CN1274602C - Cobaltosic oxide preparation method for lithium ion battery - Google Patents
Cobaltosic oxide preparation method for lithium ion battery Download PDFInfo
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- CN1274602C CN1274602C CNB2003101153167A CN200310115316A CN1274602C CN 1274602 C CN1274602 C CN 1274602C CN B2003101153167 A CNB2003101153167 A CN B2003101153167A CN 200310115316 A CN200310115316 A CN 200310115316A CN 1274602 C CN1274602 C CN 1274602C
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- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(2+);cobalt(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims description 68
- 238000002360 preparation method Methods 0.000 title claims description 46
- 239000010941 cobalt Substances 0.000 claims abstract description 61
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 61
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 59
- 238000001354 calcination Methods 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000002994 raw material Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 40
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001868 cobalt Chemical class 0.000 claims abstract description 30
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 claims abstract description 17
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims abstract description 14
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 14
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 claims abstract description 14
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000001301 oxygen Substances 0.000 claims abstract description 7
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 7
- 239000000843 powder Substances 0.000 claims description 49
- 239000003795 chemical substances by application Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- 239000007864 aqueous solution Substances 0.000 claims description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 239000000463 material Substances 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 22
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical group C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 20
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 19
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 15
- VBIXEXWLHSRNKB-UHFFFAOYSA-N ammonium oxalate Chemical compound [NH4+].[NH4+].[O-]C(=O)C([O-])=O VBIXEXWLHSRNKB-UHFFFAOYSA-N 0.000 claims description 15
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 229910000428 cobalt oxide Inorganic materials 0.000 claims description 14
- 238000005507 spraying Methods 0.000 claims description 14
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 claims description 13
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 239000012452 mother liquor Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- SVTBMSDMJJWYQN-UHFFFAOYSA-N 2-methylpentane-2,4-diol Chemical compound CC(O)CC(C)(C)O SVTBMSDMJJWYQN-UHFFFAOYSA-N 0.000 claims description 5
- 241000220317 Rosa Species 0.000 claims description 5
- 229940051250 hexylene glycol Drugs 0.000 claims description 5
- 239000012798 spherical particle Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 13
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 abstract description 8
- 229910052744 lithium Inorganic materials 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 4
- 238000007254 oxidation reaction Methods 0.000 abstract description 4
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- GPKIXZRJUHCCKX-UHFFFAOYSA-N 2-[(5-methyl-2-propan-2-ylphenoxy)methyl]oxirane Chemical compound CC(C)C1=CC=C(C)C=C1OCC1OC1 GPKIXZRJUHCCKX-UHFFFAOYSA-N 0.000 abstract 6
- 238000004227 thermal cracking Methods 0.000 abstract 2
- 229910021446 cobalt carbonate Inorganic materials 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 27
- 230000005540 biological transmission Effects 0.000 description 11
- UPWOEMHINGJHOB-UHFFFAOYSA-N oxo(oxocobaltiooxy)cobalt Chemical compound O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 description 8
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 5
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000001099 ammonium carbonate Substances 0.000 description 5
- 230000005587 bubbling Effects 0.000 description 5
- 239000012467 final product Substances 0.000 description 5
- 229910021529 ammonia Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 230000009466 transformation Effects 0.000 description 3
- 230000003245 working effect Effects 0.000 description 3
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- 238000001149 thermolysis Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- NICDRCVJGXLKSF-UHFFFAOYSA-N nitric acid;trihydrochloride Chemical compound Cl.Cl.Cl.O[N+]([O-])=O NICDRCVJGXLKSF-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- NSRBDSZKIKAZHT-UHFFFAOYSA-N tellurium zinc Chemical compound [Zn].[Te] NSRBDSZKIKAZHT-UHFFFAOYSA-N 0.000 description 1
- -1 this Chemical compound 0.000 description 1
Images
Classifications
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- 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 present invention discloses a method for preparing tricobalt tetraoxide used for a lithium ion battery. Cobalt oxalate or cobalt hydroxide or cobalt carbonate is used as a raw material and is calcined in three stages; in the calcination stage, the thermal cracking and the oxidation of cobalt salts are divided into two courses; in the thermal cracking course of the cobalt salts, no oxidizing agent is provided, and all the cobalt salts are converted into cobaltous oxide; then, temperature is increased to the oxidizing temperature, and the oxygen atmosphere or the air atmosphere is provided; thus, all the cobaltous oxide is converted into tricobalt tetraoxide. In products prepared by the method, the conversion rate of the tricobalt tetraoxide is high, and the other oxides of cobalt are less; furthermore, the tricobalt tetraoxide has the advantages of uniform granularity and large loose packed density; in addition, when the cobalt salts are prepared, various operation parameters are properly controlled, and spheroid cobalt salt particles can be obtained; tricobalt tetraoxide obtained by using the spheroid cobalt salt particles as raw materials has ideal granularity and loose packed density; when the tricobalt tetraoxide prepared by using the method provided by the present invention is used as the raw material of the lithium cobaltate of the positive electrode of the lithium ion battery, the electronic property and the service life of the lithium ion battery can be improved.
