CN1586772A - Process for preparing nano grade super fine cobalt powder - Google Patents
Process for preparing nano grade super fine cobalt powder Download PDFInfo
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- CN1586772A CN1586772A CN 200410068855 CN200410068855A CN1586772A CN 1586772 A CN1586772 A CN 1586772A CN 200410068855 CN200410068855 CN 200410068855 CN 200410068855 A CN200410068855 A CN 200410068855A CN 1586772 A CN1586772 A CN 1586772A
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Abstract
The preparation process of nano level superfine cobalt powder includes ultrasonic gas flow spraying and converting process to prepare precursor CoOx powder of average size below 60 nm, roasting, shearing to crush, centrifuging, air drying, low temperature H2 reduction at 520-550 deg.c in tube furnace to prepare nano level Co powder of average size below 80 nm. The present invention has the advantages of simple technological process, low cost, capacity of being mass produced in reducing furnace, narrow Co powder size distribution range, and spherical particle in the average size below 80 nm.
Description
Technical field
The invention belongs to the preparing technical field of metal-powder in the metallic substance, the preparation method at a kind of nano-grade superfine cobalt powder end particularly is provided, be applicable to nano level, the suitability for industrialized production of cobalt dust.
Background technology
Cobalt metal is applied in fields such as high temperature alloy, Hardmetal materials, functional materials, corrosive wear resistant alloys material, chemical industry catalysis-catalyst material, diamond tool material widely, direct applied industry of these materials and technical field all are most important departments in the national economy, all need a large amount of cobalt metals as the probing exploitation instrument in space flight and aviation engine, gas turbine generator, heavy artillery fire equipment, traffic, flint road, oil, colliery etc. etc.
Hard carbide industry almost is all industrial basic industry, only the industry China needs 700 tons of cobalt powders every year approximately, also will consume 300 tons/year every year in functional materials, countries in the world increase year by year to the demand of cobalt, and the cobalt valency rises suddenly and sharply always on the world market, since World War II, each industrial power of the world all classifies cobalt metal as strategy metal and lays in, this mainly is because the cobalt ore resource seldom focuses mostly on again in the economically less developed region, as areas such as Zaire and Africa in the world.China be poor cobalt state up to the later stage eighties, just finding has less cobalt ore resource, and reserves are very low, thus China every year except recovery part cobalt from waste alloy, still want a large amount of cobalt of import.
The annual required cobalt powder of hard carbide industry is by the metal cobalt button of import mostly, makes Co (NO through nitric acid dissolve
3)
26H
2The O Xiao Suangu is made CO through oxalic acid treatment and roasting again
2O
3, use H again
2Reduce, make the cobalt powder of ultra-fine (0.8～2 μ m).This prepared cobalt powder is all adopted in countries in the world over nearly 80 years, in recent years along with the develop rapidly of Materials science, particularly the literature search in nearly ten years in the production technology of Wimet, is adopted the cobalt powder and the tungsten carbide powder of nano level superfine as can be known, can make the bending strength of Wimet double many, hardness and wear resistance also increase substantially, so countries in the world are to nano-cobalt powder, the technology of preparing of tungsten carbide powder, show great interest, compete very violent.
Nearly 5 years literature search as can be known, the method for preparing nano-grade superfine cobalt powder mainly contains, aqueous solution reduction method, sol-gel processing, microemulsion method, (CVD) vapour deposition process, evaporation-condensation method (containing plasma evaporation, laser evaporation, electron beam evaporation cohesion).But though the nano level cobalt powder of first three methods production median size≤100nm, but production cost is too high, and production efficiency is very low, thereby over a long time can not large-scale industrial production, the cobalt powder median size that vapour deposition process is produced is thick, be generally 0.1～1.5 μ m, and facility investment is big, production efficiency is low, the evaporation-condensation method, can produce the cobalt powder of 0.1～3 μ m, its facility investment is big, and production efficiency is also very low.The ancient technology of original preparation cobalt powder, the cobalt powder though can be mass-produced, but the mean particle size of powder is thick (0.8～2 μ m), can not satisfy the needs of the scientific research and the new product development of ultrafine gain size far away, patent purpose of the present invention is to provide a kind of and directly prepares nano level superfine with ullrasonic spraying thermal conversion method (cobalt oxide powder of median size≤60nm) is through low temperature H
2Reduce, can directly make the technology of preparing of nano-cobalt powder.
