CN115872455A - Preparation method of aluminum-doped small-particle-size cobaltosic oxide - Google Patents
Preparation method of aluminum-doped small-particle-size cobaltosic oxide Download PDFInfo
- Publication number
- CN115872455A CN115872455A CN202211418377.XA CN202211418377A CN115872455A CN 115872455 A CN115872455 A CN 115872455A CN 202211418377 A CN202211418377 A CN 202211418377A CN 115872455 A CN115872455 A CN 115872455A
- Authority
- CN
- China
- Prior art keywords
- aluminum
- solution
- reaction kettle
- particle
- cobalt
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 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 abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 40
- 239000000463 material Substances 0.000 claims abstract description 21
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims abstract description 20
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 claims abstract description 20
- BLJNPOIVYYWHMA-UHFFFAOYSA-N alumane;cobalt Chemical compound [AlH3].[Co] BLJNPOIVYYWHMA-UHFFFAOYSA-N 0.000 claims abstract description 18
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract description 16
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract description 16
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 16
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 14
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 8
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 230000001276 controlling effect Effects 0.000 description 13
- 239000013078 crystal Substances 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of aluminum-doped small-particle-size cobaltosic oxide, which comprises the following steps of: preparing cobalt chloride solution and aluminum sulfate solution into cobalt aluminum solution with the aluminum content of 6000-6400 ppm; preparing a base solution in a reaction kettle, introducing the prepared cobalt-aluminum solution and an ammonium bicarbonate solution into the reaction kettle simultaneously, dividing half of materials in the reaction kettle when the particle size of the materials in the reaction kettle grows to 3.1-3.5 mu m, and continuing to react in the reaction kettle; when the particle size of the materials in the reaction kettle grows to 4.7-5.1 mu m, the reaction is finished to obtain the aluminum-doped cobalt carbonate; washing, drying and calcining to obtain the aluminum-doped small-particle-size particle cobaltosic oxide. Meanwhile, parameters such as Ph of a reaction system, reaction temperature, stirring speed, calcination temperature and the like are controlled, the cobaltosic oxide with the high-aluminum small-particle-size particles, which are centralized in particle size distribution, high in tap density and basically free of flakes, is prepared, and the electrochemical performance of the battery can be improved by the small particles obtained through calcination.
Description
Technical Field
The invention belongs to the field of lithium ion battery materials, and particularly relates to a preparation method of aluminum-doped small-particle-size cobaltosic oxide.
Background
The cobaltosic oxide is an important raw material of a lithium battery, particularly used as a precursor of a lithium cobaltate positive electrode material, and the preparation process of the cobaltosic oxide is developed towards two ends of a large particle size particle and a small particle size particle.
Patent CN202111020999.2 discloses a preparation method of high tap aluminum-doped small-particle-size cobaltosic oxide, which comprises the following steps: preparing a cobalt-aluminum solution; adding the base solution into the seed crystal kettle and starting stirring; adding a cobalt aluminum solution and an ammonium bicarbonate solution into a reaction kettle simultaneously, and stopping the reaction when the granularity D50 of the material grows to 3.0-3.5 mu m to obtain seed crystals; and (3) separating half of the seed crystal into a finished product kettle, simultaneously adding a cobalt aluminum solution and an ammonium bicarbonate solution into the finished product kettle, synthesizing to obtain a finished product cobalt carbonate, stopping reaction when the granularity D50 of the finished product cobalt carbonate grows to 5.8-6.0 mu m, and centrifugally washing and calcining the obtained finished product cobalt carbonate to obtain the high-tap aluminum-doped small-particle-size cobaltosic oxide. The calcination process of the patent is unstable, and the aluminum distribution uniformity of the cobaltosic oxide particles is not good.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a preparation method of aluminum-doped small-grain-size cobaltosic oxide.
The invention is realized by the following technical scheme.
