CA2377152C - Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process - Google Patents
Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process Download PDFInfo
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- CA2377152C CA2377152C CA2377152A CA2377152A CA2377152C CA 2377152 C CA2377152 C CA 2377152C CA 2377152 A CA2377152 A CA 2377152A CA 2377152 A CA2377152 A CA 2377152A CA 2377152 C CA2377152 C CA 2377152C
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- H01M4/00—Electrodes
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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Abstract
The invention relates to a method for preparing a cobaltous hydroxide with a high density and a large particle size or an alloy hydroxide of cobalt and some other metal, in which a complexing agent and hydroxide ion is added to an aqueous cobalt brine or an aqueous brine of cobalt and some other metal under alkaline conditions in order to form a metal hydroxide. In this method, the complexing agent is selected so as to form an ammonium complex with the metal ion. The molar ratio of complexing agent to metal is about 0.5-3, and the pH is regulated in the range 10-13.
Description
Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process The invention relates to a method for preparing cobaltous hydroxide with a high density and a large particle size or an alloy hydroxide of cobalt and some otlt;er metal. The invention also relates to the product produced with this method.
Cobaltous hydroxide is used in many applications, for instance as an additive in chargeable NiMH and NiCd accumulators in the electronics industry. In addition, it is suitable for use as a precursor in the preparation of oxide products, such as LiCo02 and LiCoM02 (M stands for metal). Cobaltous hydroxide is also used as a catalyst or a precursor in catalyst production. A hydroxide product comprising any other metal in addition to cobalt, such as nickel, manganese, magnesium or aluminium, is also suitable for use for the purposes mentioned above.
There are many known methods for preparing cobaltous hydroxide in the field.
The method of US patent 5,057,299 prepares cobaltous hydroxide by combining a cobaltous ion with a complexing agent, thus producing a water-soluble cobalt complex. Hydroxide ion is added to this, and the mixture is heated and kept in hydrothermal conditions until the cobaltous hydroxide precipitates. With the method of this US patent, the particle size increases at higher temperatures.
Nonetheless, the method of the patent allows the particle size to be controlled only in the range from approx. 0.05 to 0.5 E,un by means of the temperature.
In applications of the accumulator industry, NiCd and NIMH accumulators are required to have good capacity. The capacity can be raised by using cobaltous hydroxide with maximum density as an additive in accumulators. In addition to this, it is important that the cobaltous hydroxide used in the production of oxide products has a small specific surface and a high density. The purpose of the present invention is to provide a method for preparing cobaltous hydroxide particles with a large particle size or alloy hydroxide particles of cobalt and some other metal with a method that is easy to control. The purpose is to achieve cobaltous hydroxide particles or alloy hydroxide particles of cobalt and some other metal with a particle size above 1 pm, preferably above 3 ~,un. This has been achieved according to the invention in the manner described in the accompanying claims.
Besides cobaltous hydroxide, the method in accordance with the invention can be used to prepare alloy hydroxides of cobalt and one or more other metals. The other metals used may comprise for instance nickel, manganese, magnesium or aluminium, or alloys of these, depending on the purpose of use.
The starting material used in the method of the invention is an aqueous brine of cobalt or cobalt and alloy metals in the form of sulphate, nitrate or chloride. The concentration of the solution may vary in the range from 10 to 120 g/1 calculated on the total metal content.
A complexing agent that forms an ammonium complex with the metal ion is added to this metal brine. The complexing agent may be ammonium sulphate, aqueous ammonia or any other ammonium ion source. In principle, the complexing agent may also be some other substance forming a complex with a metal, such as for instance EDTA. In the present invention, ammonium ion has nevertheless proved a good complexing agent owing to its economic price and good complexing characteristics. The molar ratio of the ammonium complexing agent to the metal introduced in the reactor is preferably about 0.5-3, most preferably about 1.5-2Ø
The reaction is performed under alkaline conditions and NaOH is preferably used for pH regulation. The preferred pH is in the range 10-13, most preferably the pH is in the range 11.2-12Ø The reaction is carried out at a temperature of about 90 °C, preferably at a temperature of about 70 °C. The method in accordance with the invention yields cobaltous hydroxide with a density of about 0.5-2.2 g/cm3, a particle size above approx. 1 ~.nn, typically approx. 1-20 pm and a specific surface of approx. 0.5-20 m2/g.