Description
Technical field
The present invention relates to the preparation field of metal oxide, a kind of raw material preparation method of cobalt oxide that can be used as lithium ion cell anode material lithium cobaltate is provided.
Background technology
Positive electrode material in the lithium ion battery mainly is a cobalt acid lithium, and the critical material of preparation cobalt acid lithium is a tricobalt tetroxide, the performance of tricobalt tetroxide is relevant to the performance of cobalt acid lithium material, then by cobalt acid lithium to great effect is all arranged in charge/discharge capacity, electric conductivity and work-ing life etc. of battery.The tricobalt tetroxide that is used for battery has strict requirement on chemical ingredients, the method for preparing the both economical practicality of tricobalt tetroxide in the prior art is the calcining thermal decomposition method, that is: will at high temperature calcine and obtain tricobalt tetroxide such as cobalt salts such as cobaltous carbonate, cobaltous hydroxide or cobalt oxalates.
Cobalt is a valence variation element (divalent, 3 valencys), and its oxide compound has cobaltous oxide (CoO), cobalt sesquioxide (Co
2O
3) and tricobalt tetroxide (Co
3O
4), it is best that wherein tricobalt tetroxide is used as the battery raw material effect.Experiment learns, if in the calcining thermal decomposition process in Heating temperature, heat-up time and the heating space condition control such as gas atmosphere improper, more CoO or Co will appear
2O
3, make Co in the product
3O
4Production rate reduce, thereby influence the quality of the sour lithium of cobalt.In addition, be used as the Co of battery raw material
3O
4, its physical index, particularly size composition, distribution and loose density also there are particular requirement, the general requirement size ratio is more even, and loose density is bigger.To being used for the high power battery of electrical source of power, the requirement of its size-grade distribution and loose density is then strict more.The control of each operational condition is also influential to the granularity and the loose density of product in calcination process.More than these contents all do not give enough attentions in the prior art.Calcining to cobalt salt in the prior art is placed into it in calcining furnace often, and bubbling air or oxygen carry out a section calcining, is disclosed " manufacture method of tricobalt tetroxide " in the application for a patent for invention prospectus of CN1376638A as publication number.In addition, Co
3O
4The granularity of product and loose density also have very big influence with the granularity and the granule-morphology of its presoma cobalt salt, and the control of various operational conditions also is very important in the preparation cobalt salt, but does not relate in the prior art.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of cobalt oxide that is used as the high power battery raw material of lithium ion battery and electrical source of power, the transformation efficiency height of tricobalt tetroxide in the product that makes by present method, other oxide compound of cobalt is few, and epigranular, loose density are big, the electric property and the work-ing life that help improving battery.
The object of the present invention is achieved like this:
Use cobalt oxalate or cobaltous hydroxide or cobaltous carbonate to make raw material, the granularity of this cobalt raw material is D
50=2-8 μ m;
The method for preparing tricobalt tetroxide the steps include: above-mentioned raw materials is carried out three section calcinings:
A, a section calcining:
Place calciner to heat in described cobalt raw material powder, Heating temperature is at 200-450 ℃, and preferred Heating temperature is 250-350 ℃, and be 2-5 hour heat-up time, is nitrogen atmosphere in the calciner; Be that moisture remaining in the cobalt raw material powder and/or crystal water are removed in this process;
B, two section calcinings:
To place under the 500-800 ℃ of temperature through the material that previous step is handled and heat, preferred Heating temperature is 550-700 ℃, and be 1-5 hour heat-up time, still is nitrogen atmosphere in the calciner; Cobalt raw material is thermally cracked to cobaltous oxide in this process;
C, three section calcinings:
To place under the 700-1000 ℃ of temperature through the material that previous step is handled and heat, preferred Heating temperature is 750-850 ℃, and be 2-8 hour heat-up time, is air or oxygen atmosphere in the calciner; Cobaltous oxide is oxidized to tricobalt tetroxide in this process;
Then, above-mentioned cobaltosic oxide powder placed under the room temperature cool off, be packed as finished product at last.
