JP2011219328A - Colloidal solution of cobalt hydroxide and method for producing the same - Google Patents
Colloidal solution of cobalt hydroxide and method for producing the same Download PDFInfo
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- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 title claims abstract description 54
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 28
- 239000002245 particle Substances 0.000 claims abstract description 120
- 239000002270 dispersing agent Substances 0.000 claims abstract description 38
- 238000009826 distribution Methods 0.000 claims abstract description 38
- 229920000058 polyacrylate Polymers 0.000 claims abstract description 27
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 230000001186 cumulative effect Effects 0.000 claims abstract description 14
- 150000003839 salts Chemical class 0.000 claims abstract description 12
- 239000002994 raw material Substances 0.000 claims description 59
- 230000003472 neutralizing effect Effects 0.000 claims description 23
- 150000001869 cobalt compounds Chemical class 0.000 claims description 21
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 18
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 14
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 7
- 239000000243 solution Substances 0.000 description 110
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000010419 fine particle Substances 0.000 description 11
- 239000000084 colloidal system Substances 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- 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 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 239000010949 copper Substances 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 5
- 229910017052 cobalt Inorganic materials 0.000 description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 5
- 238000009775 high-speed stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229920002125 Sokalan® Polymers 0.000 description 3
- -1 alkali metal salts Chemical class 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 229910000428 cobalt oxide Inorganic materials 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000004584 polyacrylic acid Substances 0.000 description 3
- 229910001111 Fine metal Inorganic materials 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000002296 dynamic light scattering Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 230000001376 precipitating effect Effects 0.000 description 2
- 239000011164 primary particle Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 229920002126 Acrylic acid copolymer Polymers 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 235000012501 ammonium carbonate Nutrition 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
- XNZJTLSFOOXUAS-UHFFFAOYSA-N cobalt hydrochloride Chemical compound Cl.[Co] XNZJTLSFOOXUAS-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- PFQLIVQUKOIJJD-UHFFFAOYSA-L cobalt(ii) formate Chemical compound [Co+2].[O-]C=O.[O-]C=O PFQLIVQUKOIJJD-UHFFFAOYSA-L 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 159000000003 magnesium salts Chemical class 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229920003145 methacrylic acid copolymer Polymers 0.000 description 1
- 229940117841 methacrylic acid copolymer Drugs 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
Description
本発明は、水酸化コバルトのコロイド溶液及びその製造方法に関し、具体的には、シングルナノメートルサイズを有する水酸化コバルト粒子のコロイド溶液及びその製造方法に関する。 The present invention relates to a colloidal solution of cobalt hydroxide and a method for producing the same, and more specifically to a colloidal solution of cobalt hydroxide particles having a single nanometer size and a method for producing the same.
ナノメートルサイズを有する物質は、ミクロンオーダーのサイズを有する物質と比較してマトリックスとの界面が飛躍的に増大すること、また、バルク材料とは異なる特異な特性を発現しうること等の理由から、幅広い分野において様々な工学的応用が期待されている。
ナノメートルサイズを有する物質は、一般的に１ｎｍ〜数十ｎｍのサイズを有する物質を指す。中でも、１ｎｍ〜１０ｎｍのシングルナノメートルサイズを有する物質は、数十ｎｍのサイズを有する物質と比較して、さらに、上記したような効果が大きいことから、大いに期待される材料の１つである。
A material having a nanometer size has a significantly increased interface with the matrix compared to a material having a micron-order size, and can exhibit unique properties different from those of bulk materials. Various engineering applications are expected in a wide range of fields.
A substance having a nanometer size generally refers to a substance having a size of 1 nm to several tens of nm. Among them, a substance having a single nanometer size of 1 nm to 10 nm is one of highly expected materials because the above-described effect is larger than a substance having a size of several tens of nm. .
例えば、触媒の活性を向上させるためには、結晶面の制御と共に、１次粒子の微小化による比表面積の向上も有効である。また、リチウム電池等の電極活物質も、電極性能を向上させるために、均一で微小なものが求められている。そのため、触媒物質や電極活物質等のナノメートルサイズ化、さらには、シングルナノメートルサイズ化が望まれている。 For example, in order to improve the activity of the catalyst, it is effective to increase the specific surface area by miniaturizing primary particles as well as controlling the crystal plane. Also, electrode active materials such as lithium batteries are required to be uniform and minute in order to improve electrode performance. Therefore, it is desired to make a catalyst material, an electrode active material, etc., nanometer-sized, and further, single nanometer-sized.
従来、酸化コバルトやコバルト複合酸化物（例えば、コバルト酸リチウム等）等のコバルト化合物は、様々な用途に使用されている。例えば、酸化コバルトは、自動車等の内燃機関から排出される排ガス中に含まれる一酸化炭素の浄化触媒等として、また、コバルト酸リチウムは、リチウム電池等の正極活物質等として使用されている。これら酸化コバルトやコバルト複合酸化物の原料として用いられるコバルト化合物粒子にも、ナノメートルサイズ化、さらにはシングルナノメートルサイズ化が望まれている。 Conventionally, cobalt compounds such as cobalt oxide and cobalt composite oxide (for example, lithium cobaltate) have been used for various applications. For example, cobalt oxide is used as a purification catalyst for carbon monoxide contained in exhaust gas discharged from internal combustion engines such as automobiles, and lithium cobaltate is used as a positive electrode active material for lithium batteries and the like. The cobalt compound particles used as raw materials for these cobalt oxides and cobalt composite oxides are also desired to be nanometer-sized and further single nanometer-sized.