The particles obtained with the method of the invention are plate-like cobaltous hydroxide particles in the shape of a hexagon. It was found in connection with the invention that chloride solutions yield thicker particles than sulphate-based solutions, with the other reaction conditions unaltered. Thicker particles are considered more suitable for instance for the preparation of lithium cobalt oxide.
In the method of the invention, the particle size of cobaltous hydroxide can be controlled by means of the molar ratio of the ammonium ion to the cobalt ion and of the pH used. Figure 1 shows the particle size variation as a function of pH
with varied ratios NH3 ion/Co. The figure shows that a pH increase reduces the particle size, and that the higher the ratio NH3 ion/Co, the more notable the effect of the pH
on the particle size.
The invention is illuminated below by means of examples. In examples 1-3 the method has been carried out as a comparison without complexing with ammonium -, J
ions. Examples 4-6 illustrate the method of the invention, in which an ammonium complex with cobalt is formed. Example 7 exemplifies the method of the invention, in which nickel was used in addition to cobalt. The reaction temperature in the examples was 70 °C.
Comparative example 1 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into a first reactor. The pH was maintained constant in the range 11.8-12.0 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow, resulting in pH 13.5.
The overflow. from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 0.9 l.~m when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 sluiTy). The density was 0.5 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 30 m2/g.
Comparative example 2 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor. The pH was maintained constant in the range 11.6-11.8 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5.
The overflow from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 1.1 pm when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 0.7 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 29 m2/g.
Comparative example 3 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor. The pH was maintained constant in the range 11.2-11.4 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5.
The overflow from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The average particle size D~0 of the dried Co(OH)2 was 1.9 E,un when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 0.6 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 35 m2/g.
Example 4 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor, which contained an aqugous_ solution of ammonia with the molar ratio metal/ammonia. The pH was maintained constant in the range 11.8-12.0 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH
13.5. The overflow from the second reactor was filtered and washed with water.
The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 1.8 Nm when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH}z slurry). The density was 0.7 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 5.8 m2/g.
Example 5 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor, which contained an aqueous solution of ammonia with the molar ratio 2 metal/ammonium. The pH was maintained constant in the range 11.6-11.8 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5. The overflow from the second reactor was filtered and washed with water.
The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 3.9 ~,un when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 1.2 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 2.6 m2/g.
Example 6 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor, which contained an aqueous solution of ammonia with the molar ratio 2 metal/ammonium. The pH was maintained constant in the range 11.2-11.4 by 5 adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5. The overflow from the second reactor was filtered and washed with water.
The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 7.4 pm when determined with a Malvern Mastersizer particle -size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 1.7 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 1.8 m2/g.
Example 7 An alloy brine was prepared which contained CoCl2 and NiCl2 solutions (30 g/1 Co and 8g/1 Ni). The solution was introduced continually into the first reactor, which contained an aqueous solution of ammonia with the molar ratio metal/ammonium being 2. The pH was maintained constant in the range 11.2-11.4 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5.
The overflow from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The chemical analysis indicated precipitation of alloy hydroxide. The average particle size D50 of the dried Co0.8Ni0.2(OH)2 was 6.9 Eun when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 1.6 g/cm3 (ASTM
B527-93). The specific surface (BET ASTM D4567-86) was 3.2 m2/g.
To facilitate the comparison, the table below shows the physical properties of the products exemplified above. The table also shows the crystal size of the products, which was measured with an X-ray diffraction meter.
Table 1 Ezample PrecipitatComplexingAverage DensitySpecificXRD XRD
ed pH agent particle (g/cm')surface(001) I
size mz/ (nm (101) ( ) nm Comparative11.8-12.0None 0.9 0.5 30 23 27 exam 1e Comparative11.6-11.8None 1.1 0.7 29 26 30 exam 1e Comparative11.2-11.4None 1.9 0.6 35 27 32 exam 1e Exam 1e 11.8-12.0NH3 ion 1.8 0.7 5.8 50 49 Exam 1e 11.6-11.8NH3 ion 3.9 1.2 2.6 56 56 Exam 1e 11.2-11.4NH3 ion 7.4 1.7 1.8 61 64 Example 11.2-11.4NH3 ion 6.9 1.6 3.2 59 ~ 57 7 ~
The table shows that, with ammonium ion used as the complexing agent, the product had a larger particle size and higher density than without a complexing 5 agent. As an exception from this, the product of example 4 had a particle size and a density approximately equal to those of the comparative examples. In fact, the specific surface and crystal size of this product also equalled the values of the products of examples 5-7.