Summary of the invention
The object of the present invention is to provide the preparation method at a kind of nano-grade superfine cobalt powder end, realized the suitability for industrialized production at nano-grade superfine cobalt powder end, improved powder purity, and reduced cost.
The present invention adopts air-flow ullrasonic spraying thermal conversion legal system to be equipped with the CoOx precursor powder of nano level average crystal grain＜60nm, through roasting, and shearing-crushing, centrifugal, air-dry, hydrogen reduction is prepared into the Co powder of nano level average crystal grain＜100nm in tube furnace.Employed cobalt oxide powder is to adopt 68～128 ℃ of air-flow ullrasonic sprayings of low temperature thermal conversion method, the CoOx precursor powder of the nano level average crystal grain＜60nm of preparation.Concrete preparation technology is:
1, cobalt ion aqueous solution preparation:
The preparation of the cobalt ion aqueous solution is pressed following relational expression with the relationship between quality of cobalt powder and is calculated:
When employing nitrate, during preparation 1kg nano Co powder,
Co (NO
3)
26H
2The molecular weight M=291.03 of O,
Wherein: cobalt contents X
1=
58.933/
291.03=20.249%,
Need Co (NO
3)
26H
2The quality Y of O
1=
291.03 * 1000/
58.933=4938.32 grams (16.968mol) join crystal powder 4938.3 grams of above-mentioned Xiao Suangu in 4 liters of distilled water, constantly stir, fully after the dissolving, with 44 μ m screen filtration tramp materiaies, make the cobalt nitrate solution of 4.242mol/L concentration, change the ullrasonic spraying thermal conversion over to.
When selecting vitriol for use, except that the relationship between quality of pressing aqueous solution preparation of vitriol molecular formula calculating cobalt ion and cobalt powder, also the precursor powder of spraying gained should be cleaned repeatedly with distilled water before roasting, remove SO
2- 4Sulfate radical.
The preparation of the cobalt ion aqueous solution can be adopted the water-soluble cobalt salt class of any energy, as Sulfates CoSO is arranged
46H
2O; Nitrates has Co (NO
3)
26H
2O etc.By certain concentration proportioning, these salts directly are dissolved in promptly can be made into the aqueous solution that contains cobalt ion in the distilled water, acid group residual when considering follow-up roasting with reduction is different to the corrosive nature of equipment, when selecting vitriol for use, the precursor powder of spraying gained should be cleaned repeatedly with distilled water before roasting, remove SO
2- 4Sulfate radical.When selecting nitrate for use, residual NO in the precursor powder
-1 3Nitrate ion can major part resolve into NO in roasting process
2Its to the corrodibility of equipment a little less than, therefore before roasting, can not adopt distilled water to clean the operation of acid group.
The present invention mainly adopts Co (NO
3)
26H
2O is a raw material.Because of Co (NO
3)
26H
2The molecular weight M=291.03 of O wherein contains cobalt amount X
1=
58.933/
291.03=20.249%, so during preparation 1Kg nano-cobalt powder, need Co (NO
3)
26H
2The quality of O is Y
1=
291.03 * 1000/
58.933=4938.32 grams (16.968mol) join crystal powder total 4938.3 grams of above-mentioned Xiao Suangu in 4 liters of distilled water, constantly stir, and after the dissolving, with 44 μ m screen filtration tramp materiaies, make the cobalt nitrate solution of 4.242mol/L concentration fully.Change the ullrasonic spraying thermal conversion over to.
2, the thermal conversion of air-flow ullrasonic spraying prepares precursor powder:
Change the cobalt nitrate solution of preparation over to ullrasonic spraying thermal conversion tower and carry out the air-flow ultrasonic atomizatio and prepare the nanometer grade cobalt oxide precursor powder, the nozzle that uses is circumferential weld resonant mode air-flow ultrasonic atomizing nozzle.Nozzle spray angle α=45 ℃, whiff pressure (air) 2.5～3.5MPa, air-flow jet velocity 2～2.5 Mach numbers, 68～128 ℃ of hot blast temperatures, liquid stream transfer rate 200ml/ branch, the thermal conversion of air-flow ullrasonic spraying can be made into the cobalt oxide precursor powder of median size＜60nm.