In aforesaid method, material is calcined under three kinds of temperature respectively, and the atmosphere difference in the calciner.At first be provided with a pretreatment stage, cobalt raw material dewaters under lower temperature, this step all has bigger influence for the decomposition and the oxidising process of back, if contain certain moisture in the cobalt raw material, in thermolysis and oxidation, will separate out, can make the powder particle bonding like this, thereby influence the granularity and the crystal formation of finished product, also influence simultaneously the carrying out of oxidation, cause oxidation insufficient, the transformation efficiency of tricobalt tetroxide is reduced, a section calcining stage is set, this section Heating temperature is lower, and, also have an effect can avoid grain growth exactly at this process formation nitrogen atmosphere, guarantee to keep the class spherical particle shape of cobalt raw material, improve the loose density of the finished product, reach the requirement of the cobalt acid lithium raw material of making in the lithium ion battery material.In this section and two section calcining processes, the size of the flow of nitrogen is also influential to the control particle diameter, and the big crystal grain of nitrogen flow is not grown up, and nitrogen flow is less, and then crystal grain will be grown up, and the flow of generally controlling nitrogen was at 3-5M3/ minute.The characteristics that present method is outstanding are exactly in calcination process the thermo-cracking and the oxidising process of cobalt salt to be separated, nitrogen atmosphere is provided when thermo-cracking, temperature is higher than a section calcining, but be lower than three section calcinings, make all cobalt raw materials all transform into cobaltous oxide earlier, then, improve temperature again and provide air or oxygen atmosphere to make cobaltous oxide change into tricobalt tetroxide, like this, the amount of cobaltous oxide and cobalt sesquioxide is reduced to and does not contain cobaltous oxide and cobalt sesquioxide below 1% substantially.And in the prior art in disclosed many similar technology, in calcination process, directly cobalt raw material is placed under the temperature of thermo-cracking and bubbling air or oxygen.The product of Chu Liing like this, the content of cobalt element also may in fact wherein contain many cobaltous oxides and cobalt sesquioxide about 73% though record wherein, and these are found out by the X-ray diffraction figure line, even also can find out on the appearance color by product.
From the above, in preceding method, the grain shape of described cobalt raw material powder is good with the class sphere.The cobalt raw material of this kind spherical particle can be made with following chemical precipitation method, the steps include:
(1) step of preparation cobalt oxalate:
A, the preparation cobalt raw material aqueous solution, cobalt salt can be cobalt chloride or rose vitriol, its concentration is the 50-130 grams per liter, and adding in hydrochloric acid or oxalic acid or the sulfuric acid one or more, to make the pH of cobalt saline solution be 0.4-1.2;
B, configuration ammonium oxalate precipitant solution, its concentration is the 60-120 grams per liter, and feeding ammonia, to make the pH of the described precipitation agent aqueous solution be 3-5; Can also in this solution, add dispersion agent, it can be poly-hexylene glycol (molecular weight is 4000), or along divinyl, or vinylformic acid, or along divinyl and acrylic acid mixture, the addition of this dispersion agent is to add the 2-8 gram in per 10 liters of ammonium oxalate aqueous solution to get final product.
C, the described ammonium oxalate precipitation agent aqueous solution of adding of in the cobalt raw material aqueous solution, spraying, or spraying adds cobalt saline solution in the described ammonium oxalate precipitation agent aqueous solution, the ratio of cobalt salt and ammonium oxalate precipitant solution meets the amount of the equation defined of two kinds of substance reactions, till the pH that makes mixing solutions reaches 1-1.5, temperature of reaction is at normal temperature, the highlyest be no more than 60 ℃, implement to stir in reaction, the rotating speed of agitator is more suitable at 500 rev/mins; Reaction times is 2-15 minute;
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain the spherical cobalt salt powder of described class.
(2) step of preparation cobaltous hydroxide:
A, the preparation cobalt raw material aqueous solution, cobalt raw material is cobalt chloride or rose vitriol, its concentration is the 50-130 grams per liter, and adding in hydrochloric acid or oxalic acid or the sulfuric acid one or more, to make the pH of cobalt saline solution be 0.4-1.2;
B, configuration NaOH solution, its concentration is 10-30% (weight ratio), and feeds ammoniacal liquor and make precipitation agent, its feeding amount is: NaOH (10-30%) and ammoniacal liquor (the volume ratio 5-10 of proportion=0.9-1.0): 1; Also can in this solution, add described dispersion agent, poly-hexylene glycol (molecular weight is 4000), or along divinyl, or vinylformic acid, or along divinyl and acrylic acid mixture, the addition of this dispersion agent is to add the 2-8 gram in per 10 liters of NaOH solution water solution to get final product.
C, the described precipitation agent aqueous solution of adding of in the cobalt raw material aqueous solution, spraying, or spraying adds the cobalt raw material aqueous solution in the described precipitation agent aqueous solution, the material's proportion that cobalt raw material and b step obtain meets the amount of the equation defined of two kinds of substance reactions, in the reaction process, all the time the pH that keeps mixing solutions is stabilized in a certain value among the 10-12, optimum value is 10.8 ± 0.1, and it is constant to keep by regulating feed rate, temperature of reaction is at normal temperature, the highlyest be no more than 60 ℃, implement to stir in reaction, the rotating speed of agitator is more suitable at 500 rev/mins; Reaction times is 2-3 hour;
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain described class spherical cobalt hydroxide powder.
