11.5, temperature 40 DEG C, rotating speed (400-rev/min) under keeping the protective condition of nitrogen, pump into the cobalt liquid of step 1 and the alkali lye of step 2 simultaneously, and by regulating sodium hydroxide stability of flow to control pH value 11.5, successive reaction, after charging in 12 hours, detecting Slurry Granularity between 15-20 micron, is now qualified product;
4, slip granularity being reached 15-20 micron takes out, after centrifugation, washing 3 times, obtain the pink material of water content 12%, proceed to again in stills for air blowing, open stirring to heat up, temperature controls, at 120 DEG C, to blast air, after oxidation in 5 hours, obtain the hydroxy cobalt oxide material of black.
5, convection oven is put in the sabot of black material, after 120 DEG C dry, obtain black powder product, be product hydroxy cobalt oxide.The hydroxy cobalt oxide XRD figure obtained and Fig. 1 similar, SEM figure with Fig. 2 similar.
Embodiment 4
1, cobalt liquid configuration: weigh 2.5 kilograms of cobalt chloride crystal, and add deionized water and dissolve, be settled to 5 liters, for configuring enough cobalt liquid, above step can repetitive operation;
2, alkali lye configuration: weigh 2 kilogram sodium hydroxide crystal, add deionized water and dissolve, be settled to 3 liters, and then add the hydrazine hydrate solution of 1.2L ammonia content 25% ammoniacal liquor and 40 milliliters of content 80%, finally be settled to 5L, for configuring enough alkali lye, above step can repetitive operation;
3, cleaning reaction still, at pH value 12, temperature 70 C, rotating speed (380-rev/min) under keeping the protective condition of nitrogen, pump into the cobalt liquid of step 1 and the alkali lye of step 2 simultaneously, and by regulating sodium hydroxide stability of flow to control pH value 12, successive reaction, after charging in 12 hours, detecting Slurry Granularity between 15-20 micron, is now qualified product;
4, slip granularity being reached 15-20 micron takes out, after centrifugation, washing 3 times, obtain the pink material of water content 12%, proceed to again in stills for air blowing, open stirring to heat up, temperature controls, at 180 DEG C, to blast air, after oxidation in 5 hours, obtain the hydroxy cobalt oxide material of black.
5, convection oven is put in the sabot of black material, after 120 DEG C dry, obtain black powder product, be product hydroxy cobalt oxide.The hydroxy cobalt oxide XRD figure obtained and Fig. 1 similar, SEM figure with Fig. 2 similar.
Embodiment 5
1, cobalt liquid configuration: weigh 2.2 kilograms of cobalt nitrate crystalses, and add deionized water and dissolve, be settled to 5 liters, for configuring enough cobalt liquid, above step can repetitive operation;
2, alkali lye configuration: weigh 2 kilogram sodium hydroxide crystal, add deionized water and dissolve, be settled to 3 liters, and then add the hydrazine hydrate solution of 60 grams of disodium ethylene diamine tetraacetate and 40 milliliters of content 80%, finally be settled to 5L, for configuring enough alkali lye, above step can repetitive operation;
3, cleaning reaction still, at pH value 10, temperature 45 C, rotating speed (340-rev/min) under keeping the protective condition of nitrogen, pump into the cobalt liquid of step 1 and the alkali lye of step 2 simultaneously, and by regulating sodium hydroxide stability of flow to control pH value 10, successive reaction, after charging in 12 hours, detecting Slurry Granularity between 15-20 micron, is now qualified product;
4, slip granularity being reached 15-20 micron takes out, after centrifugation, washing 3 times, obtain the pink material of water content 12%, proceed to again in stills for air blowing, open stirring to heat up, temperature controls, at 200 DEG C, to blast air, after oxidation in 6 hours, obtain the hydroxy cobalt oxide material of black.
5, convection oven is put in the sabot of black material, after 120 DEG C dry, obtain black powder product, be product hydroxy cobalt oxide.The hydroxy cobalt oxide XRD figure obtained and Fig. 1 similar, SEM figure with Fig. 2 similar.
Embodiment 6
Disclosed in patent application 201210016504.3, the preparation method of hydroxy cobalt oxide, obtains product hydroxy cobalt oxide.Obtain hydroxy cobalt oxide SEM to scheme as shown in Figure 3.
By comparison diagram 2 and Fig. 3, can obviously see, the product uniformity coefficient that the present invention obtains is better, and the product obtained than documents is in shape spherical closer to class, to the stability of downstream industry batch mixing homogeneity and product, there is better effect, can be the raw material produced cobalt acid lithium in enormous quantities and provide stability strong, increase effect and the efficiency of batch mixing.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (3)
1. a preparation method for hydroxy cobalt oxide, is characterized in that, concrete steps are as follows:
(1) preparing concentration of cobalt ions is the cobalt salt solution of 0.5-2.0mol/L and the sodium hydroxide solution of 5-10mol/L, and in sodium hydroxide solution, add complexing agent and reductive agent;
(2) at pH value 10-12, temperature 40-70 DEG C, rotating speed 300-400 rev/min under condition in nitrogen protection, pump into the obtained cobalt salt solution of step (1) and sodium hydroxide solution in reactor simultaneously, and by regulating the flow control pH value 10-12 of sodium hydroxide solution, successive reaction, obtains the slip of Task-size Controlling between 15-20 micron;
(3) draw the hydroxide cobalt of sphericity, better crystallinity degree, washing and filtering, by water content control between 10-30%, proceed in stills for air blowing, at 100-200 DEG C of temperature, blast air, be oxidized; The time of oxidation is 3-6 hour;
(4) slip after oxidation is put into convection oven, dry, to obtain final product;
Wherein, add complexing agent in described step (1) for adding 0.5-1.5L ammonia content 25% ammoniacal liquor in often liter of sodium hydroxide solution, or 50-100 gram of disodium ethylene diamine tetraacetate;
Interpolation reductive agent in described step (1) is the hydrazine hydrate solution adding 20-50 milliliter content 80% in often liter of sodium hydroxide solution.
2. preparation method according to claim 1, is characterized in that, the cobalt salt solution in described step (1) is CoSO
4, CoCl
2or Co (NO
3)
2one or more.
3. preparation method according to claim 1, is characterized in that, the slip after oxidation is put into convection oven by described step (4), dries, to obtain final product in 120 DEG C of situations.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105129869A (en) * | 2015-08-28 | 2015-12-09 | 上饶市鼎鑫金属化工有限公司 | Novel ammonia-free continuous production technology of spherical large-particle-size CoOOH |
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