3, nitrate ion is removed in roasting:
In the precursor powder of nitrate preparation, because of containing NO
-1 3Nitrate ion, at 450～500 ℃, low-temperature bake is 30～50 minutes in the air, can be with NO
-1 3The nitrate radical branch is taken off, and obtains the exsiccant nano Co
2O
3Cobalt oxide powder.
4, shearing-crushing
With the high speed shear crusher machine of the cobalt oxide powder after the roasting, press cobalt oxide powder: industrial spirit=1: 5 mass ratio adds industrial spirit, together put in the batch can of shears, under 10000 rev/mins of rotating speeds, calculate shear time by 15 minutes/100 gram powder, after shearing, emit slip.This operation is the bridged particle that forms in the broken roasting process, prevents that the cobalt powder particle is grown up in reduction process.
5, high speed centrifugation separates alcohol
Oxide slurry after the fragmentation is isolated industrial spirit through high-speed continuous whizzer, and slightly alcoholic cobalt oxide slip changes over to air-dry
6, air-dry:
Slightly alcoholic cobalt oxide slip is through the air-dry exsiccant nano level Co that obtains
2O
3Powder changes the hydrogen reducing furnace reduction over to
7, hydrogen reduction prepares nano-cobalt powder
With the nano oxidized cobalt dust of exsiccant, put into stainless steel tubular type reduction furnace, at 520～560 ℃, 45～60 minutes, use H
2The gas reduction, H
2Gas cross section flow, 80～100ml/cm
2Powder after the reduction is put into acetone-oleic acid liquid immediately after coming out of the stove, prevent spontaneous combustion.Make the 1Kg cobalt powder of median size≤80nm after coming out of the stove.
8, product performance detect
Mainly carry out XRD, BET specific surface, TEM granule-morphology and granularity
9, product vacuum packaging
The product that performance is qualified carries out vacuum packaging
Advantage of the present invention:
(1) on the production technology and equipment a kind of new technology that can serialization scale operation nano-grade superfine cobalt powder is provided.Technology is simple, and cost is lower.
(2) adopt shearing-crushing and continuous centrifugal isolation technique not only can eliminate bridged particle in the powder, and solved the problem of nano powder precipitate and separate difficulty in solution, thereby can guarantee that large-scale production normally carries out.
(3) the nano level cobalt powder of Sheng Chaning, good dispersity, narrow diameter distribution, median size＜80nm, particle shape almost spherical.
Description of drawings
Fig. 1 is preparation technology's schema of the present invention.Wherein, the cobalt nitrate aqueous solution preparation 1; Cobalt nitrate aqueous solution is carried out the ullrasonic spraying thermal conversion, preparation precursor powder 2; The roasting precursor powder is removed nitrate radical 3; Shearing-crushing 4 is with the bridged particle fragmentation in the precursor powder; High speed centrifugation separates alcohol 5, adopts high-speed continuous whizzer with alcohol and powder sharp separation; Air-dry 6; With exsiccant nano level Co
2O
3Powder H
2Gas is reduced into nano level cobalt powder 7; Product performance detect 8, and powder-product is carried out the BET specific surface, and XRD, TEM measure; Product vacuum packaging 9.
Embodiment
Embodiment 1: preparation 1kg nano-cobalt powder end should follow these steps to finish.
1, weighing:
Take by weighing 4938.32 gram Co (NO
3)
26H
2The O crystal powder joins in 4 liters of distilled water, constantly stirs, and the dissolving back is transferred to solution in the atomizing flow container with behind the 44 μ m screen filtration tramp materiaies fully.
2, air-flow ullrasonic spraying thermal conversion:
Use the circumferential weld resonant mode air-flow ultrasonic atomizing nozzle of spray angle α=45 °, whiff pressure (air) 2.5MPa, 128 ℃ of hot blast temperatures, air-flow jet velocity 2 Mach numbers, liquid stream transfer rate 200ml/ branch, solution can obtain the dry precursor powder after all having atomized, and changes the roasting stage over to.
