CN1994891A - Chemical oxidation method for producing nano high valence silver oxide - Google Patents
Chemical oxidation method for producing nano high valence silver oxide Download PDFInfo
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- CN1994891A CN1994891A CN 200610000059 CN200610000059A CN1994891A CN 1994891 A CN1994891 A CN 1994891A CN 200610000059 CN200610000059 CN 200610000059 CN 200610000059 A CN200610000059 A CN 200610000059A CN 1994891 A CN1994891 A CN 1994891A
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- silver
- silver salt
- sodium hydroxide
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- hypochlorite
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Abstract
The invention discloses a making method of nanometer silvery oxide, which is characterized by the following: adding soluble silver salt solution or silver salt powder into the composite liquid of hypochlorite and alkali liquid slowly under certain temperature; stirring to obtain the product.
Description
One, the technical field of the invention
The invention belongs to domain of inorganic chemistry, specifically belong to nano inorganic salt synthetic technology.
Two, technical background of the present invention
The present invention relates to the synthetic method of a kind of nano oxidized Gao Yin (AgO).Specifically, be a kind of synthetic method of producing highly purified nano oxidized Gao Yin by soluble silver salts such as clorox and sodium hydroxide mixed chemical solution oxidation Silver Nitrates.
We know, silver usually with element or+form of 1 valency silver [Ag (I)] exists, but can obtain+divalent silver [Ag (II)] compound in the environment that strong oxidizer and strong basicity exist, it exists with the form of AgO usually.Silver oxide (AgO) has special strong oxidizing property, electromagnetic property and electrochemical activity as a kind of novel inorganic functional material, has been successfully applied to fields such as organic synthesis, superconductor and electrochemistry at present.The method of the silver oxide of traditional common particle diameter of preparation normally adopts strong oxidizer Potassium Persulphate or bromine water oxidation Silver Nitrate or silver suboxide (Ag in strong alkali solution
2Problems such as O) reaction makes, and the silver oxide that obtains so mainly exists: particle diameter is bigger, and purity is lower.
The electrode materials of exploitation height ratio capacity has become a focus in the present inorganic functional material research.Though alkaline silver-zinc battery cell is because technology maturation, moderate cost, loading capacity is big, and sparking voltage is stable to become widely used primary cell.But its anodal improved key of using is to improve the loading capacity and the specific power density of silver electrode at present, for this reason, many chemists have carried out a large amount of research from multiple angles to the property-modifying additive of silver suboxide, the additive of having reported at present has Manganse Dioxide, expanded graphite and chromic salt etc., and the use of these additives can improve the loading capacity and the storage performance of silver oxide electrode to a certain extent.We the result of study in early stage show that the silver oxide of employing+divalent replaces being extensive use of at present the Ag of+1 valency
2O can improve the loading capacity of silver electrode nearly one times.Discover that further performance after the adopting nanometer Ag O particle common AgO particle that mixes has tangible improvement, especially heavy-current discharge performance on chemical property.The improvement of this performance has benefited from the small-size effect of nanoparticle, and the high surface energy that high-specific surface area had that is had is relevant.
Therefore research synthetic fast small particle size silver oxide how, the method for silver oxide of especially inventing a kind of synthesis of nano particle size range is necessary, but the synthetic method of at present relevant highly purified nano oxidized Gao Yin is not seen relevant report so far at home and abroad.
Three, summary of the invention of the present invention
The objective of the invention is to,, provide the chemical synthesis process of a kind of nano oxidized Gao Yin newly, just prepare nanometer Ag O by liquid phase oxidation at the existing synthetic existing problem of silver oxide technology.Nanometer Ag O by this synthetic method preparation, has complete in crystal formation, the purity height, particle diameter is little, advantages such as operating procedure is simple, be specially adapted to alkaline silver-zinc battery cell or rechargeable alkaline silver zinc secondary battery anode material, also can be used for the occasion that some other needs AgO, synthetic as organic oxidation, new inorganic material research and development etc.The present invention proposes first and has invented and adopted high concentration hypochlorous acid salt and sodium hydroxide mixing solutions direct oxidation soluble silver salt to come single stage method to prepare the new synthetic method of high-purity nano AgO.The new chemical synthesis according to the present invention can the directly synthetic fast ultra-fine AgO with nano-scale.Result of study shows that controlled oxidation synthetic condition can directly obtain high purity AgO crystal.We have carried out certain improvement to the traditional technology that building-up process matches simultaneously, make it to be more suitable for new synthetic method.Novel method is compared quicker effective with other method for making, usually only need about 60 minutes, not only obviously shortened the required time of sedimentation, filtration and washing, and made more highly purified AgO, the common crystalline product purity after through washing can reach 95% or more than, can directly satisfy other raw material of cell-grade or chemical reagent requirement.