A number of applications of the invention have been presented above. The invention is naturally not restricted to the examples above, its principle being variable within the scope of protection of the claims.
Cobaltous hydroxide is used in many applications, for instance as an additive in chargeable NiMH and NiCd accumulators in the electronics industry. In addition, it is suitable for use as a precursor in the preparation of oxide products, such as LiCo02 and LiCoM02 (M stands for metal). Cobaltous hydroxide is also used as a catalyst or a precursor in catalyst production. A hydroxide product comprising any other metal in addition to cobalt, such as nickel, manganese, magnesium or aluminium, is also suitable for use for the purposes mentioned above.
There are many known methods for preparing cobaltous hydroxide in the field.
The method of US patent 5,057,299 prepares cobaltous hydroxide by combining a cobaltous ion with a complexing agent, thus producing a water-soluble cobalt complex. Hydroxide ion is added to this, and the mixture is heated and kept in hydrothermal conditions until the cobaltous hydroxide precipitates. With the method of this US patent, the particle size increases at higher temperatures.
Nonetheless, the method of the patent allows the particle size to be controlled only in the range from approx. 0.05 to 0.5 E,un by means of the temperature.
In applications of the accumulator industry, NiCd and NIMH accumulators are required to have good capacity. The capacity can be raised by using cobaltous hydroxide with maximum density as an additive in accumulators. In addition to this, it is important that the cobaltous hydroxide used in the production of oxide products has a small specific surface and a high density. The purpose of the present invention is to provide a method for preparing cobaltous hydroxide particles with a large particle size or alloy hydroxide particles of cobalt and some other metal with a method that is easy to control. The purpose is to achieve cobaltous hydroxide particles or alloy hydroxide particles of cobalt and some other metal with a particle size above 1 pm, preferably above 3 ~,un. This has been achieved according to the invention in the manner described in the accompanying claims.
Besides cobaltous hydroxide, the method in accordance with the invention can be used to prepare alloy hydroxides of cobalt and one or more other metals. The other metals used may comprise for instance nickel, manganese, magnesium or aluminium, or alloys of these, depending on the purpose of use.
The starting material used in the method of the invention is an aqueous brine of cobalt or cobalt and alloy metals in the form of sulphate, nitrate or chloride. The concentration of the solution may vary in the range from 10 to 120 g/1 calculated on the total metal content.
A complexing agent that forms an ammonium complex with the metal ion is added to this metal brine. The complexing agent may be ammonium sulphate, aqueous ammonia or any other ammonium ion source. In principle, the complexing agent may also be some other substance forming a complex with a metal, such as for instance EDTA. In the present invention, ammonium ion has nevertheless proved a good complexing agent owing to its economic price and good complexing characteristics. The molar ratio of the ammonium complexing agent to the metal introduced in the reactor is preferably about 0.5-3, most preferably about 1.5-2Ø
The reaction is performed under alkaline conditions and NaOH is preferably used for pH regulation. The preferred pH is in the range 10-13, most preferably the pH is in the range 11.2-12Ø The reaction is carried out at a temperature of about 90 °C, preferably at a temperature of about 70 °C. The method in accordance with the invention yields cobaltous hydroxide with a density of about 0.5-2.2 g/cm3, a particle size above approx. 1 ~.nn, typically approx. 1-20 pm and a specific surface of approx. 0.5-20 m2/g.
The particles obtained with the method of the invention are plate-like cobaltous hydroxide particles in the shape of a hexagon. It was found in connection with the invention that chloride solutions yield thicker particles than sulphate-based solutions, with the other reaction conditions unaltered. Thicker particles are considered more suitable for instance for the preparation of lithium cobalt oxide.
In the method of the invention, the particle size of cobaltous hydroxide can be controlled by means of the molar ratio of the ammonium ion to the cobalt ion and of the pH used. Figure 1 shows the particle size variation as a function of pH
with varied ratios NH3 ion/Co. The figure shows that a pH increase reduces the particle size, and that the higher the ratio NH3 ion/Co, the more notable the effect of the pH
on the particle size.