(3) step of preparation cobaltous carbonate:
A, preparation cobalt saline solution, cobalt salt is cobalt chloride or rose vitriol, its concentration is the 50-130 grams per liter, and adding in hydrochloric acid or oxalic acid or the sulfuric acid one or more, to make the pH of cobalt saline solution be 0.4-1.2;
B, configuration NH
4HCO
3Solution, its concentration are the 60-120 grams per liter, and feeding ammoniacal liquor, to make the pH of this precipitation agent be 7-9; In this solution, add described dispersion agent, poly-hexylene glycol (molecular weight is 4000), or along divinyl, or vinylformic acid, or along divinyl and acrylic acid mixture, the addition of this dispersion agent is to add the 2-8 gram in per 10 liters of described solution to get final product.
C, the described precipitation agent aqueous solution of adding of in cobalt saline solution, spraying, or spraying adds cobalt saline solution in the described precipitation agent aqueous solution, the material's proportion that cobalt salt and b step obtain meets the amount of the equation defined of two kinds of substance reactions, in the reaction process, all the time the pH that keeps mixing solutions is stabilized in a certain value among the 7.5-8.5, optimum value is 10.8 ± 0.1, and it is constant to keep by regulating feed rate, temperature of reaction is at normal temperature, the highlyest be no more than 60 ℃, implement to stir in reaction, the rotating speed of agitator is more suitable at 500 rev/mins; Reaction times is 1-3 hour;
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain described class spherical cobaltous carbonate powder.
The factor of the class ball shape of decision cobalt raw material crystal grain has in above-mentioned cobalt raw material preparation technology:
Feed way.In described cobalt raw material and two kinds of raw materials of precipitation agent, will be wherein any be injected in the another kind of solution can, if but two kinds of solution injected (it is reinforced promptly to liquidate) simultaneously then be not suitable in container because it is bigger to do the tendency that forms acicular grains like this.
Feed rate is arranged again.Its size can have influence on formed product loose density, if feed rate is excessive, it is too small then to form crystal grain, and loose density is less than normal, if feed rate is slow excessively, then the crystal grain of Xing Chenging is excessive, and loose density is also with less.
Add dispersion agent in addition.In reactant, add crystal grain that described dispersion agent can effectively avoid the forming gummed that sticks to each other, favourable to granularity and the crystal formation of guaranteeing product.
Certainly, reactant concn in crystallisation process, temperature of reaction, reaction times and potential of hydrogen etc. are all influential to size, degree of uniformity and the loose density of crystal grain, and the coupling of each parameter in the above-mentioned technology can be made the suitable cobalt salt powder of class ball shape grain size.
In addition, should notice when adding precipitation agent that the amount of dispersion agent wherein is too much unsuitable, otherwise, after finishing, reaction have unnecessary dispersion agent residual, and make in the finished product carbon content bigger than normal.
Preparation method of cobalt oxide provided by the invention, change a general section calcining, the same gas atmosphere that adopts in the prior art into three section calcinings, oxygenant is not provided in the cobalt salt thermolysis, make it all to change into cobaltous oxide earlier, and then be warmed up to oxidizing temperature and provide oxygen or air atmosphere.The transformation efficiency height of tricobalt tetroxide in the product that makes by present method, other oxide compound of cobalt is few, and epigranular, loose density are big, the electric property and the work-ing life that help improving battery.In addition, suitably the various operation parameters of control can obtain class ball shape cobalt salt particle in the preparation cobalt salt, desirable more on granularity and loose density with its tricobalt tetroxide that calcining obtains as raw material, wherein Co content is at 73-73.5%, and loose density is 2-2.4g/cm
3, particle diameter is at 3-5 μ m.
Description of drawings
The invention will be further described below in conjunction with accompanying drawing.
Fig. 1 carries out the process flow diagram of three section calcinings for preparation class ball shape cobalt oxalate and to it;
Fig. 2 is for using the cobalt oxalate powder of class ball shape, cobaltosic oxide powder 1 transmission electron microscope photo that obtains through three section calcinings;
Fig. 3 is the transmission electron microscope photo of the cobaltosic oxide powder that uses non-near-spherical cobalt oxalate and get through three section calcinings;
Fig. 4 is the transmission electron microscope photo of the cobaltosic oxide powder 2 that uses near-spherical cobaltous carbonate three section calcinings and obtain;
Fig. 5 is the transmission electron microscope photo of the cobaltosic oxide powder 3 that uses near-spherical cobaltous hydroxide three section calcinings and get;
Fig. 6 is a comparison example, the transmission electron microscope photo of the cobaltosic oxide powder that obtains with a section calcining;
Fig. 7 is for using three set products 1,2,3 shown in Fig. 2,4,5 and the X-ray diffraction figure line of standard cobaltosic oxide powder.