A preparation method of aluminum-doped small-particle-size cobaltosic oxide comprises the following steps:
(1) Preparing cobalt chloride solution and aluminum sulfate solution into cobalt aluminum solution with the aluminum content of 6000-6400 ppm;
(2) Preparing a base solution in a reaction kettle, heating to 38-42 ℃, and controlling the stirring speed to be 160-220 r/min;
(3) Simultaneously introducing the prepared cobalt aluminum solution and ammonium bicarbonate solution into the reaction kettle obtained in the step (2), and controlling the ph of a reaction system to be 7.1-7.5;
(4) When the particle size of the materials in the reaction kettle grows to 3.1-3.5 mu m, dividing half of the materials in the reaction kettle, adjusting the ph of a reaction system to 7.1-7.3, and continuing the reaction in the reaction kettle;
(5) When the particle size of the materials in the reaction kettle grows to 4.7-5.1 mu m, the reaction is finished to obtain the aluminum-doped cobalt carbonate;
(6) Washing, drying and calcining the obtained aluminum-doped cobalt carbonate to obtain aluminum-doped small-particle-size granular cobaltosic oxide, wherein the temperature field in the rotary kiln sequentially comprises the following steps: 540 +/-50 ℃/690 +/-50 ℃/710 +/-50 ℃/690 +/-50 ℃/600 +/-50 ℃/400 +/-50 ℃/300 +/-50 ℃, and the rotary frequency of the kiln body of the rotary kiln is 15 +/-2 Hz.
Further, the cobalt aluminum solution is prepared by adopting a cobalt chloride solution with the concentration of 140 +/-20 g/L and an aluminum sulfate solution with the concentration of 1.2 +/-0.2 g/L in the step (1).
Further, the base solution in the step (2) is prepared by adopting an ammonium bicarbonate solution with the concentration of 240 +/-20 g/L and pure water, and the base solution ph is 8.6 +/-0.2.
Further, the concentration of the ammonium bicarbonate solution in the step (3) and the concentration of the ammonium bicarbonate solution in the step (4) are both 240 +/-20 g/L.
Further, the washing process in the step (6) adopts hot water with the temperature of 40-70 ℃.
The method has the beneficial technical effects that parameters such as Ph of a reaction system, reaction temperature, stirring speed, calcining temperature and the like are controlled by adjusting the content of the cobalt-aluminum binary liquid aluminum, and the prepared material has the advantages of concentrated particle size distribution and high tap density (2.1 +/-0.1 g/cm) 3 ) The cobaltosic oxide which is basically flakeless and has high aluminum and small grain size particles has the aluminum content of 5900-6300ppm and the grain size of 4.7 +/-0.2 mu m, and the small particles obtained by calcination can improve the electrochemical performance of the battery. The stirring speed of the reaction kettle is adjusted, the growth speed of particles and the particle size distribution of the particles can be adjusted, the particle size distribution of the particles is more concentrated, the uniformity of the particles is better, and the tap density of the particles can be improved; the reaction system ph and temperature have great influence on the particle morphology, and the condition that the particle surface is flaky can be controlled by adjusting the ph and the temperature within a proper range; by controlling the sintering temperature of each temperature field in the rotary kiln and the kiln bodyThe rotation frequency is used for controlling the sintering degree of the particles, so that the tap density of the particles can be improved, and the tap density can be kept stable.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
Example 1
A preparation method of aluminum-doped small-particle-size cobaltosic oxide comprises the following steps:
(1) Preparing a cobalt aluminum solution with the aluminum content of 6110ppm by using a cobalt chloride solution with the concentration of 140g/L and an aluminum sulfate solution with the concentration of 1.18 g/L;
(2) Adding 240g/L ammonium bicarbonate solution and pure water into a reaction kettle to prepare base solution, wherein the base solution ph is 8.5, heating to 38 ℃, and controlling the stirring speed to be 160-180 r/min;
(3) Simultaneously introducing the prepared cobalt-aluminum solution and 240g/L ammonium bicarbonate solution into the reaction kettle obtained in the step (2), adjusting the flow rate, and controlling the ph of the reaction system to be 7.1-7.5;
(4) When the particle size of the materials in the reaction kettle grows to 31 mu m, dividing the materials in the reaction kettle by half, adjusting the flow, controlling the ph of a reaction system to be 7.1-7.3, and continuing the reaction;