The invention is illuminated below by means of examples. In examples 1-3 the method has been carried out as a comparison without complexing with ammonium -, J
ions. Examples 4-6 illustrate the method of the invention, in which an ammonium complex with cobalt is formed. Example 7 exemplifies the method of the invention, in which nickel was used in addition to cobalt. The reaction temperature in the examples was 70 °C.
Comparative example 1 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into a first reactor. The pH was maintained constant in the range 11.8-12.0 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow, resulting in pH 13.5.
The overflow. from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 0.9 l.~m when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 sluiTy). The density was 0.5 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 30 m2/g.
Comparative example 2 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor. The pH was maintained constant in the range 11.6-11.8 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5.
The overflow from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 1.1 pm when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 0.7 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 29 m2/g.
Comparative example 3 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor. The pH was maintained constant in the range 11.2-11.4 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5.
The overflow from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The average particle size D~0 of the dried Co(OH)2 was 1.9 E,un when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 0.6 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 35 m2/g.
Example 4 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor, which contained an aqugous_ solution of ammonia with the molar ratio metal/ammonia. The pH was maintained constant in the range 11.8-12.0 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH
13.5. The overflow from the second reactor was filtered and washed with water.
The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 1.8 Nm when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH}z slurry). The density was 0.7 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 5.8 m2/g.
Example 5 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor, which contained an aqueous solution of ammonia with the molar ratio 2 metal/ammonium. The pH was maintained constant in the range 11.6-11.8 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5. The overflow from the second reactor was filtered and washed with water.
The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 3.9 ~,un when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 1.2 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 2.6 m2/g.
Example 6 An aqueous solution of CoCl2 (30 g/1 Co) was introduced continually into the first reactor, which contained an aqueous solution of ammonia with the molar ratio 2 metal/ammonium. The pH was maintained constant in the range 11.2-11.4 by 5 adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5. The overflow from the second reactor was filtered and washed with water.
The washed Co(OH)2 cake was dried.
The average particle size D50 of the dried Co(OH)2 was 7.4 pm when determined with a Malvern Mastersizer particle -size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 1.7 g/cm3 (ASTM B527-93). The specific surface (BET ASTM D4567-86) was 1.8 m2/g.
Example 7 An alloy brine was prepared which contained CoCl2 and NiCl2 solutions (30 g/1 Co and 8g/1 Ni). The solution was introduced continually into the first reactor, which contained an aqueous solution of ammonia with the molar ratio metal/ammonium being 2. The pH was maintained constant in the range 11.2-11.4 by adding sodium hydroxide solution. The overflow of the first reactor was conducted to the second reactor, where sodium hydroxide was added to the flow so as to obtain pH 13.5.
The overflow from the second reactor was filtered and washed with water. The washed Co(OH)2 cake was dried.
The chemical analysis indicated precipitation of alloy hydroxide. The average particle size D50 of the dried Co0.8Ni0.2(OH)2 was 6.9 Eun when determined with a Malvern Mastersizer particle size analyser (the determination was performed with laser diffraction on an aqueous Co(OH)2 slurry). The density was 1.6 g/cm3 (ASTM
B527-93). The specific surface (BET ASTM D4567-86) was 3.2 m2/g.
To facilitate the comparison, the table below shows the physical properties of the products exemplified above. The table also shows the crystal size of the products, which was measured with an X-ray diffraction meter.
Table 1 Ezample PrecipitatComplexingAverage DensitySpecificXRD XRD
ed pH agent particle (g/cm')surface(001) I
size mz/ (nm (101) ( ) nm Comparative11.8-12.0None 0.9 0.5 30 23 27 exam 1e Comparative11.6-11.8None 1.1 0.7 29 26 30 exam 1e Comparative11.2-11.4None 1.9 0.6 35 27 32 exam 1e Exam 1e 11.8-12.0NH3 ion 1.8 0.7 5.8 50 49 Exam 1e 11.6-11.8NH3 ion 3.9 1.2 2.6 56 56 Exam 1e 11.2-11.4NH3 ion 7.4 1.7 1.8 61 64 Example 11.2-11.4NH3 ion 6.9 1.6 3.2 59 ~ 57 7 ~
The table shows that, with ammonium ion used as the complexing agent, the product had a larger particle size and higher density than without a complexing 5 agent. As an exception from this, the product of example 4 had a particle size and a density approximately equal to those of the comparative examples. In fact, the specific surface and crystal size of this product also equalled the values of the products of examples 5-7.