3, roasting:
With precursor powder, in stoving oven 450 ℃, roasting under 50 fens air atmospheres is further decomposed eliminating with residual water in the precursor powder and micro-acid group.Obtain exsiccant nano level Co
2O
3Cobalt oxide powder
4, shearing-crushing:
Press cobalt oxide powder: industrial spirit=1: 5 mass ratio, add industrial spirit and together pour in the flow container of shears, under 10000 rev/mins of rotating speeds, calculate shear time by (15 minutes/100 gram powder), emit slip after the shearing.
5, high speed centrifugation separates alcohol
Oxide slurry after the shearing is isolated industrial spirit with high-speed continuous whizzer, and slightly alcoholic cobalt oxide slip changes air-dry operation over to.
6, air-dry
Slightly alcoholic cobalt oxide slip obtains exsiccant nano level Co through natural air drying
2O
3Powder changes the hydrogen reducing furnace reduction over to.
7, hydrogen reducing prepares nano-cobalt powder
In stainless steel tubular type reduction furnace,, 60 minutes, use H at 520 ℃
2Gas reduction exsiccant nano level Co
2O
3Powder, H
2Gas cross section flow, 80ml/cm
2Put into acetone-oleic acid liquid when the powder after the reduction is come out of the stove immediately, prevent spontaneous combustion.Promptly make the 1Kg cobalt powder of median size≤80nm.
8, product performance detect
Mainly carry out XRD, BET specific surface, TEM granule-morphology and granularity
9, product vacuum aluminium bag packing
The product that performance is qualified carries out vacuum packaging
Embodiment 2 preparation 10kg nano-cobalt powder ends should follow these steps to finish.
1, weighing
Take by weighing 49.384kg Co (NO
3)
26H
2The O crystal powder joins in 40 liters of distilled water in the stainless steel NaOH solution tank NaOH, constantly stir dissolving fully after, the thermal conversion of in 44 μ m screen filtration pipelines are injected into solution with liquid pump the flow container of atomisation tower, spraying.
2, air-stream spraying thermal conversion
Use the circumferential weld resonant mode air-flow ultrasonic atomizing nozzle of jet angle α=45 °, whiff pressure (air) 3.5MPa, 68 ℃ of hot blast temperatures, liquid stream transfer rate 200ml/ branch, air-flow jet velocity 2.5 Mach numbers, solution can obtain the dry precursor powder after all having atomized, and change calcining process over to.
3, roasting
With the precursor powder that obtains in above-mentioned 2, directly put into stoving oven, under the air atmosphere, temperature is 500 ℃, roasting 30 minutes can obtain the exsiccant cobalt oxide powder after the cooling of coming out of the stove, and changes the shearing-crushing operation over to.
4, shearing-crushing
Press cobalt oxide powder: industrial spirit=1: 5 mass ratio, add industrial spirit and together pour in the shears flow container, calculate shear time by (15 minutes/100 gram powder), emit slip after the shearing.
5, high speed centrifugation separates
Cobalt oxide slurry after the shearing is isolated industrial spirit with high-speed continuous whizzer, and slightly alcoholic cobalt oxide slip changes air-dry operation over to.
6, air-dry
Slightly alcoholic cobalt oxide slip obtains exsiccant nano level Co through natural air drying
2O
3Powder changes H over to
2The reduction operation
7, H
2The gas reduction
In stainless steel tubular type reduction furnace, 560 ℃, 45 minutes, use H
2Gas reduction exsiccant nano level Co
2O
3Powder, H
2Cross section flow 100ml/cm
2, 7 identical among all the other and the embodiment 1.Make the 10Kg cobalt powder of median size≤80nm after coming out of the stove
8,9 and embodiment 1 in 8,9 identical.
Claims (3)
1, a kind of preparation method of nano-grade superfine cobalt powder, it is characterized in that: adopt air-flow ullrasonic spraying thermal conversion legal system to be equipped with the CoOx precursor powder of nano level median size＜60nm, through roasting, shearing-crushing, centrifugal, air-dry, hydrogen reduction is prepared into the Co powder of nano level median size＜100nm in tube furnace; Employed cobalt oxide powder is to adopt 68～128 ℃ of air-flow ullrasonic sprayings of low temperature thermal conversion method, the CoOx precursor powder of the nano level median size＜60nm of preparation.