Building-up process of the present invention is to realize like this.With certain density silver ion solution, Silver Nitrate or silver acetate solution as 5～45% (weight percents) (also can be other silver salt, as Sulfuric acid disilver salt) under control certain temperature condition, hypochlorite and concentration of lye condition, join at leisure in the mixed solution of hypochlorite and alkali lye, separate out the active A g of pale brown look look this moment earlier
2The O crystallite is converted into the nanometer Ag O crystal of black then rapidly.This hypochlorite can be the mixed solution of clorox, Lithium oxychloride, Losantin or their arbitrary proportions.Because the chlorine bleach liquor cheaply is easy to get, our preferred clorox is as raw material.This alkali lye can be the mixed solution of sodium hydroxide solution, lithium hydroxide solution or their arbitrary proportions.The temperature of reaction of common above-mentioned reaction is at 10～45 ℃, and the concentration of lye scope is 5～53% (weight percents).Wherein preferable reaction temperature is 15～30 ℃, and concentration of lye is the sodium hydroxide of 20～45% (weight percents).This nanometer Ag O does through suction filtration or press filtration filter through behind centrifuge dehydration or the standing sedimentation, washs with 0.1～3mol/L NaOH earlier, washs pH to washings between 8～12 through pure water again.Control under 15～90 ℃ of conditions dry 1～10h, preferably dry 3～16h under vacuum condition and 50～70 ℃ of conditions obtains water content at the nanometer Ag O crystal below 1.5%.Also can directly obtain nanometer hydrated AgO crystal, again through washing and the dry nanocrystal that obtains same crystal formation by silver salt (as Silver Nitrate, Sulfuric acid disilver salt etc.) pressed powder with above-mentioned mixing solutions direct reaction.
Concrete synthesis process of the present invention is achieved in that Cl
2Feed in 22～40% (weight percent) NaOH solution, when alkali lye absorbs chlorine and reaches the chlorine bleach liquor of available chlorine content between 20%～30%, stop to feed chlorine, the usually preferred available chlorine content of this law is between 20～25%.Then the appropriate amount of NaOH solid is added in the above-mentioned solution, make NaOH content reach 30～50% (weight percents).In NaOH solid adition process, can separate out some solid sodium chloride, remove by filter sodium-chlor after, obtain being fit to nanometer sodium bismuthate synthetic NaClO-NaOH solution.Under agitation will be through the bismuth salt powder or the bismuth salts solution of porphyrize, add in the above-mentioned solution gradually at leisure, under maintenance violent stirring and room temperature, reacted 30～160 minutes, inject an amount of saturated sodium hydroxide solution to above-mentioned solution at last, separate out fully until the nanometer sodium bismuthate, above-mentioned reaction is controlled at 5～50 ℃, preferred 15～40 ℃.Thick product is done through refiltering filter after the centrifugation, with 0.1～3mol/L NaOH washing, washs to filtrate pH＜12 with pure water then, and final product is 20～60 ℃ of following vacuum-dryings.Products obtained therefrom purity is 92.1～95.9% with its purity of chromite chemistry titration.
Experimental data shows, mixes strong solution with clorox one sodium hydroxide and replaces Potassium Persulphate to make oxygenant, and not only cost of material is cheap, and under strictness control synthesis condition, not only can obtain having the AgO crystal of highly purified nano-scale.Experiment shows, at equal synthesis condition, mixes strong solution with clorox one sodium hydroxide and replaces Potassium Persulphate to make oxygenant, does silver-colored source with silver nitrate solution, and product purity has improved 4～6%, and productive rate has improved 5～9%.This is because exist the silver ions of ionic species in the solution, both guaranteed the sufficient contact between the reactant ion to greatest extent, avoided simultaneously adopting silver suboxide and low solubility Potassium Persulphate self again since the low reaction that causes of the low oxygenant that produces of solubleness not exclusively and be mingled with other impurity.In addition, in the TG-DSC experiment, find that highly purified nanometer Ag O crystal has very high stability at normal temperatures, when envrionment temperature is elevated to 115 ℃, just begin slowly to lose the Ag that oxygen forms+1 valency
2O, this shows that nanometer Ag O has very high stability at normal temperatures.
Four, description of drawings
Accompanying drawing 1 is synthetic sample is analyzed its thing phase crystalline structure at Japanese Rigaku D/max2500VB2+/PC X-ray diffractometer a XRD figure.It is 40kV that Cu target, tube voltage are used in test, and electric current is 200mA, and sweep velocity is 10 °/min, and scanning angle (2 θ) scope is 10 °～90 °.X-coordinate is 2 θ angles of X-ray diffraction among the figure, and ordinate zou is represented the intensity of X diffraction.Curve among the figure is a synthetic sample, according to the JCPDS standard card (PDF#84-1547) of AgO, confirms that synthetic sample is the AgO crystal.
Accompanying drawing 2 is that nanometer Ag O crystal is being gone up the transmission photo of sample being done the particle photograph at the H-800 of Hitachi transmission electron microscope (TEM), and the scale among the figure is to be expressed as 100nm.Photo among the figure shows that sample is that width is 40-150nm, and height is the nanocrystal of 20-50nm.
Five, the specific embodiment of the present invention
To further the present invention be described below by embodiment.