例えば、特許文献１には、粒度分布幅の狭い四酸化三コバルトを製造することを目的の１つとする製造方法であって、水溶性二価コバルト化合物を水系媒液中で中和・酸化することを特徴とする四酸化三コバルトの製造方法が開示されている。特許文献１に記載の製造方法では、分散剤は用いられていない。
For example,
また、特許文献２には、一次粒子の平均粒径１〜１５０ｎｍ銅微粒子が少なくともその表面の一部が分散剤で覆われて水溶液中に分散されている、銅微粒子分散水溶液の製造方法であって、（ｉ）銅イオンを分散剤の存在下で、特定のｐＨに調整したアンモニア水溶液中でアンモニアとの反応により水溶性の銅アンミン錯体を得る工程（工程１）、（ｉｉ）前記工程１で得られた銅アンミン錯体を含む水溶液に、還元剤を添加して還元反応により少なくとも表面の一部が分散剤で覆われた銅微粒子を形成する工程（工程２）を含むことを特徴とする銅微粒子分散水溶液の製造方法が開示されている。
Patent Document 2 discloses a method for producing an aqueous copper fine particle dispersion in which copper fine particles having an average primary particle diameter of 1 to 150 nm are dispersed in an aqueous solution with at least a part of the surface covered with a dispersant. (I) a step of obtaining a water-soluble copper ammine complex by reaction with ammonia in an aqueous ammonia solution adjusted to a specific pH in the presence of a dispersant in the presence of a dispersant (step 1), (ii) the step 1 A step (step 2) of adding a reducing agent to the aqueous solution containing the copper ammine complex obtained in
一方、特許文献３には、微小サイズで単分散性に優れた金属微粒子を製造することを目的として、金属微粒子の製造過程における還元剤分解による副生ガス発生を抑制した金属微粒子の製造方法が開示されている。具体的には、分解性の還元剤と析出性物質とを少なくとも含有する第１の溶液と、金属微粒子を作製する金属原子又は金属イオンを含有する第２の溶液とを液相法により混合反応させて金属微粒子を形成する混合工程を備えた金属微粒子の製造方法であって、前記混合工程の前に、前記第１の溶液を所定温度に冷却する冷却工程又は前記第１の溶液のｐＨを所定領域に調整するｐＨ調整工程を備えることを特徴とする金属微粒子の製造方法が開示されている。 On the other hand, Patent Document 3 discloses a method for producing metal fine particles that suppresses by-product gas generation due to decomposition of a reducing agent in the production process of metal fine particles for the purpose of producing fine metal particles having excellent monodispersibility. It is disclosed. Specifically, a first reaction solution containing at least a decomposable reducing agent and a precipitating substance and a second solution containing metal atoms or metal ions for producing metal fine particles are mixed by a liquid phase method. A metal fine particle manufacturing method comprising a mixing step of forming metal fine particles, wherein the cooling step of cooling the first solution to a predetermined temperature or the pH of the first solution is performed before the mixing step. Disclosed is a method for producing fine metal particles, which comprises a pH adjusting step for adjusting to a predetermined region.
しかしながら、特許文献１に記載の製造方法で得られる四酸化三コバルトは、平均粒子径が０．０３〜０．１μｍというサブミクロンオーダーであり、比表面積が小さい。
一方、特許文献２において、分散剤としてポリアクリル酸が例示されているが、実施例で実際に使用されているのは、ポリビニルピロリドンのみである。本発明者らの知見によれば、ポリビニルピロリドンのようなアミン系の高分子分散剤では、金属微粒子の凝集を充分に抑制することができないため、シングルナノサイズを有し、且つ、均一な粒度分布を有する（すなわち、粒度分布が狭い）金属微粒子、特に水酸化コバルト微粒子を得ることはできない。
以上のように、従来、シングルナノサイズを有し且つ均一な粒度分布を有する水酸化コバルト粒子を得ることは困難であった。
However, tricobalt tetroxide obtained by the production method described in
On the other hand, in Patent Document 2, polyacrylic acid is exemplified as a dispersant, but only polyvinylpyrrolidone is actually used in the examples. According to the knowledge of the present inventors, an amine-based polymer dispersant such as polyvinylpyrrolidone cannot sufficiently suppress the aggregation of metal fine particles, and therefore has a single nanosize and a uniform particle size. Metal fine particles having a distribution (that is, narrow particle size distribution), particularly cobalt hydroxide fine particles, cannot be obtained.
As described above, conventionally, it has been difficult to obtain cobalt hydroxide particles having a single nanosize and a uniform particle size distribution.
本発明は、上記実情を鑑みて成し遂げられたものであり、本発明の目的は、シングルナノサイズを有し且つ狭い粒度分布を有する水酸化コバルト粒子を含むコロイド溶液を提供することである。 The present invention has been accomplished in view of the above circumstances, and an object of the present invention is to provide a colloidal solution containing cobalt hydroxide particles having a single nanosize and a narrow particle size distribution.
本発明のコロイド溶液は、水酸化コバルト粒子と高分子分散剤とを含むコロイド溶液であって、
前記高分子分散剤が、アクリル系重合体及び／又はその塩から選ばれる少なくとも１種であり、
前記水酸化コバルト粒子の粒度分布の累積質量の５０％となる粒子径Ｄ５０が３．５〜４．５ｎｍであり、且つ、前記水酸化コバルト粒子の粒度分布の累積質量の９０％となる粒子径Ｄ９０が前記粒子径Ｄ５０の２．０倍以下であることを特徴とするものである。
The colloidal solution of the present invention is a colloidal solution containing cobalt hydroxide particles and a polymer dispersant,
The polymer dispersant is at least one selected from an acrylic polymer and / or a salt thereof,
The particle diameter D 50 which is 50% of the cumulative weight particle size distribution of the cobalt hydroxide particles are 3.5～4.5Nm, and, is 90% of the cumulative mass of the particle size distribution of the cobalt hydroxide particles particles is characterized in that the diameter D 90 of at most 2.0 times the particle diameter D 50.
本発明のコロイド溶液は、シングルナノサイズを有し且つ粒度分布が狭い水酸化コバルト粒子を含むものであり、該コロイド溶液を原料として用いることで、高比表面積を有するコバルト酸化物粒子等のコバルト化合物粒子を得ることが可能である。 The colloidal solution of the present invention includes cobalt hydroxide particles having a single nanosize and a narrow particle size distribution. By using the colloidal solution as a raw material, cobalt such as cobalt oxide particles having a high specific surface area is used. Compound particles can be obtained.
本発明のコロイド溶液の製造方法は、水酸化コバルト粒子と高分子分散剤とを含むコロイド溶液の製造方法であって、
（１）溶媒溶解性コバルト化合物と該コバルト化合物を溶解可能な溶媒とを含む第１の原料溶液、及び
（２）中和剤とアクリル系重合体及び／又はその塩からなる高分子分散剤とを含み、前記中和剤の含有量が前記第１の原料溶液に含まれる全てのコバルトイオンを中和するために必要な量の０．５倍を超えて１．２倍未満である第２の原料溶液を、
せん断速度３０００ｓｅｃ−１以上の領域で混合することを特徴とするものである。
The method for producing a colloidal solution of the present invention is a method for producing a colloidal solution containing cobalt hydroxide particles and a polymer dispersant,
(1) a first raw material solution containing a solvent-soluble cobalt compound and a solvent capable of dissolving the cobalt compound, and (2) a polymer dispersant comprising a neutralizing agent and an acrylic polymer and / or a salt thereof. And the content of the neutralizing agent is more than 0.5 times and less than 1.2 times the amount necessary for neutralizing all cobalt ions contained in the first raw material solution. The raw material solution
The mixing is performed in a region where the shear rate is 3000 sec −1 or more.