(5) When the particle size of the materials in the reaction kettle grows to 4.8 mu m, the reaction is finished to obtain the aluminum-doped cobalt carbonate;
(6) Washing the obtained aluminum-doped cobalt carbonate with hot water at 65 ℃, drying the cobalt carbonate by a flash evaporation machine, and then calcining the cobalt carbonate in a rotary kiln, wherein the temperature field in the kiln is 530 ℃/660 ℃/700 ℃/680 ℃/550 ℃/400 ℃/320 ℃ in sequence, the rotation frequency of a kiln body is 13Hz, and the aluminum-doped small-particle-size particle cobaltosic oxide finished product is obtained, wherein the aluminum content is 5970ppm, the particle size is 4.5 mu m, and the tap density is 2.1g/cm 3 。
Example 2
A preparation method of aluminum-doped small-particle-size cobaltosic oxide is characterized by comprising the following steps of:
(1) Preparing cobalt chloride solution with the concentration of 125g/L and aluminum sulfate solution with the concentration of 1.07g/L into cobalt-aluminum solution with the aluminum content of 6200 ppm;
(2) Adding 225g/L ammonium bicarbonate solution and pure water into a reaction kettle to prepare base solution, wherein the base solution ph is 8.4, heating to 40 ℃, and controlling the stirring speed to be 180-200 r/min;
(3) Simultaneously introducing the prepared cobalt-aluminum solution and 225g/L ammonium bicarbonate solution into the reaction kettle obtained in the step (2), regulating the flow rate, and controlling the ph of a reaction system to be 7.1-7.5;
(4) When the particle size of the materials in the reaction kettle grows to 3.3 mu m, dividing the materials in the reaction kettle into half, adjusting the flow, controlling the ph of a reaction system to be 7.1-7.3, and continuing to react;
(5) When the particle size of the materials in the reaction kettle grows to 4.9 mu m, the reaction is finished to obtain the aluminum-doped cobalt carbonate;
(6) Washing the obtained aluminum-doped cobalt carbonate with hot water at the temperature of 45 ℃, drying the cobalt carbonate by a flash evaporation machine, and then calcining the cobalt carbonate in a rotary kiln, wherein the temperature field in the kiln is 550 ℃/690 ℃/750 ℃/650 ℃/550 ℃/410 ℃/300 ℃ in sequence, the rotation frequency of a kiln body is 15Hz, and the aluminum-doped small-particle-size particle cobaltosic oxide finished product is obtained, wherein the aluminum content is 6070ppm, the particle size is 4.6 mu m, and the tap density is 2.15g/cm 3 。
Example 3
A preparation method of aluminum-doped small-particle-size cobaltosic oxide is characterized by comprising the following steps of:
(1) Preparing cobalt aluminum solution with aluminum content of 6250ppm by using cobalt chloride solution with concentration of 150g/L and aluminum sulfate solution with concentration of 1.29 g/L;
(2) Adding an ammonium bicarbonate solution with the concentration of 255g/L and pure water into a reaction kettle to prepare a base solution, wherein the base solution ph is 8.62, heating to 42 ℃, and controlling the stirring speed to be 200-220 r/min;
(3) Simultaneously introducing the prepared cobalt-aluminum solution and an ammonium bicarbonate solution with the concentration of 255g/L into the reaction kettle obtained in the step (2), and controlling the ph of a reaction system to be 7.1-7.5;
(4) When the particle size of the materials in the reaction kettle grows to 3.5 mu m, dividing the materials in the reaction kettle into half, adjusting the flow, controlling the ph of the reaction system to be 7.1-7.3, and continuing to react;
(5) When the particle size of the materials in the reaction kettle grows to 5.1 mu m, the reaction is finished to obtain the aluminum-doped cobalt carbonate;
(6) Washing the obtained aluminum-doped cobalt carbonate with hot water at the temperature of 55 ℃, drying the cobalt carbonate by a flash evaporation machine, and then calcining the cobalt carbonate in a rotary kiln, wherein the temperature field in the kiln is 570 ℃/710 ℃/750 ℃/700 ℃/580 ℃/450 ℃/330 ℃ in sequence, the rotation frequency of a kiln body is 16Hz, and the aluminum-doped small-particle-size particle cobaltosic oxide finished product is obtained, wherein the aluminum content is 6180ppm, the particle size is 4.9 mu m, and the tap density is 2.2g/cm 3 。
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention. It should be noted that those skilled in the art, on the basis of the teachings provided herein, may make other modifications equivalent to those already described, and should be considered within the scope of the present invention.