A number of applications of the invention have been presented above. The invention is naturally not restricted to the examples above, its principle being variable within the scope of protection of the claims.
Claims (9)
1. Cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal, characterised in having a density of about 0.5-2.2 g/cm3, a particle size above about 1 µm, typically about 1-20 µm, and a specific surface of about 0.5-20 m2/g, and that it is prepared by adding a complexing agent and hydroxide ion under alkaline conditions to an aqueous cloride solution of cobalt or to an aqueous cloride solution of an alloy of cobalt and some other metal in order to form metal hydroxide, wherein the complexing agent is selected so as to form an ammonium complex with the metal ion, the molar ratio of complexing agent to metal being approx. 0.5-3 and the pH being adjusted in the range 10-13.
2. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that the pH is regulated in the range 11.2-12Ø
3. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that the other metal is nickel, manganese, magnesium or aluminium, or alloys of these.
4. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that the concentration of the cloride solution is in the range from 10 to 120 g/l calculated on the total metal content.
5. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that the complexing agent is ammonium sulphate or aqueous ammonia
6. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that the molar ratio of complexing agent to metal is approx. 1.5-2.
7. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that NaOH is used for pH regulation.
8. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 1, characterised in that the reaction is carried out at a temperature of about 40-90 °C.
9. A cobaltous hydroxide or alloy hydroxide formed of cobalt and some other metal as defined in claim 8, characterised in that the reaction is carried out at a temperature of about 70 °C.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FI991478A FI110093B (en) | 1999-06-29 | 1999-06-29 | High volume, large particle size cobalt hydroxide or cobalt alloy hydroxide |
| FI991478 | 1999-06-29 | ||
| PCT/FI2000/000581 WO2001000532A1 (en) | 1999-06-29 | 2000-06-28 | Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2377152A1 CA2377152A1 (en) | 2001-01-04 |
| CA2377152C true CA2377152C (en) | 2010-05-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA2377152A Expired - Lifetime CA2377152C (en) | 1999-06-29 | 2000-06-28 | Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP1210295B1 (en) |
| JP (1) | JP3961826B2 (en) |
| CN (1) | CN1164499C (en) |
| AT (1) | ATE286855T1 (en) |
| AU (1) | AU5829800A (en) |
| CA (1) | CA2377152C (en) |
| DE (1) | DE60017421T2 (en) |
| ES (1) | ES2235906T3 (en) |
| FI (1) | FI110093B (en) |
| NO (1) | NO20016394L (en) |
| WO (1) | WO2001000532A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP4359092B2 (en) * | 2003-08-21 | 2009-11-04 | Ａｇｃセイミケミカル株式会社 | Method for producing lithium cobalt composite oxide for positive electrode of secondary battery |
| CN1733599B (en) * | 2004-08-13 | 2010-04-28 | 中国人民解放军63971部队 | Preparation method of transition metal oxide or hydroxide wet gel |
| JP4846280B2 (en) * | 2005-06-23 | 2011-12-28 | 株式会社田中化学研究所 | Cobalt oxyhydroxide particles and method for producing the same |
| JP4846309B2 (en) * | 2005-09-09 | 2011-12-28 | 株式会社田中化学研究所 | Method for producing nickel manganese cobalt composite oxide |
| JP4746476B2 (en) * | 2006-05-10 | 2011-08-10 | 三井金属鉱業株式会社 | Cobalt hydroxide particles and cobalt oxide particles |
| JP4746477B2 (en) * | 2006-05-10 | 2011-08-10 | 三井金属鉱業株式会社 | Cobalt hydroxide particles and cobalt oxide particles |
| CN101955234B (en) * | 2009-07-15 | 2012-04-04 | 海南金亿新材料股份有限公司 | Preparation method of high-purity nanoscale cobalt hydroxide |