本発明のコロイド溶液の製造方法によれば、シングルナノサイズの水酸化コバルト粒子を高分散状態で含有する、上記本発明のコロイド溶液を得ることができる。 According to the method for producing a colloidal solution of the present invention, the above-described colloidal solution of the present invention containing single nano-sized cobalt hydroxide particles in a highly dispersed state can be obtained.
本発明のコロイド溶液の製造方法において、前記第２の原料溶液（２）における前記中和剤の含有量は、前記第１の原料溶液（１）に含まれる全てのコバルトイオンを中和するために必要な量の０．８倍以上１．１倍以下であることが好ましい。
また、前記中和剤の具体例としてはアンモニアが挙げられる。
In the method for producing a colloidal solution of the present invention, the content of the neutralizing agent in the second raw material solution (2) is to neutralize all cobalt ions contained in the first raw material solution (1). It is preferable that it is 0.8 times or more and 1.1 times or less of the amount required for.
A specific example of the neutralizing agent is ammonia.
本発明によれば、シングルナノサイズを有し且つ狭い粒度分布を有する水酸化コバルト粒子を含むコロイド溶液を得ることができる。従って、本発明により提供されるコロイド溶液を用いることによって、シングルナノサイズ及び狭い粒度分布を有し、高比表面積を有するコバルト化合物粒子を得ることが可能である。 According to the present invention, a colloidal solution containing cobalt hydroxide particles having a single nanosize and a narrow particle size distribution can be obtained. Therefore, by using the colloidal solution provided by the present invention, it is possible to obtain cobalt compound particles having a single nanosize and a narrow particle size distribution and a high specific surface area.
まず、本発明のコロイド溶液について説明する。
本発明のコロイド溶液は、水酸化コバルト粒子と高分子分散剤とを含むコロイド溶液であって、
前記高分子分散剤が、アクリル系重合体及び／又はその塩から選ばれる少なくとも１種であり、
前記水酸化コバルト粒子の粒度分布の累積質量の５０％となる粒子径Ｄ５０（以下、単に「粒子径Ｄ５０」ということがある。）が３．５〜４．５ｎｍであり、且つ、前記水酸化コバルト粒子の粒度分布の累積質量の９０％となる粒子径Ｄ９０（以下、単に「粒子径Ｄ９０」ということがある）が前記粒子径Ｄ５０の２．０倍以下であることを特徴とするものである。
First, the colloid solution of the present invention will be described.
The colloidal solution of the present invention is a colloidal solution containing cobalt hydroxide particles and a polymer dispersant,
The polymer dispersant is at least one selected from an acrylic polymer and / or a salt thereof,
The particle diameter D 50 (hereinafter sometimes simply referred to as “particle diameter D 50 ”), which is 50% of the cumulative mass of the particle size distribution of the cobalt hydroxide particles, is 3.5 to 4.5 nm, and The particle diameter D 90 (hereinafter sometimes simply referred to as “particle diameter D 90 ”) that is 90% of the cumulative mass of the particle size distribution of the cobalt hydroxide particles is 2.0 times or less of the particle diameter D 50. It is a feature.
本発明のコロイド溶液に含有される水酸化コバルト粒子は、まず、粒子径Ｄ５０、つまり累積質量換算における平均粒径が３．５〜４．５ｎｍであり、シングルナノサイズの累積質量平均粒径を有している。
さらに、本発明のコロイド溶液に含有される水酸化コバルト粒子は、粒子径Ｄ９０が粒子径Ｄ５０の２．０倍以下、つまり、Ｄ９０／Ｄ５０≦２．０を満たす粒度分布を有している。Ｄ９０／Ｄ５０は、粒径分布の広さを示す指標値であり、実質１以上となるが、１に近いほど単分散状態に近く、粒度分布が狭いことを示す。
The cobalt hydroxide particles contained in the colloidal solution of the present invention first have a particle diameter D 50 , that is, an average particle diameter in terms of cumulative mass of 3.5 to 4.5 nm, and a single nano-sized cumulative mass average particle diameter. have.
Furthermore, the cobalt hydroxide particles contained in the colloidal solution of the present invention have a particle size distribution in which the particle diameter D 90 is 2.0 times or less of the particle diameter D 50 , that is, D 90 / D 50 ≦ 2.0. is doing. D 90 / D 50 is an index value indicating the breadth of the particle size distribution, and is substantially 1 or more, but the closer to 1, the closer to the monodispersed state and the narrower the particle size distribution.
すなわち、本発明のコロイド溶液は、均一な粒度分布を有するシングルナノサイズの水酸化コバルト粒子を含有する。このように、シングルナノサイズ及び狭い粒度分布を有する水酸化コバルト粒子を含有する、本発明のコロイド溶液を原料として用いることによって、シングルナノサイズを有し、比表面積が大きなコバルト化合物粒子を製造することが可能となる。 That is, the colloidal solution of the present invention contains single nano-sized cobalt hydroxide particles having a uniform particle size distribution. In this way, cobalt compound particles having a single nanosize and a large specific surface area are produced by using the colloidal solution of the present invention containing cobalt hydroxide particles having a single nanosize and a narrow particle size distribution as a raw material. It becomes possible.
本発明のコロイド溶液は、例えば、後述する本発明のコロイド溶液の製造方法によって、調製することができる。 The colloidal solution of the present invention can be prepared, for example, by the method for producing the colloidal solution of the present invention described later.
本発明において、水酸化コバルト粒子の粒度分布の累積質量５０％となる粒子径Ｄ５０及び累積質量９０％となる粒子径Ｄ９０は、コロイド溶液に含まれる水酸化コバルト粒子の粒度分布曲線から求めることができる。水酸化コバルト粒子の粒度分布曲線は、公知の方法により求めることができ、例えば、動的光散乱法を利用した粒度分布測定装置等、光散乱法を利用した装置を用いることができる。具体的な装置として、例えば、大塚電子株式会社製、ＥＬＳ−Ｚが挙げられる。 In the present invention, the particle diameter D 50 which is 50% of the cumulative mass of the particle size distribution of the cobalt hydroxide particles and the particle diameter D 90 which is 90% of the cumulative mass are determined from the particle size distribution curve of the cobalt hydroxide particles contained in the colloidal solution. be able to. The particle size distribution curve of the cobalt hydroxide particles can be obtained by a known method. For example, a device using a light scattering method such as a particle size distribution measuring device using a dynamic light scattering method can be used. Specific examples include ELS-Z manufactured by Otsuka Electronics Co., Ltd.