2, according to claim 1 or 2 described methods, it is characterized in that: concrete technology is:
A, the preparation of the cobalt ion aqueous solution:
The preparation of the cobalt ion aqueous solution is pressed following relational expression with the relationship between quality of cobalt powder and is calculated:
When employing nitrate, during preparation 1kg nano Co powder,
Co (NO
3)
26H
2The molecular weight M=291.03 of O,
Wherein: cobalt contents X
1=
58.933/
291.03=20.249%,
Need Co (NO
3)
26H
2The quality Y of O
1=
291.03 * 1000/
58.933=4938.32 grams (16.968mol) join crystal powder 4938.3 grams of above-mentioned Xiao Suangu in 4 liters of distilled water, constantly stir, fully after the dissolving, with 44 μ m screen filtration tramp materiaies, make the cobalt nitrate solution of 4.242mol/L concentration, change the ullrasonic spraying thermal conversion over to;
B, the thermal conversion of air-flow ullrasonic spraying prepare precursor powder:
Changing the cobalt nitrate solution of preparation over to ullrasonic spraying thermal conversion tower carries out the ullrasonic spraying thermal conversion and prepares the nanometer grade cobalt oxide precursor powder, the nozzle that uses is circumferential weld resonant mode air-flow ultrasonic atomizing nozzle, nozzle spray angle α=45 ℃, whiff pressure air 2.5～3.5MPa, air-flow jet velocity 2～2.5 Mach numbers, 68～128 ℃ of hot blast temperatures, liquid flow transfer rate 200ml/ branch, can be made into the cobalt oxide precursor powder of median size＜60nm after the thermal conversion of air-flow ullrasonic spraying;
Nitrate ion is removed in c, roasting:
In the precursor powder of nitrate preparation, because of containing NO
-1 3Nitrate ion, at 450～500 ℃, low-temperature bake is 30～50 minutes in the air, can be with NO
-1 3The nitrate radical branch is taken off, and obtains the exsiccant nano Co
2O
3Cobalt oxide powder;
D, shearing-crushing:
With the high speed shear crusher machine of the cobalt oxide powder after the roasting, this operation is the bridged particle that forms in the broken roasting process, prevent that the cobalt powder particle is grown up in reduction process, press cobalt oxide powder: industrial spirit=1: 5 mass ratio adds industrial spirit, together put in the batch can of shears, under 10000 rev/mins of rotating speeds,, calculate shear time by 15 minutes/100 gram powder, after the shearing, emit slip;
E, high speed centrifugation separate alcohol:
With industrial spirit and nanometer grade cobalt oxide powder separation, slightly alcoholic cobalt oxide slip changes over to air-dry oxide slurry after the fragmentation with high-speed continuous whizzer;
F, air-dry:
Slightly alcoholic cobalt oxide slip obtains exsiccant nano level Co through air-dry
2O
3Powder changes the hydrogen reducing furnace reduction over to;
G, hydrogen reducing prepare nano-cobalt powder:
With exsiccant nano level Co
2O
3Powder is put into stainless steel tubular type reduction furnace, at 520～560 ℃, 45～60 minutes, uses H
2The gas reduction, H
2Gas cross section flow 80～100ml/cm
2Powder after the reduction is put into acetone-oleic acid liquid after coming out of the stove, prevent spontaneous combustion, promptly makes the 1Kg cobalt powder of median size≤80nm;
H, product performance detect:
Carry out XRD, BET specific surface, TEM granule-morphology and granularity;
I, product vacuum packaging
3, according to claim 1 or 2 described methods, it is characterized in that: CoSO is selected in the preparation of the cobalt ion aqueous solution for use
46H
2During O vitriol, except that the relationship between quality of pressing aqueous solution preparation of vitriol molecular formula calculating cobalt ion and cobalt powder, also the precursor powder of spraying gained should be cleaned repeatedly with distilled water before roasting, remove SO