Embodiment
Embodiment 1:
Prepare tricobalt tetroxide with as shown in Figure 1 processing method, the steps include:
1, preparation near-spherical cobalt oxalate powder:
A, preparation cobalt chloride solution are with chloroazotic acid (HCl: HNO
3=3: 1) be heated to 80-90 ℃, electrolytic cobalt sheet is dissolved in wherein, form cobalt chloride solution, its concentration is 100 grams per liters, and adds the oxalic acid acidifying, and the pH that makes cobalt chloride solution is 0.6-0.8;
B, the preparation ammonium oxalate aqueous solution: in oxalic acid, feed NH
3, making its concentration is 90 grams per liters, and to make the pH of the ammonium oxalate aqueous solution be 4.3-4.5; Add dispersion agent in ammonium oxalate solution, it is poly-hexylene glycol (molecular weight is 4000), and the addition of this dispersion agent is to add 6.25 grams in per 10 liters of ammonium oxalate aqueous solution.
C, the ammonium oxalate aqueous solution that makes by spray pattern adding step b in the cobalt chloride solution that step a makes, the amount that adds ammonium oxalate makes the pH of reaction solution reach 1.0-1.5.The interpolation speed of cobalt oxalate is to make at 5 minutes to make the pH value of reaction solution reach requirement.Temperature of reaction is controlled between 36-42 ℃, implements to stir in reaction, and the rotating speed of agitator is at 500 rev/mins; Reinforced finishing continues reaction end in 2-3 minute.
D, reaction finish, and above-mentioned crystallisate is separated with mother liquor, and dehydration, drying can obtain described class spherical cobalt oxalate powder.
2, preparation cobaltosic oxide powder:
A, a section calcining:
The cobalt oxalate powder that aforementioned operation is made places calciner to heat, and Heating temperature is at 300 ℃, and be 3 hours heat-up time, is nitrogen atmosphere in the calciner, and the flow of nitrogen is 3M
3/ minute, be that moisture remaining in the cobalt salt powder and crystal water are removed in this process;
B, two section calcinings:
To place under 500 ℃ of temperature through the material that last dehydrating step is handled and heat, be 2 hours heat-up time, still is nitrogen atmosphere in the calciner, and the flow of nitrogen is 5M
3/ minute; In this process, make the cobalt oxalate more than 99% be thermally cracked to cobaltous oxide;
C, three section calcinings:
To place under 750 ℃ of temperature through the material that previous step is handled and heat, be 3 hours heat-up time, and bubbling air in the calciner, the air pressure of air are 980kPa (1Kg/cm
2); In this process, make whole CoO all be oxidized to Co
3O
4
Then, with above-mentioned Co
3O
4Powder places under the room temperature and cools off, and is packed as finished product at last.
The length of the heat-up time of each section calcining often depends on the stacking thickness of material, in addition, also with other particular case of material, as the water content that depends on material heat-up time in a section calcining process what or the like.
The Co that makes by above-mentioned technology
3O
4The visible Co as shown in Figure 2 of its crystal grain
3O
4The powder transmission electron microscope photo, Co wherein
3O
4Particle be near-spherical, its Co content is 73.31, particle diameter d
50=3.58 μ m, its loose density is 2.18g/cm
3Its powder color is black-and-blue, and this production code member is 1, the transmission electron microscope photo of this powder as shown in Figure 2, the figure line 1 of its X-ray diffraction figure line in as shown in Figure 7.
Be a comparison example below:
It uses non-near-spherical cobalt oxalate powder, not through nitrogen atmosphere control, and is one-part form calcining blowing air, and its powder color of the product that obtains is a grey black.Because the color of CoO is a greyish-green, therefore, the explanation of the color of the said products wherein exists some not to be oxidized to Co
3O
4CoO, its granularity is also bigger, and is inhomogeneous, loose density is 1.7g/cm
3, lower.Its transmission electron microscope photo as shown in Figure 6.
Be illustrated in figure 3 as the transmission electron microscope photo of the product that obtains after adopting non-class spherical cobalt oxalate process as embodiments of the invention 1 essentially identical method calcining, can clearly be seen that by photo, the gabarit of the crystal grain of product is the obelisk shape, and its Co content is 73.49, particle diameter d
50=4.45 μ m, its loose density is 1.60g/cm
3Its powder color is black-and-blue, represents that wherein the content of tricobalt tetroxide is high.But its loose density but is lower than the corresponding physical index of the near-spherical crystal grain of prepared provided by the invention.
Embodiment 2:
1, preparation near-spherical cobaltous carbonate powder:
A, preparation cobalt chloride solution, its concentration is 60 grams per liters, and adding sulfuric acid, to make the pH of cobalt saline solution be 0.5-0.6;
B, preparation ammonium bicarbonate aqueous solution, its concentration is 70 grams per liters, and feeding ammonia, to make the pH of ammonium bicarbonate aqueous solution be 7-9; Add dispersion agent in ammonium bicarbonate soln, it is that its ratio is along divinyl and acrylic acid mixture: 1: 1, the addition of this dispersion agent was to add 7 grams in per 10 liters of ammonium bicarbonate aqueous solutions to get final product.