本発明のコロイド溶液において、水酸化コバルト粒子は、アクリル系重合体及び／又はその塩からなる高分子分散剤（以下、単に「アクリル系高分子分散剤」ということがある）によってその表面が覆われ、保護されている。尚、水酸化コバルト粒子は、表面全体がアクリル系高分子分散剤に覆われている状態の他、少なくとも一部の表面がアクリル系高分子分散剤に覆われている状態でもよい。
アクリル系高分子分散剤は、コロイド溶液中の水酸化コバルト粒子の表面を覆うように存在し、水酸化コバルト粒子の分散性を良好に維持する作用を有するものであればよく、特に限定されない。
In the colloidal solution of the present invention, the surface of the cobalt hydroxide particles is covered with a polymer dispersant comprising an acrylic polymer and / or a salt thereof (hereinafter sometimes simply referred to as “acrylic polymer dispersant”). And protected. The cobalt hydroxide particles may be in a state in which at least a part of the surface is covered with the acrylic polymer dispersant in addition to the state where the entire surface is covered with the acrylic polymer dispersant.
The acrylic polymer dispersant is not particularly limited as long as it is present so as to cover the surface of the cobalt hydroxide particles in the colloidal solution and has an action of maintaining good dispersibility of the cobalt hydroxide particles.
具体的なアクリル系高分子分散剤としては、例えば、ポリアクリル酸エステル、ポリメタクリル酸エステル、ポリアクリル酸、ポリメタクリル酸、アクリル酸エステル共重合体、メタクリル酸エステル共重合体、アクリル酸共重合体、メタクリル酸共重合体等のアクリル系重合体、並びに、これらアクリル系重合体の塩が挙げられる。アクリル系重合体の塩としては、ナトリウム塩、カリウム塩等のアルカリ金属塩、カルシウム塩、マグネシウム塩等のアルカリ土類金属塩等が挙げられる。
好ましいアクリル系高分子分散剤としては、例えば、ポリアクリル酸ナトリウムが挙げられる。
本発明のコロイド溶液は、アクリル系高分子分散剤を１種のみ含有していても或いは２種以上を含有していてもよい。
Specific examples of the acrylic polymer dispersant include polyacrylic acid ester, polymethacrylic acid ester, polyacrylic acid, polymethacrylic acid, acrylic acid ester copolymer, methacrylic acid ester copolymer, and acrylic acid copolymer. Examples thereof include acrylic polymers such as a polymer and a methacrylic acid copolymer, and salts of these acrylic polymers. Examples of the salt of the acrylic polymer include alkali metal salts such as sodium salt and potassium salt, and alkaline earth metal salts such as calcium salt and magnesium salt.
A preferable acrylic polymer dispersant is, for example, sodium polyacrylate.
The colloid solution of the present invention may contain only one type of acrylic polymer dispersant or may contain two or more types.
コロイド溶液におけるアクリル系高分子分散剤の量は、水酸化コバルト粒子の分散性を良好に維持することができればよく、特に限定されないが、コロイド溶液中に含まれるコバルトイオン１モルに対して、７００ｇ以上であることが好ましく、２４００ｇ以下であることが好ましい。
コロイド溶液おけるアクリル系高分子分散剤とコバルトイオンの比率は、コロイド溶液調製時における各材料の仕込み比率で調整すればよい。
The amount of the acrylic polymer dispersant in the colloidal solution is not particularly limited as long as the dispersibility of the cobalt hydroxide particles can be maintained satisfactorily, but is 700 g with respect to 1 mol of cobalt ions contained in the colloidal solution. It is preferable that it is above, and it is preferable that it is 2400 g or less.
What is necessary is just to adjust the ratio of the acrylic polymer dispersing agent and cobalt ion in a colloidal solution with the preparation ratio of each material at the time of colloidal solution preparation.
コロイド溶液の溶媒は特に限定されず、コロイド溶液調製時に使用するコロイド化合物の溶解性、アクリル系高分子分散剤の親水性や親油性等に応じて、適宜選択すればよい。具体的には、例えば、イオン交換水等が挙げられる。
本発明のコロイド溶液には、その他成分が含有されていてもよい。
The solvent of the colloidal solution is not particularly limited, and may be appropriately selected according to the solubility of the colloidal compound used when preparing the colloidal solution, the hydrophilicity or lipophilicity of the acrylic polymer dispersant. Specifically, ion exchange water etc. are mentioned, for example.
The colloid solution of the present invention may contain other components.
次に、本発明のコロイド溶液の製造方法について説明する。
本発明のコロイド溶液の製造方法は、水酸化コバルト粒子と高分子分散剤とを含むコロイド溶液の製造方法であって、
（１）溶媒溶解性コバルト化合物と該コバルト化合物を溶解可能な溶媒とを含む第１の原料溶液、及び
（２）中和剤とアクリル系重合体及び／又はその塩からなる高分子分散剤とを含み、前記中和剤の含有量が前記第１の原料溶液に含まれるコバルトイオンを中和するために必要な量の０．５倍を超えて１．２倍未満である第２の原料溶液を、
せん断速度３０００ｓｅｃ−１以上の領域で混合することを特徴とするものである。
Next, the manufacturing method of the colloidal solution of this invention is demonstrated.
The method for producing a colloidal solution of the present invention is a method for producing a colloidal solution containing cobalt hydroxide particles and a polymer dispersant,
(1) a first raw material solution containing a solvent-soluble cobalt compound and a solvent capable of dissolving the cobalt compound, and (2) a polymer dispersant comprising a neutralizing agent and an acrylic polymer and / or a salt thereof. And the content of the neutralizing agent is 0.5 to less than 1.2 times the amount necessary to neutralize the cobalt ions contained in the first raw material solution. The solution
The mixing is performed in a region where the shear rate is 3000 sec −1 or more.
第１の原料溶液（１）は、少なくとも溶媒溶解性コバルト化合物及び溶媒を含む。
溶媒溶解性コバルト化合物は、コバルトイオンの供給源であり、溶媒溶解性を有していれば特に限定されず、例えば、硝酸コバルト、硫酸コバルト、塩酸コバルト、酢酸コバルト、ギ酸コバルト等が挙げられ、中でも硝酸コバルトが好ましい。溶媒溶解性コバルト化合物は、無水物でも水和物でもよい。
溶媒は、上記コバルト化合物を溶解し、コバルトイオンを生成させることができれば特に限定されず、例えば、イオン交換水等が挙げられる。
The first raw material solution (1) contains at least a solvent-soluble cobalt compound and a solvent.
