CN1733599B - Process for preparing moisture gel of transition metal oxide and hydroxide - Google Patents
Process for preparing moisture gel of transition metal oxide and hydroxide Download PDFInfo
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- CN1733599B CN1733599B CN 200410058106 CN200410058106A CN1733599B CN 1733599 B CN1733599 B CN 1733599B CN 200410058106 CN200410058106 CN 200410058106 CN 200410058106 A CN200410058106 A CN 200410058106A CN 1733599 B CN1733599 B CN 1733599B
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Abstract
The invention relates to a wet gel of transitional metallic oxides and hydroxides and method for preparation, which comprises charging solution B into a buffering solution A containing one or more transitional metal ions, making the miscible liquid have a predetermined pH range. The prepared wet gel has rather high electrochemical capacity, and can be widely applied to the fields of battery, supercapacitor and catalyzed industry.
Description
Technical field
The present invention relates to the preparation method of a kind of transition metal oxide or oxyhydroxide wet gel, belong to chemical engineering and field of new.Can be widely used in fields such as battery, ultracapacitor, fuel cell and catalysis industry.
Background technology
Transition metal oxide, oxyhydroxide have a wide range of applications.Mostly the catalyzer of Application in Chemical Engineering is transition metal oxide, as molybdenum oxide, barium oxide; Paint and pigment use ferric oxide, chromic oxide etc.; The electrode materials of battery industry much all is transition metal oxide, oxyhydroxide, as lithium ion cell anode material lithium cobaltate, lithium manganate etc., Ni-H cell positive electrode material nickel hydroxide, lead-acid cell positive electrode material plumbous oxide, drying battery positive electrode material Manganse Dioxide or the like.
Conventional material has certain defective at aspect of performance, as the pigment ferric oxide, precipitates easily; And catalystic material in order to increase reaction area, generally needs carrier, involves dispersion and supports technology etc., technique means complexity, cost height.In addition, in battery, electrochemical capacitor were used, owing to improving constantly of demand, the performance of conventional material can not satisfy growing power supply requirement gradually, required the new material of research and development.When the yardstick of material is little to nano level the time, performance and conventional yardstick material have tangible change, nano effect promptly occurs.Had research to point out that nano material can improve the performance of electrochemical energy source material, thereby nano material may be the key that solves existing problem.But nano material itself is owing to the flourishing problem that has stable aspect of specific surface area.
Material is made aerogel or xerogel, then because gel itself has the solid net of a large amount of cavities and commissure, effectively Nanosurface is separated, thereby more stable, so the gelation material may be the unique stabilized nanoscale material and the approach of structure than general nano material.
Gel is a vesicular structure, be solid material by nano-scale by the continuous space network that a large amount of space of crosslinked envelope constitutes, have higher specific surface area and high surface, have flourishing molecular channel, the stabilized nano structure is the material of a class excellent performance.Gelatinous material is having extensive studies and application as the material of a kind of nano level hole, low density, high-ratio surface aspect thermal isolation, heterocatalysis, X-ray detection X, physics, engineering, the catalysis.And conducting metal oxide, hydroxide gel will be the extremely promising novel materials of a class owing to can performance be improved and begin one's study as the novel material of electrochemistry aspect using aspect battery, electric capacity, the fuel cell.
Existing patent, CN1418230A provides a kind of method for preparing silicone gel, uses four kinds of silicone gels that the component hybrid reaction obtains having the shape hold facility, is mainly used in electron trade; CN1446848A has invented a kind of gel electrolyte, generates gel with electrolytic salt, solvent and polymeric matrix hybrid reaction, is mainly used in battery, electrochemical capacitor etc.; CN1057443A has invented the preparation technology of aluminum hydroxide gel, with CO
2Method prepares aluminum hydroxide gel by the CONTROL PROCESS condition.The existing invention of other relevant gel is many at aspects such as oil production, medical treatment, and relevant transition metal oxide, hydroxide gel and preparation method thereof also do not have relevant patent report.
Summary of the invention
The preparation method who the purpose of this invention is to provide transition metal oxide or oxyhydroxide wet gel to reduce the preparation cost of gelatinous material, makes gelatinous material can really bring into play the effect of its stabilized nano material.
The object of the present invention is achieved like this, and the preparation method of transition metal oxide or oxyhydroxide wet gel comprises following each step:
1. material solution A preparation: transistion metal compound and solvent preparation contain the transistion metal compound solution of complexing agent, concentration 0.01～2 mol;
2. material solution B preparation: alkali and oxidisability reagent and solvent are mixed with solution, alkali concn 0.1～15 mol wherein, oxidisability reagent concentration 0.001～5 mol;
3. controlled temperature is 0～100 ℃, material solution B is slowly joined among the material solution A endpoint pH 10～14 of control reaction system;
4. product is removed mother liquor, obtains transition metal oxide or oxyhydroxide wet gel after the cleaning.