Claims (5)
1. A preparation method of aluminum-doped small-particle-size cobaltosic oxide is characterized by comprising the following steps of:
(1) Preparing cobalt chloride solution and aluminum sulfate solution into cobalt aluminum solution with the aluminum content of 6000-6400 ppm;
(2) Preparing a base solution in a reaction kettle, heating to 38-42 ℃, and controlling the stirring speed to be 160-220 r/min;
(3) Simultaneously introducing the prepared cobalt aluminum solution and ammonium bicarbonate solution into the reaction kettle obtained in the step (2), and controlling the ph of a reaction system to be 7.1-7.5;
(4) When the particle size of the materials in the reaction kettle grows to 3.1-3.5 mu m, dividing half of the materials in the reaction kettle, adjusting the ph of a reaction system to be 7.1-7.3, and continuing to react in the reaction kettle;
(5) When the grain diameter of the materials in the reaction kettle grows to 4.7-5.1 mu m, the reaction is finished to obtain the aluminum-doped cobalt carbonate;
(6) Washing, drying and calcining the obtained aluminum-doped cobalt carbonate to obtain aluminum-doped small-particle-size granular cobaltosic oxide, wherein the temperature field in the rotary kiln sequentially comprises the following steps: 540 +/-50 ℃/690 +/-50 ℃/710 +/-50 ℃/690 +/-50 ℃/600 +/-50 ℃/400 +/-50 ℃/300 +/-50 ℃, and the rotary frequency of the kiln body of the rotary kiln is 15 +/-2 Hz.
2. The method according to claim 1, wherein the step (1) is carried out by preparing a cobalt aluminum solution from a cobalt chloride solution having a concentration of 140 ± 20g/L and an aluminum sulfate solution having a concentration of 1.2 ± 0.2 g/L.
3. The method according to claim 1, wherein the base solution in step (2) is prepared from 240 ± 20g/L ammonium bicarbonate solution and pure water, and the base solution ph is 8.6 ± 0.2.
4. The method according to claim 1, wherein the concentration of the ammonium bicarbonate solution in each of the step (3) and the step (4) is 240 ± 20g/L.