The solvent-soluble cobalt compound is a supply source of cobalt ions, and is not particularly limited as long as it has solvent solubility, such as cobalt nitrate, cobalt sulfate, cobalt hydrochloride, cobalt acetate, cobalt formate, Of these, cobalt nitrate is preferable. The solvent-soluble cobalt compound may be an anhydride or a hydrate.
A solvent will not be specifically limited if the said cobalt compound can be melt | dissolved and a cobalt ion can be produced | generated, For example, ion-exchange water etc. are mentioned.
第１の原料溶液（１）において、溶媒溶解性コバルト化合物と溶媒との比率は特に限定されないが、通常、コバルトイオン濃度が０．０１モル／Ｌ以上であることが好ましく、０．５モル／Ｌ以下であることが好ましい。
第１の原料溶液（１）の調製方法は特に限定されず、溶媒と溶媒溶解性コバルト化合物とを任意の方法で混合すればよい。
In the first raw material solution (1), the ratio of the solvent-soluble cobalt compound and the solvent is not particularly limited, but usually the cobalt ion concentration is preferably 0.01 mol / L or more, and preferably 0.5 mol / L. L or less is preferable.
The method for preparing the first raw material solution (1) is not particularly limited, and the solvent and the solvent-soluble cobalt compound may be mixed by any method.
第２の原料溶液（２）は、少なくとも中和剤とアクリル系重合体及び／又はその塩からなる高分子分散剤とを含む。
中和剤は、溶媒溶解性コバルト化合物が溶解した第１の原料溶液（１）を中和して、水酸化コバルト粒子を析出できるものであればよく、使用する溶媒溶解性コバルト化合物に合わせて適宜選択すればよい。
溶媒溶解性コバルト化合物として上記に記載したような化合物を用いる場合には、例えば、アンモニアガス、アンモニア水、炭酸アンモニウム等のアンモニウム化合物、水酸化ナトリウム、水酸化カリウム等のアルカリが挙げられる。
The second raw material solution (2) includes at least a neutralizing agent and a polymer dispersant composed of an acrylic polymer and / or a salt thereof.
The neutralizing agent only needs to neutralize the first raw material solution (1) in which the solvent-soluble cobalt compound is dissolved and precipitate the cobalt hydroxide particles, and matches the solvent-soluble cobalt compound to be used. What is necessary is just to select suitably.
When a compound as described above is used as the solvent-soluble cobalt compound, examples thereof include ammonia compounds such as ammonia gas, aqueous ammonia and ammonium carbonate, and alkalis such as sodium hydroxide and potassium hydroxide.
本発明の製造方法の大きな特徴の１つは、第２の原料溶液（２）における中和剤の含有量を、上記第１の原料溶液（１）に含まれる全てのコバルトイオン（Ｃｏ２＋）を中和するために必要な量(以下、「中和量」ということがある)の０．５倍を超えて１．２倍未満とする点にある。中和剤の含有量を、中和量の０．５倍を超える量とすることで中和反応を確実に進行させることができると共に、中和量の１．２倍未満とすることで生成した水酸化コバルト粒子の溶解を防止することができる。
第２の原料溶液（２）の中和剤含有量は、上記第１の原料溶液に含まれる全てのコバルトイオンを中和するために必要な量の０．８倍以上１．１倍以下であることが好ましく、特に１．０以上１．１倍以下であることが好ましい。
One of the major features of the production method of the present invention is that the content of the neutralizing agent in the second raw material solution (2) is changed to all the cobalt ions (Co 2+ ) contained in the first raw material solution (1). The amount is 0.5 to less than 1.2 times the amount necessary for neutralizing (hereinafter, sometimes referred to as “neutralization amount”). By making the content of the neutralizing agent more than 0.5 times the amount of neutralization, the neutralization reaction can surely proceed, and it is generated by making the amount less than 1.2 times the amount of neutralization. It is possible to prevent the dissolved cobalt hydroxide particles.
The neutralizing agent content of the second raw material solution (2) is 0.8 to 1.1 times the amount necessary for neutralizing all cobalt ions contained in the first raw material solution. It is preferable that it is 1.0 to 1.1 times in particular.
アクリル系重合体及び／又はその塩からなる高分子分散剤（アクリル系高分子分散剤）を用いることも、本発明の製造方法の大きな特徴の１つである。アクリル系高分子分散剤については、上記本発明のコロイド溶液において説明したものと同様であるため、ここでの説明は省略する。
第２の原料溶液（２）におけるアクリル系高分子分散剤の含有量は、第１の原料溶液（１）と第２の原料溶液（２）とから得られるコロイド溶液において、水酸化コバルト粒子の分散性を良好に維持することができればよく、特に限定されない。好ましくは、第１の原料溶液（１）に含まれるコバルト１モルに対して、４５０ｇ以上であることが好ましく、９００ｇ以下であることが好ましい。
The use of a polymer dispersant (acrylic polymer dispersant) comprising an acrylic polymer and / or a salt thereof is also one of the major features of the production method of the present invention. Since the acrylic polymer dispersant is the same as that described in the colloidal solution of the present invention, description thereof is omitted here.
The content of the acrylic polymer dispersant in the second raw material solution (2) is that of the cobalt hydroxide particles in the colloidal solution obtained from the first raw material solution (1) and the second raw material solution (2). There is no particular limitation as long as the dispersibility can be maintained well. Preferably, it is preferably 450 g or more and more preferably 900 g or less with respect to 1 mol of cobalt contained in the first raw material solution (1).
第２の原料溶液（２）の溶媒は、中和剤を溶解できれば、特に限定されず、例えば、イオン交換水等を用いることができる。
第２の原料溶液（２）における溶媒量は、得られる第２の原料溶液の体積が、第１の原料溶液の体積と同じになるように調整することが好ましい。
第２の原料溶液の調製方法は特に限定されず、中和剤、アクリル系高分子分散剤及び溶媒を任意の方法で混合すればよい。
The solvent of the second raw material solution (2) is not particularly limited as long as it can dissolve the neutralizing agent, and for example, ion-exchanged water or the like can be used.
The amount of solvent in the second raw material solution (2) is preferably adjusted so that the volume of the obtained second raw material solution is the same as the volume of the first raw material solution.
The method for preparing the second raw material solution is not particularly limited, and the neutralizing agent, the acrylic polymer dispersant and the solvent may be mixed by any method.
本発明において、第１の原料溶液（１）及び第２の原料溶液（２）は、せん断速度３０００ｓｅｃ−１以上の領域で混合される。せん断速度３０００ｓｅｃ−１以上の領域で第１及び第２の原料溶液を混合することも本発明の大きな特徴である。３０００ｓｅｃ−１以上の高せん断条件下、コバルトイオンを中和し、水酸化コバルトを析出させることによって、シングルナノサイズを有し、粒度分布が狭い水酸化コバルト粒子を得ることができる。せん断速度が３０００ｓｅｃ−１未満であると、水酸化コバルト粒子の凝集が起こってしまう。上記せん断速度は、好ましくは、４５００ｓｅｃ−１以上である。
尚、上記第１の原料溶液及び第２の原料溶液をスターラーで混合（つまり、せん断速度３０００ｓｅｃ−１未満）しても、本発明のコロイド溶液に含まれるような粒度分布を有する水酸化コバルト粒子は得られないことが本発明者らにより確認されている。
In the present invention, the first raw material solution (1) and the second raw material solution (2) are mixed in a region having a shear rate of 3000 sec −1 or more. It is also a major feature of the present invention that the first and second raw material solutions are mixed in a region where the shear rate is 3000 sec −1 or more. By neutralizing cobalt ions and precipitating cobalt hydroxide under high shear conditions of 3000 sec −1 or more, cobalt hydroxide particles having a single nanosize and a narrow particle size distribution can be obtained. If the shear rate is less than 3000 sec −1 , aggregation of cobalt hydroxide particles occurs. The shear rate is preferably 4500 sec −1 or more.
In addition, even if the first raw material solution and the second raw material solution are mixed with a stirrer (that is, a shear rate of less than 3000 sec −1 ), the cobalt hydroxide particles having a particle size distribution that is included in the colloidal solution of the present invention. Have been confirmed by the present inventors.
上記のような高せん断速度で第１及び第２の原料溶液を混合する装置としては、次のような高速攪拌装置を用いることができる。すなわち、少なくとも２つ以上の異なる原料溶液を別々に下記反応室内に導入できる機構（以下、導入機構という場合がある。）と、２つ以上の異なる原料溶液を３０００ｓｅｃ−１以上のせん断速度で混合させるせん断機構を有する反応室と、を備える装置である。
導入機構としては、具体的には、高速攪拌装置内に２つ以上の異なる原料溶液を独立に供給できる装置、及び、該溶液供給装置から供給される原料溶液を反応室へと運搬するノズルを備える構成が挙げられる。
反応室は、第１及び第２の原料溶液を上記高せん断条件で混合できるよう、微小空間を有している。ここで微小空間とは、上記第１及び第２の原料溶液を反応させて、水酸化コバルト粒子を得ることができるのに充分な容積を有する空間であり、具体的には、数ナノ立方メートル〜数マイクロ立方メートルの容積を有する空間が好ましい。また、反応室は、反応室への原料溶液の導入路及び反応室からの目的生成物の排出路を除いて密閉された空間であることが好ましい。
反応室におけるせん断機構としては、２つ以上の異なる原料溶液を３０００ｓｅｃ−１以上のせん断速度で混合させることができる高速攪拌機構であれば特に限定されない。具体的には、ローターとステーターとを備えたホモジナイザーであって、ローターの回転数を調整することでせん断速度を調整できるものが挙げられる。
As a device for mixing the first and second raw material solutions at a high shear rate as described above, the following high-speed stirring device can be used. That is, a mechanism capable of separately introducing at least two different raw material solutions into the following reaction chamber (hereinafter sometimes referred to as an introduction mechanism) and two or more different raw material solutions are mixed at a shear rate of 3000 sec −1 or higher. And a reaction chamber having a shearing mechanism.
Specifically, the introduction mechanism includes a device capable of independently supplying two or more different raw material solutions into the high-speed stirring device, and a nozzle for conveying the raw material solution supplied from the solution supply device to the reaction chamber. The structure provided is mentioned.
The reaction chamber has a minute space so that the first and second raw material solutions can be mixed under the high shear condition. Here, the minute space is a space having a volume sufficient to allow the first and second raw material solutions to react to obtain cobalt hydroxide particles. A space having a volume of a few microcubic meters is preferred. The reaction chamber is preferably a sealed space except for the introduction path of the raw material solution to the reaction chamber and the discharge path of the target product from the reaction chamber.
The shearing mechanism in the reaction chamber is not particularly limited as long as it is a high-speed stirring mechanism capable of mixing two or more different raw material solutions at a shear rate of 3000 sec −1 or more. Specifically, a homogenizer provided with a rotor and a stator, which can adjust the shear rate by adjusting the rotation speed of the rotor, can be mentioned.
得られた水酸化コバルト粒子含有コロイド溶液は、必要に応じて、水酸化コバルト粒子をろ過、洗浄、乾燥して使用することができる。 The obtained cobalt hydroxide particle-containing colloidal solution can be used after filtering, washing and drying the cobalt hydroxide particles as required.
本発明により提供されるコロイド溶液は、既述したように、シングルナノサイズを有する均一な水酸化コバルト粒子を含有する。従って、本発明のコロイド溶液を用いることによって、高比表面積を有するコバルト化合物粒子を得ることが可能であり、触媒物質や電極活物質等の性能向上が期待できる。 The colloidal solution provided by the present invention contains uniform cobalt hydroxide particles having a single nanosize as described above. Therefore, by using the colloidal solution of the present invention, it is possible to obtain cobalt compound particles having a high specific surface area, and an improvement in performance of a catalyst material, an electrode active material, etc. can be expected.
（実施例１）
＜水酸化コバルト粒子含有コロイド溶液の調製＞
Ｃｏ（ＮＯ３）２・６Ｈ２Ｏ ３．６４ｇ（０．０１２５モル）と、イオン交換水１２５ｇとを混合し、第１の原料溶液(コバルトイオン濃度０．１モル／Ｌ)を調製した。
一方、アンモニア水（アンモニア濃度２５％）１．８７ｇ（アンモニア０．０２７５モル）と、ポリアクリル酸ナトリウム（重量平均分子量１２００）２１．９ｇと、イオン交換水１００ｇとを混合し、第２の原料溶液を調製した。
Example 1
<Preparation of cobalt hydroxide particle-containing colloidal solution>
Co (NO 3 ) 2 .6H 2 O 3.64 g (0.0125 mol) and 125 g of ion-exchanged water were mixed to prepare a first raw material solution (cobalt ion concentration 0.1 mol / L).
On the other hand, 1.87 g of ammonia water (ammonia concentration 25%) (ammonia 0.0275 mol), 21.9 g of sodium polyacrylate (weight average molecular weight 1200), and 100 g of ion-exchanged water are mixed, and the second raw material is mixed. A solution was prepared.