C, the described ammonium bicarbonate aqueous solution of adding of in cobalt saline solution, spraying, till the pH that makes mixing solutions reaches 7.5-8.5, and it is constant to keep above-mentioned pH in reaction process, and keeping the constant method of pH is to make the add-on of cobalt salt solution constant, and the add-on of adjusting bicarbonate of ammonia realizes.Temperature of reaction is at normal temperature, the highlyest is no more than 50 ℃, implements to stir in reaction, and the rotating speed of agitator is at 500 rev/mins; Reaction times is 1-3 hour.
The preparation cobaltous carbonate, precipitin reaction can be a continuous processing, wherein the feed rate of two kinds of materials is: cobalt chloride solution 30-60L/hr, the adding speed of bicarbonate of ammonia is mated by pH.
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain described class spherical cobaltous carbonate powder.
2, preparation cobaltosic oxide powder:
A, a section calcining:
The cobaltous carbonate powder that aforementioned operation is made places calciner to heat, and Heating temperature is at 250 ℃, and be 5 hours heat-up time, is nitrogen atmosphere in the calciner, and the flow of nitrogen is 3M
3/ minute;
B, two section calcinings:
To place under 500 ℃ of temperature through the material that last dehydrating step is handled and heat, be 4 hours heat-up time, still is nitrogen atmosphere in the calciner, and the flow of nitrogen is 5M
3/ minute;
C, three section calcinings:
To place under 700 ℃ of temperature through the material that previous step is handled and heat, be 8 hours heat-up time, bubbling air in the calciner; In this process, make whole cobaltous oxides all be oxidized to tricobalt tetroxide;
Then, above-mentioned cobaltosic oxide powder placed under the room temperature cool off, be packed as finished product at last.
The Co that makes by above-mentioned technology
3O
4Particle is a near-spherical, and its Co content is 73.26, particle diameter d
50=4.50 μ m, its loose density is 2.15g/cm
3Its powder color is black-and-blue, and being numbered of this product mixes 2, the transmission electron microscope photo of this powder as shown in Figure 4, the figure line 2 of its X-ray diffraction figure line in as shown in Figure 7.
Embodiment 3:
1, preparation near-spherical cobaltous hydroxide powder:
A, preparation cobalt chloride solution, its concentration is 120 grams per liters, and adding hydrochloric acid, to make the pH of the aqueous solution be 0.9-1.1;
B, preparation contain ammonia NaOH solution, and its concentration is 20%, and to feed proportion d be 95% ammoniacal liquor, and NaOH (20%) is 8: 1 with the volume ratio of ammoniacal liquor (proportion=0.95); Add dispersion agent in this solution, it is that its ratio is along divinyl and acrylic acid mixture: 1: 1, the addition of this dispersion agent was to add 7 grams in per 10 liters of NaOH aqueous solution to get final product.
C, spraying adds the NaOH solution that step b makes in the cobalt raw material aqueous solution, and to keep pH be 10-11, makes to be reflected under the stable p H and carries out.The mode of keeping pH is to stablize the add-on of cobalt chloride, the add-on of regulating NaON solution at any time.Temperature of reaction is at normal temperature, the highlyest is no more than 60 ℃, implements to stir in reaction, and the rotating speed of agitator is at 500 rev/mins; Reaction times is 2-3 hour.
The preparation cobaltous hydroxide, precipitin reaction can be a continuous processing, wherein the feed rate of two kinds of materials is: cobalt chloride solution 50-70L/hr, the adding speed of NaOH is mated by pH.
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain described class spherical cobalt hydroxide powder.
2, preparation cobaltosic oxide powder:
A, a section calcining:
The cobaltous hydroxide powder that aforementioned operation is made places calciner to heat, and Heating temperature is at 450 ℃, and be 2 hours heat-up time, is nitrogen atmosphere in the calciner, and the flow of nitrogen is 3M
3/ minute;
B, two section calcinings:
To place under 550 ℃ of temperature through the material that last dehydrating step is handled and heat, be 4 hours heat-up time, still is nitrogen atmosphere in the calciner, and the flow of nitrogen is 5M
3/ minute;
C, three section calcinings:
To place under 900 ℃ of temperature through the material that previous step is handled and heat, be 5 hours heat-up time, bubbling air in the calciner; In this process, make whole cobaltous oxides all be oxidized to tricobalt tetroxide;
Then, above-mentioned cobaltosic oxide powder placed under the room temperature cool off, be packed as finished product at last.