Transition metal of the present invention comprises following: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Cd, W, Ir, Pt, Au, Pb.Complexing agent of the present invention be following one or more: acetate, acetate, oxalate, oxalic acid, succsinic acid, succinate, L-GLUTAMICACID, glutamate, oxysuccinic acid, malate, lactic acid, lactic acid salt, mandelic acid, amygdalate, boric acid, borate, Thiovanic acid, thioglycolate salt, citric acid, Citrate trianion, tartrate, tartrate, Whitfield's ointment, salicylate, sulphosalicylic acid, sulfosalicylate, bicine N-, bicine N-salt, EDTA, thiocarbamide, S
2O
3 3-, quadrol, trolamine, tri-polyphosphate, ammonia, pyrophosphate salt, hexametaphosphate, alkyl-sulphate.Solvent of the present invention be following one or more: water, ethanol, propyl alcohol, butanols, amylalcohol, hexalin, benzene, toluene, ethylbenzene.Transistion metal compound of the present invention be following one or more: phosphoric acid salt, vitriol, nitrate, hydrochloride, alkoxide, organic acid salt, ketone salt, diketone.Alkali of the present invention be following one or more: NH
4OH, Ba (OH)
2, NaOH, KOH, LiOH, alkoxide.Temperature range of the present invention is at 0～100 ℃.Oxidisability reagent of the present invention be following one or more: hydrogen peroxide, potassium permanganate, ammonium persulphate, ammonium molybdate.
This method is simple, convenient, be easy to industrialization.The transition metal oxide or the oxyhydroxide wet gel of preparation are compared with conventional material, and chemical property exceeds more than 20%.
Description of drawings
Fig. 1 is to use the XRD curve of the nickel hydroxide xerogel of the inventive method preparation
X-coordinate is a diffraction angle
Ordinate zou is a diffracted intensity
Brief description transition metal oxide of the present invention or oxyhydroxide wet gel and preparation method thereof for two example two below
Embodiment 1
Adjust PH to 8 with water as solvent solution-forming with single nickel salt, sodium acetate, trisodium phosphate, ammoniacal liquor, as solution A.With the KOH of water, as solution B as 5 moles every liter of solvent preparation.Constantly stirring, under the situation of 60 ℃ of constant temperature, slowly solution B joined in the solution A, pH to 14 is as reaction end in control, stops to add solution B, keeps constant temperature 2 hours.Centrifugation product and mother liquor discard mother liquor, and product cleaning promptly obtains nickel hydroxide wet gel material to neutral.The XRD figure of product is seen Figure of description, and calculating shows that its grain-size is 6～7nm.
Embodiment 2
Adjust pH to 4 with water as solvent solution-forming with lead nitrate, sodium acetate, trisodium phosphate, nitric acid, as solution A.With the mixing solutions of water, as solution B as solvent 5 moles of every liter of KOH of preparation and 0.2 mole of every liter of hydrogen peroxide.Constantly stirring, under the situation of 40 ℃ of constant temperature, slowly solution B joined in the solution A, pH to 14 is as reaction end in control, stops to add solution B, keeps constant temperature 5 hours.Centrifugation product and mother liquor discard mother liquor, and product cleaning promptly obtains the plumbic oxide gelatinous material to neutral.
Claims (6)
1. the preparation method of transition metal oxide or oxyhydroxide wet gel is characterized in that this preparation method comprises following each step:
1. material solution A preparation: transistion metal compound and solvent preparation contain the transistion metal compound solution of complexing agent, concentration 0.01～2 mol;
2. material solution B preparation: alkali and oxidisability reagent and solvent are mixed with solution, alkali concn 0.1～15 mol wherein, oxidisability reagent concentration 0.001～5 mol, wherein oxidisability reagent is one or more of hydrogen peroxide, potassium permanganate, ammonium persulphate, ammonium molybdate;
3. controlled temperature is 0～100 ℃, material solution B is slowly joined among the material solution A endpoint pH 10～14 of control reaction system;
4. product is removed mother liquor, obtains transition metal oxide or oxyhydroxide wet gel after the cleaning.
2. according to the preparation method of described transition metal oxide of claim 1 or oxyhydroxide wet gel, it is following to it is characterized in that transition metal comprises: Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Cd, W, Ir, Pt, Au, Pb.