尚、第１の原料溶液の調製と第２の原料溶液の調製において使用したイオン交換水の量は、第１の原料溶液と第２の原料溶液の体積が同じになる量とした。
また、第２の原料溶液に含有されるアンモニア量は、第１の原料溶液に含有される全てのＣｏ２＋イオンを中和するのに必要な量の１．１倍（０．０１２５×２×１．１＝０．０２７５モル）である。
The amount of ion-exchanged water used in the preparation of the first raw material solution and the preparation of the second raw material solution was such that the volume of the first raw material solution and that of the second raw material solution were the same.
Further, the amount of ammonia contained in the second raw material solution is 1.1 times (0.0125 × 2 ×) the amount necessary to neutralize all Co 2+ ions contained in the first raw material solution. 1.1 = 0.0275 mol).
次に、得られた第１の原料溶液と第２の原料溶液とを、高速攪拌装置を用いて混合し、Ｃｏ（ＯＨ）２粒子含有コロイドを得た。高速攪拌装置による混合は、第１の原料溶液及び第２の原料溶液を、それぞれ、２．５ｍｌ／ｍｉｎで供給しながら、せん断速度７０００ｓｅｃ−１（回転速度１００００ｒｐｍ）、室温で１時間行った。尚、反応室に供給する、スタートアップ溶液のｐＨは９．２〜９．６になるようにアンモニアを加えて調整した。
攪拌開始初期のコロイドの色は桃色で、時間経過と共に青緑色に変化した。桃色及び青緑色は、粉末状態のＣｏ（ＯＨ）２の色（結晶の色）と一致することから、得られたコバルト含有コロイド溶液には、Ｃｏ（ＯＨ）２粒子を含有すると考えられる。
Next, the obtained 1st raw material solution and 2nd raw material solution were mixed using the high-speed stirring apparatus, and the Co (OH) 2 particle containing colloid was obtained. The mixing with the high-speed stirring device was performed at room temperature for 1 hour at a shear rate of 7000 sec −1 (rotational speed of 10,000 rpm) while supplying the first raw material solution and the second raw material solution at 2.5 ml / min, respectively. The pH of the startup solution supplied to the reaction chamber was adjusted by adding ammonia so that the pH was 9.2 to 9.6.
The color of the colloid at the beginning of stirring was pink and changed to blue-green with time. Pink and blue-green colors match the color of Co (OH) 2 in the powder state (crystal color), and thus the obtained cobalt-containing colloidal solution is considered to contain Co (OH) 2 particles.
＜水酸化コバルト粒子の評価＞
得られたＣｏ（ＯＨ）２粒子含有コロイド溶液について、動的光散乱法による粒度分布測定装置（大塚電子株式会社製、ＥＬＳ−Ｚ）を用いて、粒度分布を測定した。結果を図１（累積分布）及び図２（頻度分布）に示す。尚、図１及び図２の累積及び頻度は、質量換算して求めたものである。
図１に示すように、得られたコロイド中のＣｏ（ＯＨ）２粒子は、Ｄ５０＝４．５ｎｍ、Ｄ９０＝８．１ｎｍ、Ｄ９０／Ｄ５０＝１．８であった。また、図２より、得られたコロイド中のＣｏ（ＯＨ）２粒子は、粒度分布がシャープであり、均一な粒径を有していることがわかる。
尚、上記と同様にして複数回（ｎ＝３）、水酸化コバルト粒子含有コロイド溶液を調製したところ、Ｄ５０＝３．５〜４．５ｎｍ、Ｄ９０＝３．５〜８．１ｎｍ、ｐＨ９．２のコロイド溶液が得られた。尚、得られたコロイド溶液中に含まれる粒子について、散乱強度分布から得られた平均粒径及びσ値（分散）より平均粒径を求めたところ、５．５±３．３ｎｍであった。また、得られたコロイド溶液は、調製後１日経過した後においても緑青色を呈しており、水酸化コバルト粒子に変化は生じなかった。
<Evaluation of cobalt hydroxide particles>
About the obtained Co (OH) 2 particle containing colloid solution, the particle size distribution was measured using the particle size distribution measuring apparatus (Otsuka Electronics Co., Ltd. product, ELS-Z) by a dynamic light scattering method. The results are shown in FIG. 1 (cumulative distribution) and FIG. 2 (frequency distribution). The accumulation and frequency in FIGS. 1 and 2 are calculated in terms of mass.
As shown in FIG. 1, the Co (OH) 2 particles in the obtained colloid had D 50 = 4.5 nm, D 90 = 8.1 nm, and D 90 / D 50 = 1.8. Moreover, FIG. 2 shows that the Co (OH) 2 particles in the obtained colloid have a sharp particle size distribution and a uniform particle size.
In addition, when a cobalt hydroxide particle-containing colloidal solution was prepared a plurality of times (n = 3) in the same manner as described above, D 50 = 3.5 to 4.5 nm, D 90 = 3.5 to 8.1 nm, pH 9 A colloidal solution of 2 was obtained. In addition, about the particle | grains contained in the obtained colloid solution, when the average particle diameter was calculated | required from the average particle diameter obtained from scattering intensity distribution, and (sigma) value (dispersion), it was 5.5 +/- 3.3nm. Further, the obtained colloidal solution had a greenish blue color even after 1 day had passed after the preparation, and the cobalt hydroxide particles did not change.
Claims (4)
前記高分子分散剤が、アクリル系重合体及び／又はその塩から選ばれる少なくとも１種であり、
前記水酸化コバルト粒子の粒度分布の累積質量の５０％となる粒子径Ｄ５０が３．５〜４．５ｎｍであり、且つ、前記水酸化コバルト粒子の粒度分布の累積質量の９０％となる粒子径Ｄ９０が前記粒子径Ｄ５０の２．０倍以下であることを特徴とする、コロイド溶液。 A colloidal solution containing cobalt hydroxide particles and a polymer dispersant,
The polymer dispersant is at least one selected from an acrylic polymer and / or a salt thereof,
The particle diameter D 50 which is 50% of the cumulative weight particle size distribution of the cobalt hydroxide particles are 3.5～4.5Nm, and, is 90% of the cumulative mass of the particle size distribution of the cobalt hydroxide particles particles wherein the diameter D90 is less than 2.0 times the particle diameter D 50, colloidal solution.