The Co that makes by above-mentioned technology
3O
4Particle is a near-spherical, and its Co content is 73.26, particle diameter d
50=4.50 μ m, its loose density is 2.15g/cm
3Its powder color is black-and-blue, this product be numbered 3, the transmission electron microscope photo of this powder as shown in Figure 5, the figure line 3 of its X-ray diffraction figure line in as shown in Figure 7.
Being illustrated in figure 4 as with method of the present invention is the Co that the raw material calcining is made with class spheric cobalt oxalate, cobaltous carbonate and cobaltous hydroxide respectively
3O
4The Co that product 1, product 2 and product 3 are generally acknowledged with the industry
3O
4The X-ray diffraction figure line of standard, through and standard contrast, the product that preparation method of the present invention makes has identical X ray spectral line, explanation thus, this product has identical structure with standard, i.e. Co wherein
3O
4Content is more than 99%.
Claims (10)
1, a kind of lithium ion battery preparation method of cobalt oxide uses cobalt oxalate or cobaltous hydroxide or cobaltous carbonate to make raw material, and the granularity of this cobalt raw material is D
50=2-8 μ m; Preparation process is: above-mentioned raw materials is carried out three section calcinings:
A, a section calcining:
Place calciner to heat in described cobalt raw material powder, Heating temperature is at 200-450 ℃, and be 2-5 hour heat-up time, is nitrogen atmosphere in the calciner; Be that moisture remaining in the cobalt raw material powder and/or crystal water are removed in this process;
B, two section calcinings:
To place under the 500-800 ℃ of temperature through the material that previous step is handled and heat, be 1-5 hour heat-up time, still is nitrogen atmosphere in the calciner; Be thermally cracked to cobaltous oxide at cobalt raw material described in this process;
C, three section calcinings:
To place under the 700-1000 ℃ of temperature through the material that previous step is handled and heat, be 2-8 hour heat-up time, is air or oxygen atmosphere in the calciner; Cobaltous oxide is oxidized to tricobalt tetroxide in this process;
Then, above-mentioned cobaltosic oxide powder placed under the room temperature cool off, be packed as finished product at last.
2, preparation method of cobalt oxide according to claim 1 is characterized in that: in described method, the grain shape of described cobalt raw material powder is the class sphere.
3, preparation method of cobalt oxide according to claim 2 is characterized in that: the cobalt raw material of such spherical particle is a cobalt oxalate, and it comprises and is prepared as follows step:
A, preparation cobalt chloride solution, its concentration is the 50-130 grams per liter, and adding in hydrochloric acid or oxalic acid or nitric acid or the sulfuric acid one or more, to make the pH of cobalt saline solution be 0.4-1.2;
B, configuration ammonium oxalate solution, its concentration is the 60-120 grams per liter, and feeds ammoniacal liquor and make the precipitation agent aqueous solution, making its pH is 3-5;
C, the described ammonium oxalate precipitation agent aqueous solution of adding of in cobalt saline solution, spraying, or spraying adds cobalt saline solution in the described ammonium oxalate precipitation agent aqueous solution, the ratio of cobalt salt and ammonium oxalate meets the amount of the equation defined of two kinds of substance reactions, till the pH that makes mixing solutions reaches 1-1.5, temperature of reaction is at normal temperature, implement to stir in reaction, the rotating speed of agitator is at 500 rev/mins; Reaction times is 2-15 minute;
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying promptly obtains the spherical cobalt salt powder of described class.
4, preparation method of cobalt oxide according to claim 2 is characterized in that: the cobalt raw material of such spherical particle is a cobaltous carbonate, and it comprises and is prepared as follows step:
A, the preparation cobalt raw material aqueous solution, cobalt salt is cobalt chloride or rose vitriol, its concentration is the 50-130 grams per liter, and adding in hydrochloric acid or the sulfuric acid one or more, to make the pH of cobalt saline solution be 0.4-1.2;
B, configuration NH
4HCO
3Solution, its concentration are the 60-120 grams per liter, and feed ammoniacal liquor and make the precipitation agent aqueous solution, and making its pH is 7-9;
C, the described precipitation agent aqueous solution of adding of in cobalt saline solution, spraying, or spraying adds cobalt saline solution in the described precipitation agent aqueous solution, the material's proportion that cobalt salt and b step obtain meets the amount of the equation defined of two kinds of substance reactions, the pH of mixing solutions is stabilized in 7.5-8.5 in the reaction process, temperature of reaction is at normal temperature, implement to stir in reaction, the rotating speed of agitator is at 500 rev/mins; Reaction times is 1-3 hour;
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain described class spherical cobaltous carbonate powder.
5, preparation method of cobalt oxide according to claim 2 is characterized in that: the cobalt raw material of such spherical particle is a cobaltous hydroxide, and it comprises and is prepared as follows step:
A, preparation cobalt saline solution, cobalt salt is cobalt chloride or rose vitriol, its concentration is the 50-130 grams per liter, and adding in hydrochloric acid or the sulfuric acid one or more, to make the pH of cobalt saline solution be 0.4-1.2;
B, configuration NaOH solution, its concentration is the 10-30% weight ratio, and feeds ammoniacal liquor and make precipitation agent, its feeding amount is: the volume ratio 5-10 of the NaOH of 10-30% and the ammoniacal liquor of proportion=0.9-1.0: 1;
C, the described precipitation agent aqueous solution of adding of in cobalt saline solution, spraying, or spraying adds cobalt saline solution in the described precipitation agent aqueous solution, the material's proportion that cobalt salt and b step obtain meets the amount of the equation defined of two kinds of substance reactions, make the pH of mixing solutions be stabilized in a certain value among the 10-12 in the reaction process, and keep constant, temperature of reaction is implemented to stir in reaction at normal temperature, and the rotating speed of agitator is at 500 rev/mins; Reaction times is 2-3 hour;
D, the crystallisate that above-mentioned reaction is produced separate with mother liquor, drying can obtain described class spherical cobalt hydroxide powder.
6, preparation method of cobalt oxide according to claim 1 is characterized in that: the Heating temperature of a described section calcining is 250-350 ℃.
7, preparation method of cobalt oxide according to claim 1 is characterized in that: the Heating temperature of described two section calcinings heating is 550-650 ℃.
8, preparation method of cobalt oxide according to claim 1 is characterized in that: described three section calcining Heating temperatures are 750-850 ℃.
9, according to claim 3 or 4 or 5 described preparation method of cobalt oxide, it is characterized in that: in described precipitation agent, add dispersion agent, it is that molecular weight is 4000 poly-hexylene glycol, or along divinyl, or vinylformic acid, or along divinyl and acrylic acid mixture, the addition of this dispersion agent is to add the 2-8 gram in per 10 liters of precipitation agent aqueous solution.
10, preparation method of cobalt oxide according to claim 1 is characterized in that: the amount that feeds nitrogen in a described section calcining or two section calcinings is 3-5M
3/ min.
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| CN100345324C (en) * | 2005-09-06 | 2007-10-24 | 天津力神电池股份有限公司 | Method for preparing lithium ion cell cobaltic-cobaltous oxide negative pole material |
| CN102886525B (en) * | 2011-07-20 | 2015-04-29 | 深圳市格林美高新技术股份有限公司 | Cobalt powder with large grain size and preparation method thereof |
| CN102978419B (en) * | 2012-12-17 | 2014-06-18 | 江西稀有稀土金属钨业集团有限公司 | Electrically-heating and integrally-rotating resistance furnace capable of sintering anhydrous cobalt chloride into cobalt oxide product |
| CN103086369B (en) * | 2013-01-18 | 2015-03-25 | 湖南元素密码石墨烯研究院（有限合伙） | Preparation method of graphene/nano cobaltosic oxide composite material |
| CN104852039B (en) * | 2015-04-16 | 2017-05-10 | 中南大学 | Preparation method of cathode material for lithium ion battery |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105800699A (en) * | 2016-04-20 | 2016-07-27 | 湖南海纳新材料有限公司 | Method for preparing high-sphericity-degree and large-particle cobaltosic oxide |
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| CN110935886A (en) * | 2018-09-21 | 2020-03-31 | 荆门市格林美新材料有限公司 | Class C60Preparation method of type cobalt powder |
| CN111115704A (en) * | 2018-10-31 | 2020-05-08 | 格林美（江苏）钴业股份有限公司 | Preparation method of cobaltosic oxide |
| CN109817929B (en) * | 2019-01-25 | 2020-11-03 | 安徽师范大学 | Spiral silicon dioxide/cobaltosic oxide composite nano material, preparation method thereof and application thereof in lithium ion battery |
| CN113663672B (en) * | 2020-05-15 | 2023-08-15 | 香港城市大学深圳研究院 | Cobalt oxide photocatalytic material with high photoelectrocatalytic activity and preparation method thereof |
| CN113697864B (en) * | 2020-05-21 | 2023-08-15 | 江西理工大学 | Preparation method of cobaltosic oxide |
| CN111620386A (en) * | 2020-05-22 | 2020-09-04 | 兰州理工大学 | Method for preparing cobaltosic oxide powder through Fenton-like catalytic reaction |
| CN112563487B (en) * | 2020-11-18 | 2022-12-09 | 上海空间电源研究所 | CoS for thermal battery 2 Method for producing a material |
| CN113233516B (en) * | 2021-05-28 | 2023-01-06 | 金川集团股份有限公司 | Preparation method of single crystal small-granularity cobaltosic oxide |
| CN115108591A (en) * | 2022-08-31 | 2022-09-27 | 金川集团股份有限公司 | Preparation method of low-sulfur cobaltosic oxide |
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