3. according to the preparation method of described transition metal oxide of claim 1 or oxyhydroxide wet gel, it is characterized in that complexing agent be following one or more: acetate, acetate, oxalate, oxalic acid, succsinic acid, succinate, L-GLUTAMICACID, glutamate, oxysuccinic acid, malate, lactic acid, lactic acid salt, mandelic acid, amygdalate, boric acid, borate, Thiovanic acid, thioglycolate salt, citric acid, Citrate trianion, tartrate, tartrate, Whitfield's ointment, salicylate, sulphosalicylic acid, sulfosalicylate, bicine N-, bicine N-salt, EDTA, thiocarbamide, S
2O
3 3-, quadrol, trolamine, tri-polyphosphate, ammonia, pyrophosphate salt, hexametaphosphate, alkyl-sulphate.
4. according to the preparation method of described transition metal oxide of claim 1 or oxyhydroxide wet gel, it is characterized in that solvent be following one or more: water, ethanol, propyl alcohol, butanols, amylalcohol, hexalin, benzene, toluene, ethylbenzene.
5. according to the preparation method of described transition metal oxide of claim 1 or oxyhydroxide wet gel, it is characterized in that transistion metal compound be following one or more: phosphoric acid salt, vitriol, nitrate, hydrochloride, alkoxide, organic acid salt, ketone salt, diketone.
6. according to the preparation method of described transition metal oxide of claim 1 or oxyhydroxide wet gel, it is characterized in that alkali be following one or more: NH
4OH, Ba (OH)
2, NaOH, KOH, LiOH, alkoxide.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410058106 CN1733599B (en) | 2004-08-13 | 2004-08-13 | Process for preparing moisture gel of transition metal oxide and hydroxide |
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| CN 200410058106 CN1733599B (en) | 2004-08-13 | 2004-08-13 | Process for preparing moisture gel of transition metal oxide and hydroxide |
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| CN1733599A CN1733599A (en) | 2006-02-15 |
| CN1733599B true CN1733599B (en) | 2010-04-28 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE102007014914B4 (en) | 2007-03-26 | 2013-09-12 | Heraeus Precious Metals Gmbh & Co. Kg | Catalytically highly effective noble metal carboxylate compounds of Ir, Ru, Rh, Pd, Pt and Au |
| US9540249B2 (en) * | 2012-09-05 | 2017-01-10 | The University Of Hong Kong | Solution-processed transition metal oxides |
| CN104425815B (en) * | 2013-08-19 | 2018-07-03 | 日电（中国）有限公司 | The preparation method of high density spherical nickel-cobalt aluminic acid lithium material and its presoma |
| CN104556337B (en) * | 2013-10-14 | 2017-06-16 | 陕西太昱科技发展有限公司 | One kind suppresses screener |
| CN105350104B (en) * | 2015-12-01 | 2017-10-27 | 东华大学 | A kind of preparation method of Mesoporous zirconium phosphate loaded copper oxide antibacterial polyethylene alcohol fiber |
| CN109126643B (en) * | 2017-06-15 | 2020-06-02 | 湖南尚成新材料科技有限责任公司 | Self-light-modulation type transparent composite aerogel and preparation method thereof |
| CN108439409A (en) * | 2018-04-18 | 2018-08-24 | 南京工业大学 | A kind of preparation method of bulk boron carbide aeroge |
| CN112390298B (en) * | 2019-08-19 | 2022-08-23 | Tcl科技集团股份有限公司 | Modified metal oxide, preparation method thereof and quantum dot light-emitting diode |
| CN111052909A (en) * | 2020-01-19 | 2020-04-24 | 四川省天晟源环保股份有限公司 | Safe passivation and planting method for heavy metal cadmium in rice field |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107442A (en) * | 1994-02-26 | 1995-08-30 | 王维波 | Process for preparing nickel hydroxide |
| CN1359353A (en) * | 1999-06-29 | 2002-07-17 | Omg芬兰公司 | Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process |
-
2004
- 2004-08-13 CN CN 200410058106 patent/CN1733599B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1107442A (en) * | 1994-02-26 | 1995-08-30 | 王维波 | Process for preparing nickel hydroxide |
| CN1359353A (en) * | 1999-06-29 | 2002-07-17 | Omg芬兰公司 | Process for making high density and large particle size cobalt hydroxide or cobalt mixed hydroxides and a product made by this process |
Non-Patent Citations (2)
| Title |
|---|
| 李冬梅、夏熙.络合沉淀法合成纳米氧化铜粉体及其性能表征.无机材料学报第16卷 第6期.2001,16(6),第1207-1210页. |
| 李冬梅、夏熙.络合沉淀法合成纳米氧化铜粉体及其性能表征.无机材料学报第16卷 第6期.2001,16(6),第1207-1210页. * |
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