（１）溶媒溶解性コバルト化合物と該コバルト化合物を溶解可能な溶媒とを含む第１の原料溶液、及び
（２）中和剤とアクリル系重合体及び／又はその塩からなる高分子分散剤とを含み、前記中和剤の含有量が前記第１の原料溶液に含まれる全てのコバルトイオンを中和するために必要な量の０．５倍を超えて１．２倍未満である第２の原料溶液を、
せん断速度３０００ｓｅｃ−１以上の領域で混合することを特徴とする、コロイド溶液の製造方法。 A method for producing a colloidal solution containing cobalt hydroxide particles and a polymer dispersant,
(1) a first raw material solution containing a solvent-soluble cobalt compound and a solvent capable of dissolving the cobalt compound, and (2) a polymer dispersant comprising a neutralizing agent and an acrylic polymer and / or a salt thereof. And the content of the neutralizing agent is more than 0.5 times and less than 1.2 times the amount necessary for neutralizing all cobalt ions contained in the first raw material solution. The raw material solution
A method for producing a colloidal solution, wherein mixing is performed in a region where the shear rate is 3000 sec −1 or more.
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Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5891103A (en) * | 1981-11-25 | 1983-05-31 | Konishiroku Photo Ind Co Ltd | Production of dispersion of colloidal silver particles |
| JPS605027A (en) * | 1983-05-31 | 1985-01-11 | Sumitomo Metal Mining Co Ltd | Production of cobalt hydroxide soluble easily in organic acid |
| JPH09175825A (en) * | 1995-12-19 | 1997-07-08 | Samsung Display Devices Co Ltd | Production of compound oxide using sol-gel method |
| JP2005139029A (en) * | 2003-11-06 | 2005-06-02 | Toyota Central Res & Dev Lab Inc | Oxide powder, its preparation process, and catalyst |
| JP2006272250A (en) * | 2005-03-30 | 2006-10-12 | Nissan Motor Co Ltd | Method for arraying fine particle, catalyst for cleaning exhaust gas, electrode catalyst and magnetic material |
| JP2008248136A (en) * | 2007-03-30 | 2008-10-16 | Toyota Motor Corp | Method for producing dispersion liquid of metal oxide minute particles, method for producing metal oxide minute particle dispersion paste, resin composition, and coating composition |
| JP2009184884A (en) * | 2008-02-07 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | Core-shell type cobalt oxide fine particles or dispersion containing the same, method for producing them, and their application |
| WO2009116378A1 (en) * | 2008-02-29 | 2009-09-24 | 国立大学法人東京大学 | SOLID TRANSITION METAL HYDROXIDE FILM, α-COBALT HYDROXIDE FILM, MANUFACTURING METHOD FOR SOLID TRANSITION METAL HYDROXIDE, MANUFACTURING METHOD FOR α-COBALT HYDROXIDE, MANUFACTURING DEVICE FOR SOLID TRANSITION METAL HYDROXIDE, MANUFACTURING METHOD FOR TRANSITION METAL HYDROXIDE, MANUFACTURING METHOD FOR HYDRATED LITHIUM COBALT OXIDE, TRANSITION METAL OXIDE FILM, AND ELECTRODE MATERIAL |
| JP2010110720A (en) * | 2008-11-07 | 2010-05-20 | Toyota Central R&D Labs Inc | Colloidal solution of metallic compound, and method of producing the same |
-
2010
- 2010-04-13 JP JP2010092481A patent/JP5672754B2/en not_active Expired - Fee Related
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5891103A (en) * | 1981-11-25 | 1983-05-31 | Konishiroku Photo Ind Co Ltd | Production of dispersion of colloidal silver particles |
| JPS605027A (en) * | 1983-05-31 | 1985-01-11 | Sumitomo Metal Mining Co Ltd | Production of cobalt hydroxide soluble easily in organic acid |
| JPH09175825A (en) * | 1995-12-19 | 1997-07-08 | Samsung Display Devices Co Ltd | Production of compound oxide using sol-gel method |
| JP2005139029A (en) * | 2003-11-06 | 2005-06-02 | Toyota Central Res & Dev Lab Inc | Oxide powder, its preparation process, and catalyst |
| JP2006272250A (en) * | 2005-03-30 | 2006-10-12 | Nissan Motor Co Ltd | Method for arraying fine particle, catalyst for cleaning exhaust gas, electrode catalyst and magnetic material |
| JP2008248136A (en) * | 2007-03-30 | 2008-10-16 | Toyota Motor Corp | Method for producing dispersion liquid of metal oxide minute particles, method for producing metal oxide minute particle dispersion paste, resin composition, and coating composition |
| JP2009184884A (en) * | 2008-02-07 | 2009-08-20 | National Institute Of Advanced Industrial & Technology | Core-shell type cobalt oxide fine particles or dispersion containing the same, method for producing them, and their application |
| WO2009116378A1 (en) * | 2008-02-29 | 2009-09-24 | 国立大学法人東京大学 | SOLID TRANSITION METAL HYDROXIDE FILM, α-COBALT HYDROXIDE FILM, MANUFACTURING METHOD FOR SOLID TRANSITION METAL HYDROXIDE, MANUFACTURING METHOD FOR α-COBALT HYDROXIDE, MANUFACTURING DEVICE FOR SOLID TRANSITION METAL HYDROXIDE, MANUFACTURING METHOD FOR TRANSITION METAL HYDROXIDE, MANUFACTURING METHOD FOR HYDRATED LITHIUM COBALT OXIDE, TRANSITION METAL OXIDE FILM, AND ELECTRODE MATERIAL |
| JP2010110720A (en) * | 2008-11-07 | 2010-05-20 | Toyota Central R&D Labs Inc | Colloidal solution of metallic compound, and method of producing the same |
Non-Patent Citations (1)
| Title |
|---|
| JPN6014005273; ＨＯＵ， Ｙ ｅｔ ａｌ: 'Ｈｉｇｈ-Ｙｉｅｌｄ Ｐｒｅｐａｒａｔｉｏｎ ｏｆ Ｕｎｉｆｏｒｍ Ｃｏｂａｌｔ Ｈｙｄｒｏｘｉｄｅ ａｎｄ Ｏｘｉｄｅ Ｎａｎｏｐｌａｔｅｌｅｔｓ ａｎｄ Ｔｈｅｉｒ Ｃｈａｒａｃｔｅｒｉｚａｔｉｏ' Ｊ． Ｐｈｙｓ． Ｃｈｅｍ． Ｂ Ｖｏｌ．１０９， Ｎｏ．４１, 20050924, ｐ．１９０９４-１９０９８ * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2020054236A1 (en) | 2018-09-14 | 2020-03-19 | 花王株式会社 | Method for producing positive electrode active material for lithium ion secondary battery |
| EP3852175A4 (en) * | 2018-09-14 | 2022-06-29 | Kao Corporation | Method for producing positive electrode active material for lithium ion secondary battery |
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