Embodiment 1
30% the NaOH of 80ml after absorbing 20g chlorine under 15～30 ℃ of temperature, is added 50g sodium hydroxide, leach the sodium-chlor of separating out, obtain the mixed solution of clorox and sodium hydroxide this moment.With 25 gram AgNO
3Crystal is silver-colored source, behind its mechanical porphyrize, under violent stirring it is added in the above-mentioned clorox test solution on a small quantity repeatedly, and above-mentioned reaction control temperature is at 25～40 ℃, and the reaction times is 60min, obtains the AgO precipitation of black.After should precipitating standing demix, transfer on the glass filter funnel, after 1%NaOH and pure water drip washing, drain, in vacuum drying oven, behind 50 ℃ of dry 24h, obtain the silver oxide sample with the filter flask vacuum.Measuring products obtained therefrom purity through chemical analysis is 93.5%.
Embodiment 2
30% the NaOH of 80ml after absorbing 21g chlorine, is added 66g sodium hydroxide, leach the sodium-chlor of separating out.Add the 1mol/L silver nitrate solution of 100ml in this solution, the temperature of controlling above-mentioned reaction is 20～30 ℃, after fully reacting 60 minutes, and the saturated NaOH solution of the 20ml that reinjects, filtering separation obtains nanometer Ag O crude product, and above-mentioned reaction is controlled at 30 ℃.Filter is dried after filtration again for thick product, behind the NaOH and pure water washing with 0.5mlo/L, 0.1mol/L, promptly obtains nanometer Ag O product successively, and final product is 60 ℃ of following vacuum-dryings.Products obtained therefrom purity is 95.2%.
Embodiment 3
35% the NaOH of 120g after absorbing 30g chlorine under 15～25 ℃ of temperature, is added 55g sodium hydroxide, thereby filters the mixed solution that the sodium-chlor of separating out obtains clorox and sodium hydroxide.AgNO with 50ml1.8mol/L
3Strong solution is silver-colored source, under violent stirring it is added with Sprayable in the mixed solution test solution of above-mentioned clorox and sodium hydroxide, and above-mentioned reaction control temperature is at 26～42 ℃, and the reaction times is 50min, obtains the AgO precipitation of black.After should precipitating standing demix, transfer on the glass filter funnel, after 1%NaOH and pure water drip washing, drain, in vacuum drying oven, behind 50 ℃ of dry 18h, obtain nanometer Ag O sample with the filter flask vacuum.Measuring products obtained therefrom purity through chemical analysis is 94.2%.
Claims (6)
1. the new silver-colored synthetic method of nano oxidized height is characterized in that a kind of synthetic method that obtains highly purified nano oxidized Gao Yin by the mixing solutions oxidation soluble silver salt of hypochlorite and sodium hydroxide.
2. soluble silver salt as claimed in claim 1, its feature can be a kind of silver salt in Silver Nitrate, Sulfuric acid disilver salt or the silver acetate, the mixture of two or more in the perhaps above-mentioned silver salt, usually preferred Silver Nitrate.
3. soluble silver salt as claimed in claim 1, its feature can be the dense aqueous solution of this silver salt, also can be the silver salt powder through mechanical porphyrize.
4. hypochlorite as claimed in claim 1 is characterized in that it can being a kind of material in clorox, Lithium oxychloride, the Losantin or the mixed solution of their arbitrary proportions, wherein preferred clorox.
5. the new silver-colored synthetic method of nano oxidized height as claimed in claim 1 is characterized in that in temperature of reaction be 5～35 ℃, and the concentration of lye scope is a synthetic under the reaction conditions of 5～53% (weight percents).Wherein preferable reaction temperature is 15～30 ℃, and concentration of lye is the sodium hydroxide of 20～45% (weight percents).
6. the mixing solutions of hypochlorite as claimed in claim 1 and sodium hydroxide, it is characterized in that wherein available chlorine content is at 20～30% hypochlorites, NaOH content is 30～50% (weight percents), and wherein preferred mixing solutions available chlorine content is between 20～25%.
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| CN 200610000059 CN1994891A (en) | 2006-01-06 | 2006-01-06 | Chemical oxidation method for producing nano high valence silver oxide |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811724A (en) * | 2010-04-23 | 2010-08-25 | 西安理工大学 | Method for preparing silver peroxide superfine powder |
| CN110150316A (en) * | 2019-06-02 | 2019-08-23 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of nano silver/subchloride composite bactericidal liquid |
| CN115849431A (en) * | 2022-10-11 | 2023-03-28 | 贵州梅岭电源有限公司 | Zinc-silver battery and high-specific-capacity AgO positive electrode material thereof |
-
2006
- 2006-01-06 CN CN 200610000059 patent/CN1994891A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101811724A (en) * | 2010-04-23 | 2010-08-25 | 西安理工大学 | Method for preparing silver peroxide superfine powder |
| CN110150316A (en) * | 2019-06-02 | 2019-08-23 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of nano silver/subchloride composite bactericidal liquid |
| CN115849431A (en) * | 2022-10-11 | 2023-03-28 | 贵州梅岭电源有限公司 | Zinc-silver battery and high-specific-capacity AgO positive electrode material thereof |
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