| CA2812231C (en) * | 2011-05-31 | 2020-04-07 | Omg Kokkola Chemicals Oy | Lithium cobalt oxide material |
| US10351440B2 (en) | 2011-05-31 | 2019-07-16 | Freeport Colbalt Oy | Lithium cobalt oxide material |
| JP5961004B2 (en) * | 2012-02-21 | 2016-08-02 | 日本化学工業株式会社 | Method for producing cobalt hydroxide, method for producing cobalt oxide, and method for producing lithium cobaltate |
| CN103232076A (en) * | 2013-05-16 | 2013-08-07 | 漳州师范学院 | Synthesis method of cobalt hydroxide with different grain diameters |
| JP6233175B2 (en) | 2014-02-05 | 2017-11-22 | 住友金属鉱山株式会社 | Cobalt hydroxide particles and method for producing the same, and positive electrode active material and method for producing the same |
| CN105304897B (en) * | 2014-11-29 | 2017-09-15 | 广东天劲新能源科技股份有限公司 | A kind of preparation method of bulky grain cobalt hydroxide battery material |
| CN104439280A (en) * | 2014-12-09 | 2015-03-25 | 英德佳纳金属科技有限公司 | Simultaneous preparing method of cobalt hydroxide and cobalt powder |
| CN104445442B (en) * | 2014-12-09 | 2016-05-11 | 英德佳纳金属科技有限公司 | A kind of low chlorine/sulphur, large particle diameter cobalt hydroxide and preparation method thereof |
| CN106552630A (en) * | 2016-10-26 | 2017-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of spherical CoOX-based catalyst and its preparation method and application |
| CN110676063A (en) * | 2019-08-19 | 2020-01-10 | 深圳职业技术学院 | High-conductivity cobalt hydroxide electrode material, preparation method thereof, electrode and capacitor |
| CN113753965B (en) * | 2021-08-24 | 2022-11-15 | 广东邦普循环科技有限公司 | Cobalt hydroxide synthesis method and cobalt hydroxide |
| CN114735759A (en) * | 2022-05-20 | 2022-07-12 | 宁波互邦新材料有限公司 | Method for recycling lithium battery cathode material to produce lithium battery cobaltous hydroxide |
| CN114835172B (en) * | 2022-05-31 | 2023-11-03 | 荆门市格林美新材料有限公司 | Cobalt hydroxide particles and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5057299A (en) * | 1989-12-08 | 1991-10-15 | Minnesota Mining And Manufacturing Company | Method for making beta cobaltous hydroxide |
| US5569444A (en) * | 1990-06-18 | 1996-10-29 | Blanchard; Philippe | Process of obtaining a metal hydroxide powder and powder obtained by the process |
-
1999
- 1999-06-29 FI FI991478A patent/FI110093B/en not_active IP Right Cessation
-
2000
- 2000-06-28 AT AT00944062T patent/ATE286855T1/en not_active IP Right Cessation
- 2000-06-28 ES ES00944062T patent/ES2235906T3/en not_active Expired - Lifetime
- 2000-06-28 AU AU58298/00A patent/AU5829800A/en not_active Abandoned
- 2000-06-28 CA CA2377152A patent/CA2377152C/en not_active Expired - Lifetime
- 2000-06-28 CN CNB008097429A patent/CN1164499C/en not_active Expired - Lifetime
- 2000-06-28 WO PCT/FI2000/000581 patent/WO2001000532A1/en not_active Ceased
- 2000-06-28 JP JP2001506951A patent/JP3961826B2/en not_active Expired - Lifetime
- 2000-06-28 DE DE60017421T patent/DE60017421T2/en not_active Expired - Lifetime
- 2000-06-28 EP EP00944062A patent/EP1210295B1/en not_active Expired - Lifetime
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Also Published As
| Publication number | Publication date |
|---|---|
| CN1359353A (en) | 2002-07-17 |
| NO20016394D0 (en) | 2001-12-27 |
| WO2001000532A1 (en) | 2001-01-04 |
| FI991478L (en) | 2000-12-30 |
| EP1210295A1 (en) | 2002-06-05 |
| NO20016394L (en) | 2002-02-28 |
| ES2235906T3 (en) | 2005-07-16 |
| DE60017421D1 (en) | 2005-02-17 |
| DE60017421T2 (en) | 2005-12-22 |
| JP2003503300A (en) | 2003-01-28 |
| ATE286855T1 (en) | 2005-01-15 |
| CN1164499C (en) | 2004-09-01 |
| EP1210295B1 (en) | 2005-01-12 |
| FI991478A0 (en) | 1999-06-29 |
| CA2377152A1 (en) | 2001-01-04 |
| AU5829800A (en) | 2001-01-31 |
| JP3961826B2 (en) | 2007-08-22 |
| FI110093B (en) | 2002-11-29 |
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