2- 4Sulfate radical.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410068855 CN1248813C (en) | 2004-07-09 | 2004-07-09 | Process for preparing nano grade super fine cobalt powder |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410068855 CN1248813C (en) | 2004-07-09 | 2004-07-09 | Process for preparing nano grade super fine cobalt powder |
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| Publication Number | Publication Date |
|---|---|
| CN1586772A true CN1586772A (en) | 2005-03-02 |
| CN1248813C CN1248813C (en) | 2006-04-05 |
Family
ID=34604187
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|---|---|---|---|
| CN 200410068855 Expired - Fee Related CN1248813C (en) | 2004-07-09 | 2004-07-09 | Process for preparing nano grade super fine cobalt powder |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071108A1 (en) * | 2005-12-21 | 2007-06-28 | Shenzhen Gem High-Tech Joint-Stock Co., Ltd. | Process of produceing superfine cobalt powder with circulation technology and its apparatus |
| CN100439014C (en) * | 2006-01-26 | 2008-12-03 | 湖南凯丰新材料有限公司 | Preparation method and equipment for nano-grade superfine cobalt powder |
| CN102631882A (en) * | 2012-04-23 | 2012-08-15 | 常州亚环环保科技有限公司 | Preparation method of magnetic nanometer material for treating 2-chlorine-3-pyridinecarbaldehydes waste |
| CN106077694A (en) * | 2016-08-08 | 2016-11-09 | 南昌大学 | A kind of preparation method of spherical cobalt powder |
| CN107570723A (en) * | 2017-08-10 | 2018-01-12 | 湖南工业大学 | Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof |
| CN111072073A (en) * | 2019-12-20 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of Ni monatomic doped cobaltosic oxide nano material, product and application thereof |
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| CN113909485A (en) * | 2021-10-11 | 2022-01-11 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN115555575A (en) * | 2022-09-21 | 2023-01-03 | 安徽格派锂电循环科技有限公司 | Method for preparing nano cobalt particles by utilizing thermal spraying method |
-
2004
- 2004-07-09 CN CN 200410068855 patent/CN1248813C/en not_active Expired - Fee Related
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007071108A1 (en) * | 2005-12-21 | 2007-06-28 | Shenzhen Gem High-Tech Joint-Stock Co., Ltd. | Process of produceing superfine cobalt powder with circulation technology and its apparatus |
| CN100439014C (en) * | 2006-01-26 | 2008-12-03 | 湖南凯丰新材料有限公司 | Preparation method and equipment for nano-grade superfine cobalt powder |
| CN102631882A (en) * | 2012-04-23 | 2012-08-15 | 常州亚环环保科技有限公司 | Preparation method of magnetic nanometer material for treating 2-chlorine-3-pyridinecarbaldehydes waste |
| CN106077694A (en) * | 2016-08-08 | 2016-11-09 | 南昌大学 | A kind of preparation method of spherical cobalt powder |
| CN107570723A (en) * | 2017-08-10 | 2018-01-12 | 湖南工业大学 | Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof |
| CN107570723B (en) * | 2017-08-10 | 2019-12-03 | 湖南工业大学 | Method for producing superfine cobalt powder for hard alloy by fluidized reduction of cobalt carbonate and production system thereof |
| CN111072073A (en) * | 2019-12-20 | 2020-04-28 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of Ni monatomic doped cobaltosic oxide nano material, product and application thereof |
| CN111689478A (en) * | 2020-06-11 | 2020-09-22 | 黄湛明 | Preparation method and preparation system of high-purity nano selenium powder |
| CN111689478B (en) * | 2020-06-11 | 2022-01-28 | 黄湛明 | Preparation method and preparation system of high-purity nano selenium powder |
| CN113909485A (en) * | 2021-10-11 | 2022-01-11 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN113909485B (en) * | 2021-10-11 | 2023-11-17 | 先导薄膜材料（广东）有限公司 | Preparation method of superfine cobalt powder |
| CN115555575A (en) * | 2022-09-21 | 2023-01-03 | 安徽格派锂电循环科技有限公司 | Method for preparing nano cobalt particles by utilizing thermal spraying method |
| CN115555575B (en) * | 2022-09-21 | 2024-03-29 | 安徽格派锂电循环科技有限公司 | Method for preparing nano cobalt particles by using thermal spraying method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1248813C (en) | 2006-04-05 |
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