5. The method according to claim 1, wherein the washing in the step (6) is performed with hot water at 40-70 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211418377.XA CN115872455A (en) | 2022-11-14 | 2022-11-14 | Preparation method of aluminum-doped small-particle-size cobaltosic oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211418377.XA CN115872455A (en) | 2022-11-14 | 2022-11-14 | Preparation method of aluminum-doped small-particle-size cobaltosic oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115872455A true CN115872455A (en) | 2023-03-31 |
Family
ID=85759823
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211418377.XA Pending CN115872455A (en) | 2022-11-14 | 2022-11-14 | Preparation method of aluminum-doped small-particle-size cobaltosic oxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115872455A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115710A (en) * | 2018-10-31 | 2020-05-08 | 格林美（江苏）钴业股份有限公司 | Preparation method of aluminum-doped cobalt oxide |
| CN113213550A (en) * | 2021-05-08 | 2021-08-06 | 荆门市格林美新材料有限公司 | Preparation method of aluminum-doped cobaltosic oxide for 4.5V lithium cobaltate |
| CN113772746A (en) * | 2021-09-01 | 2021-12-10 | 荆门市格林美新材料有限公司 | Preparation method of high-tap-density aluminum-doped small-particle-size cobaltosic oxide |
| CN114804221A (en) * | 2022-04-28 | 2022-07-29 | 荆门市格林美新材料有限公司 | Cobaltous oxide and preparation method and application thereof |
-
2022
- 2022-11-14 CN CN202211418377.XA patent/CN115872455A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111115710A (en) * | 2018-10-31 | 2020-05-08 | 格林美（江苏）钴业股份有限公司 | Preparation method of aluminum-doped cobalt oxide |
| CN113213550A (en) * | 2021-05-08 | 2021-08-06 | 荆门市格林美新材料有限公司 | Preparation method of aluminum-doped cobaltosic oxide for 4.5V lithium cobaltate |
| CN113772746A (en) * | 2021-09-01 | 2021-12-10 | 荆门市格林美新材料有限公司 | Preparation method of high-tap-density aluminum-doped small-particle-size cobaltosic oxide |
| CN114804221A (en) * | 2022-04-28 | 2022-07-29 | 荆门市格林美新材料有限公司 | Cobaltous oxide and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106784800B (en) | High-activity spherical cobaltosic oxide for power lithium ion battery and preparation method thereof | |
| CN110817975B (en) | Method for reducing sulfur content of ternary precursor | |
| CN101973592B (en) | Preparation method of high-gravity spherical cobalt carbonate | |
| CN113830839B (en) | Preparation method and application of flaky aluminum-doped cobalt carbonate | |
| CN109411718B (en) | Preparation method of doping modified ternary cathode material | |
| WO2022179291A1 (en) | Method for separating ferronickel from lateritic nickel ore leach solution and preparing iron phosphate, and application | |
| CN110808369B (en) | Preparation method of low-sodium-sulfur nickel-cobalt-aluminum ternary precursor | |
| CN111600015B (en) | Narrow-distribution small-granularity spherical nickel-cobalt-manganese hydroxide precursor and preparation method thereof | |
| CN107150127B (en) | Preparation method of spherical cobalt powder | |
| CN113307308A (en) | Doped large-particle cobalt carbonate and preparation method thereof | |
| CN108264095B (en) | Preparation method of battery-grade spherical cobalt carbonate | |
| CN104828869B (en) | A kind of sodium manganese oxide micropowder and preparation method thereof | |
| CN110611098B (en) | High-radiation and high-tap-density nickel-cobalt lithium aluminate precursor and preparation method thereof | |
| CN114349066B (en) | Preparation method of magnesium-aluminum co-doped lithium cobaltate precursor | |
| CN112661199B (en) | Preparation method of high-tap-density aluminum oxide coated magnesium-manganese co-doped cobaltosic oxide | |
| CN113636604A (en) | Preparation method of high-aluminum-doped small-particle-size cobalt carbonate particles | |
| CN115385399B (en) | Nickel-cobalt-manganese ternary precursor and intermittent preparation process thereof | |
| CN114291850A (en) | Method for controlling morphology of ternary precursor in preparation process of ternary precursor | |
| CN105810894A (en) | Multilayer coated structure lithium ion battery positive electrode material preparation method | |
| CN114751465B (en) | Method for preparing high Al uniform cobaltosic oxide by replacing staged elements | |
| CN113277572B (en) | Low-sodium-sulfur-nickel-cobalt composite hydroxide precursor and preparation method thereof | |
| CN115872455A (en) | Preparation method of aluminum-doped small-particle-size cobaltosic oxide | |
| JP2000077070A (en) | Nickel hydroxide powder and its manufacture | |
| CN111115705A (en) | Preparation method of cobalt oxide coated with zirconium | |
| CN114940515A (en) | Aluminum-doped cobalt carbonate and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |