CN108269991A - Preparation method of zinc-bismuth alloy powder for flexible battery cathode - Google Patents
Preparation method of zinc-bismuth alloy powder for flexible battery cathode Download PDFInfo
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Abstract
The invention provides a preparation method of corrosion-resistant zinc-bismuth alloy powder, which comprises the following steps: the method comprises the following specific preparation processes of chemically reacting metal bismuth with plating solution in a chemical immersion plating mode, and plating bismuth on the surface of zinc powder: zinc powder deoiling, cleaning, acid pickling and activating, cleaning, bismuth plating of zinc powder in bismuth immersion plating solution, alloy powder filtering, alloy powder cleaning and drying, high-temperature heating in an inert atmosphere, and cooling to obtain a target product. The invention belongs to the field of zinc-manganese battery cathode materials, and discloses a cathode for a zinc-manganese battery prepared from zinc-bismuth alloy powder, which is suitable for an alkaline or acid zinc-manganese battery, in particular suitable for the fields of flexible, thin film and special zinc-manganese batteries which need to prepare cathodes by using superfine zinc powder. The invention uses the green nontoxic metal bismuth to replace highly toxic mercury, lead and the like as the battery corrosion inhibitor, has simple and easy operation, can greatly improve the self-discharge phenomenon of the zinc-manganese battery in the storage process, and has great application and popularization values.
Description
Technical Field
The invention relates to a preparation method of zinc-bismuth alloy powder, in particular to a preparation method of zinc-bismuth alloy powder for preparing a zinc-manganese battery cathode material.
Background
For a long time, people always adopt mercury as a corrosion inhibitor of a zinc-manganese battery cathode, but due to the requirement on environmental protection, the use of mercury in the zinc-manganese battery is strictly controlled by legislation in Europe, america and China at present, and various countries in the world actively research and develop zinc-manganese batteries without mercury additives. With the increasing awareness of environmental protection, inorganic corrosion inhibitors represented by toxic heavy metals such as mercury and lead are inevitably eliminated in the near future in the field of zinc-manganese batteries.
Research on the hydrogen evolution overpotential of metal shows that the metal tin, bismuth, indium, gallium and the like have higher hydrogen evolution overpotential and can replace the application of mercury, lead and other heavy metals which have great harm to the environment in the zinc-manganese battery corrosion inhibitor. From the hydrogen evolution overpotentials of various metals, metals such as Ga, in, pb, sn and Bi have high hydrogen evolution overpotentials and can be used as inorganic corrosion inhibitors for replacing mercury. From the current research results, they are added to the electrolyte either in the form of zinc alloy or in the form of salt.
Bismuth is a recognized "green metal" and is the least toxic of all heavy metals. Its melting point is 271.3 deg.C, and it is often used together with zinc, tin, indium and antimony to prepare low-melting point alloy.
From the research results at present, the inorganic corrosion inhibitor containing bismuth (Bi) has good effect in zinc-manganese batteries, but the addition of electrolyte in the form of bismuth salt has the limitation of solubility, and the existing bismuth chloride or bismuth nitrate has very low solubility in water and is particularly easy to hydrolyze, so that the corrosion inhibition system is unstable.
Disclosure of Invention
Aiming at the defects of the existing zinc powder bismuth plating process, the invention aims to provide a preparation method of corrosion-resistant zinc bismuth alloy powder, and a cathode for a zinc-manganese battery is prepared by using the prepared zinc bismuth alloy powder. The prepared zinc-bismuth alloy powder is suitable for alkaline or acid zinc-manganese batteries, is particularly suitable for the fields of flexible, thin-film and special-shaped zinc-manganese batteries, and greatly improves the self-discharge phenomenon of the batteries in the storage process.
The preparation method of the zinc-bismuth alloy powder adopts chemical dip coating, zinc powder is put into a dip coating solution to enable metal bismuth to react with the chemical coating solution, and bismuth is coated on the surface of the zinc powder through chemical reaction to prepare the zinc-bismuth alloy, and the preparation method of the zinc-bismuth alloy is characterized by comprising the following specific processes:
(1) Zinc powder is used for oil removal, acid washing and activation;
(2) Chemically plating bismuth by using a plating solution;
(3) Filtering, cleaning and drying the alloy powder;
(4) Heating the alloy powder at high temperature in an inert gas atmosphere;
(5) And obtaining the zinc-bismuth alloy powder.
Further, the immersion plating solution formula comprises the following components: bismuth salt, complexing agent, auxiliary complexing agent, stabilizer, pH buffer, surfactant and solvent.
Further, the bismuth salt is one or more of bismuth trioxide, bismuth nitrate, bismuth chloride, bismuth methanesulfonate and bismuth sulfamate; the bismuth salt content is 1-100g/L, preferably 5-50g/L, more preferably 20-40g/L, wherein when bismuth trioxide is selected, bismuth trioxide is dissolved in one or more of nitric acid, hydrochloric acid, methanesulfonic acid or sulfamic acid during actual preparation.
Furthermore, the complexing agent is one or more of lactic acid, tartaric acid, malic acid and citric acid, and the content of the complexing agent is 10-200g/L, preferably 20-150g/L, and more preferably 30-100g/L.
Further, the auxiliary complexing agent is one or more of salicylic acid, pyridine carboxylic acid, 2-piperazine carboxylic acid, 1, 6-pyridine dicarboxylic acid, 2, 3-pyridine dicarboxylic acid, 2, 5-pyridine dicarboxylic acid, 2, 3-piperazine dicarboxylic acid, nitrilotriacetic acid, thiourea and thiosemicarbazide; the content of the auxiliary complexing agent is 10-100g/L, preferably 20-80g/L, and more preferably 30-70g/L.
Further, the stabilizer is one or more of glycerol, mannitol, ethylene glycol and triethanolamine; the content of the stabilizer is 10 to 50g/L, preferably 15 to 45g/L, and more preferably 20 to 40g/L.
Further, the pH buffer agent is boric acid; the boric acid content is 10-50g/L, preferably 20-40g/L, more preferably 25-35g/L.
Further, the surfactant is one or more of turkey red oil, sulfonated castor oil and tween 40; the content of the surfactant is 0.01-10g/L.
Further, the solvent is a mixed solution of water and ethanol, and the ratio of.
Furthermore, the zinc powder is dipped in the dipping solution in a manner that the zinc powder is added into a dipping solution container which starts magnetic stirring or mechanical stirring, and the zinc powder and the dipping solution are stirred until reaching the time required for dipping.
Furthermore, the zinc powder after chemical immersion plating bismuth can be cleaned and dried and then can be tiled and put into a high-temperature oven filled with argon or nitrogen for high-temperature alloying, the specific process is that the temperature is increased to 300-400 ℃ at the speed of 10 ℃/min, the temperature is kept for 6-12h, then the heating is closed, and the new coin alloy powder is prepared by natural cooling.
Further, the zinc bismuth alloy powder is used for preparing zinc manganese battery cathode slurry, and the zinc bismuth alloy powder, the organic corrosion inhibitor, the conductive agent, the high molecular adhesive, the curing agent, the stabilizer, the leveling agent, the dispersing agent, the defoaming agent, the solvent and the like are uniformly stirred by the stirring device.
The preparation method of the bismuth immersion plating solution comprises the steps of slowly adding the complexing agent and the auxiliary complexing agent into the mixed solvent to be dissolved uniformly to obtain colorless transparent liquid; slowly adding bismuth salt into the liquid to obtain colorless transparent liquid, and adding corresponding nitric acid, hydrochloric acid, sulfamic acid and methanesulfonic acid into the system until colorless transparent liquid is generated if the colorless transparent liquid is turbid; then adding a stabilizer and a PH buffer reagent in sequence; the surfactant is firstly dissolved uniformly by a mixed solvent and then added into the system according to the required amount; replenishing the solvent to a specified liquid level; the PH is measured to 1-6, preferably PH =2-5, more preferably PH =3-4.
Further, the immersion plating process of the immersion plating solution for chemically plating bismuth is carried out according to different specific conditions, the immersion plating temperature can be 15-35 ℃, and the immersion plating time can be 0.1-100min; vacuum filtration or centrifugal filtration is adopted for the zinc-bismuth alloy powder after dip plating, filtrate is recovered after filtration, and the recovered filtrate can be reused; and (3) cleaning the filtered zinc-bismuth alloy powder by using a mixed solution of water and ethanol, then cleaning by using ethanol, and repeating the steps until the alloy powder is cleaned.
The zinc powder used in the invention has the size of 0.005-500 um, and is in the shape of sphere, sphere-like, flake, needle and irregularity, wherein the zinc powder does not contain toxic heavy metals such as mercury, lead, cadmium and the like, and the content of metal impurities such as iron, cobalt, nickel, copper and the like is less than 100ppm.
Further, the degreasing process of the zinc powder before dip plating comprises surfactant degreasing, alkaline degreasing and solvent degreasing; wherein the surfactant is the conventional common surfactant, such as polyoxyethylene ether alkylphenol, polyoxyethylene sorbitan monostearate, sodium dodecyl sulfate, alkylbenzene sulfonate, triethanolamine oleate soap, coconut oil fatty acid diethanolamide, alkyl phosphate, alkyl sulfonate, polyethylene glycol and the like, and the content is 0.1-10g/L. The alkaline degreasing fluid used for zinc powder degreasing comprises 15-20g/L of sodium carbonate and 1-10g/L of surfactant at 40-60 ℃ for 5-15min, 15-20g/L of sodium carbonate, 20-30g/L of sodium metasilicate and 1-10g/L of surfactant at 40-60 ℃ for 5-15min, and the solvent degreasing solvent is acetone or ethanol, and ultrasonic degreasing is carried out.
Furthermore, the pH adjusting reagent in the process of preparing the immersion plating solution is corresponding nitric acid, hydrochloric acid, sulfamic acid, methanesulfonic acid and ammonia water.
In the preparation process of the zinc-bismuth alloy powder, deionized water is used for cleaning the alloy powder after oil removal, and acid solution with 10% sulfuric acid content is used for acid washing and activation after cleaning, wherein the activation time is 5-60s.
The preparation method of the invention has the process that the dip plating temperature of the zinc powder is 15-35 ℃, the dip plating time is 0.1-100min, and the dip plating time can be adjusted according to the required bismuth content. The higher the temperature and the longer the time in the immersion plating process, the higher the content of bismuth in the obtained zinc-bismuth alloy. The high-temperature heating makes the metal bismuth atoms dipped on the surface of the zinc powder move to the interior of the zinc atoms at high temperature, so that the zinc atoms are really alloyed, and the bismuth content in the alloy can be controlled by the dipping time. In order to prevent the difficult discharge caused by the fact that the bismuth content in the alloy is too high and the surfaces of the zinc powder are all dipped with bismuth, the prepared zinc-bismuth alloy powder can be crushed by a ball mill, and meanwhile, the surface area of the negative active material zinc powder can be increased, so that the discharge of the battery is facilitated.
The zinc-bismuth alloy powder prepared by the method can be used for preparing a cathode for a zinc-manganese battery, and the prepared cathode slurry is suitable for an alkaline or acid zinc-manganese battery, and is particularly suitable for the fields of flexible, thin film and special-shaped zinc-manganese batteries which need to prepare cathodes by using superfine zinc powder. The invention uses green nontoxic metal bismuth to replace highly toxic mercury, lead and the like as the battery corrosion inhibitor, has simple and easy operation in the preparation process, can greatly improve the self-discharge phenomenon of the zinc-manganese battery in the storage process, and has great application and popularization values.
Detailed Description
Example 1
100g of zinc powder with the size of 0.5um is taken for oil removal;
degreasing by using a surfactant: cleaning polyoxyethylene sorbitan monostearate at a concentration of 5g/L for 10min;
alkaline degreasing: the alkaline degreasing liquid contains 20g/L of sodium carbonate, 25g/L of sodium metasilicate and 1g/L of polyoxyethylene ether alkylphenol, the temperature is 45 ℃, the degreasing time is 10min, and the alkaline degreasing liquid is cleaned by deionized water;
solvent degreasing: removing oil with acetone as solvent for 10min;
cleaning: washing with deionized water;
acid washing and activating: activating with 10% sulfuric acid for 30s;
cleaning: washing with deionized water, and vacuum drying at 45 deg.C;
immersion plating solution: 40g/L of bismuth nitrate, 20g/L of tartaric acid, 20g/L of malic acid, 30g/L of thiosemicarbazide, 25g/L of glycerol, 30g/L of boric acid, 0.5g/L of Turkey red oil and 0.5g/L of Tween, wherein the solvent is a mixed solution of water and ethanol 1, and the pH value of the solution is regulated to 5 by using dilute nitric acid and ammonia water;
the dip plating process comprises the following steps: the temperature is room temperature, and the immersion plating time is 2min;
and (3) immersion plating mode: starting magnetic stirring in a 500ml three-neck flask containing 300ml of dip-plating solution, slowly adding the dried zinc powder into the flask, and stirring for a specified time;
filtering and cleaning: recovering filtrate in a vacuum filtration mode, firstly cleaning the particles by using a 1;
high-temperature heating: and flatly spreading the solid particles, putting the solid particles into a high-temperature oven filled with argon, heating to 400 ℃ at the speed of 10 ℃/min, keeping the temperature for 6 hours, closing the heating, naturally cooling to room temperature, and taking out the solid particles to obtain the zinc-bismuth alloy powder.
Example 2
150g of zinc powder with the size of 5um is taken for deoiling;
degreasing by using a surfactant: washing coconut oil fatty acid diethanolamide 10g/L for 5min;
alkaline degreasing: the alkaline degreasing liquid contains 30g/L of sodium carbonate, 30g/L of sodium metasilicate and 2g/L of polyoxyethylene ether alkylphenol, the temperature is 50 ℃, the degreasing time is 15min, and the alkaline degreasing liquid is cleaned by deionized water;
solvent degreasing: ultrasonically removing oil for 10min by using ethanol as a solvent;
cleaning: washing with deionized water;
acid washing and activating: activating with 10% sulfuric acid for 20s;
cleaning: washing with deionized water, and vacuum drying at 45 deg.C;
plating solution immersion: 50g/L of bismuth methanesulfonate, 25g/L of lactic acid, 25g/L of citric acid, 35g/L of pyridine carboxylic acid, 10g/L of ethylene glycol, 10g/L of mannitol, 40g/L of boric acid, 1g/L of sulfonated castor oil and 1g/L of Tween 40, wherein a solvent is a mixed solution of water and ethanol 1, and the pH value of the solution is adjusted to 4 by using dilute nitric acid and ammonia water;
and (3) dip plating process: the temperature is room temperature, and the immersion plating time is 5min;
and (3) immersion plating mode: starting magnetic stirring in a 500ml three-neck flask containing 300ml of immersion plating solution, slowly adding the dried zinc powder into the flask, and stirring for a specified time;
filtering and cleaning: recovering filtrate in a vacuum filtration mode, firstly cleaning the particles by using a 1;
high-temperature heating: and flatly spreading the solid particles, putting the solid particles into a high-temperature oven filled with argon, heating to 300 ℃ at the speed of 10 ℃/min, keeping the temperature for 12 hours, closing the heating, naturally cooling to room temperature, and taking out the solid particles to obtain the zinc-bismuth alloy powder.
Example 3
200g of zinc powder with the size of 20um is taken for oil removal;
degreasing by using a surfactant: cleaning with triethanolamine oleate soap 8g/L for 10min;
alkaline degreasing: the alkaline degreasing liquid contains 20g/L of sodium carbonate, 20g/L of sodium metasilicate and 5g/L of polyethylene glycol, the temperature is 50 ℃, the degreasing time is 10min, and the alkaline degreasing liquid is cleaned by deionized water;
solvent degreasing: ultrasonic degreasing for 15min by using ethanol as a solvent;
cleaning: washing with deionized water;
acid washing and activating: activating with 10% sulfuric acid for 60s;
cleaning: washing with deionized water, and vacuum drying at 45 deg.C;
plating solution immersion: 25g/L of bismuth chloride, 15g/L of malic acid, 15g/L of citric acid, 30g/L of nitrilotriacetic acid, 15g/L of mannitol, 30g/L of boric acid, 0.5g/L of sulfonated castor oil and 0.5g/L of tween, wherein the solvent is a mixed solution of water and ethanol 1, and the pH value of the solution is adjusted to 3 by using dilute hydrochloric acid and ammonia water;
and (3) dip plating process: the temperature is 30 ℃, and the immersion plating time is 10min;
and (3) immersion plating mode: starting magnetic stirring in a 500ml three-neck flask containing 300ml of immersion plating solution, slowly adding the dried zinc powder into the flask, and stirring for a specified time;
filtering and cleaning: recovering the filtrate by vacuum filtration, cleaning the particles by using a mixed solution of ethanol and water of 1;
high-temperature heating: flatly spreading the solid particles, putting the solid particles into a high-temperature oven filled with argon, heating to 350 ℃ at a speed of 10 ℃/min, keeping the temperature for 9 hours, closing the heating, naturally cooling to room temperature, and taking out the solid particles to obtain zinc-bismuth alloy powder;
ball milling: the prepared zinc-bismuth alloy powder is put into an agate ball mill for ball milling, and the zinc-bismuth alloy powder with smaller size can be prepared.
The corrosion-resistant zinc-bismuth alloy powder prepared by the invention is used for preparing the cathode of a zinc-manganese battery, and the prepared cathode is suitable for alkaline or acidic zinc-manganese batteries, and is particularly suitable for the fields of flexible, thin-film and special-shaped zinc-manganese batteries which need to prepare cathodes by using superfine zinc powder. The method for preparing the zinc-bismuth alloy powder has the advantages that the zinc-bismuth alloy powder is prepared by the method, the plating solution and the zinc powder are subjected to chemical reaction, and the green nontoxic metal bismuth in the plating solution is used for replacing mercury, lead and the like with high toxicity as a battery corrosion inhibitor, so that the self-discharge phenomenon in the storage process of the zinc-manganese battery can be greatly improved, the storage life of the zinc-manganese battery is greatly prolonged, meanwhile, the preparation method has the advantages of simple process, convenience in operation, low requirements on operation equipment and operation environment, low preparation cost and great industrial application value in the field of zinc-manganese battery cathode materials.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Those skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which may be made by those skilled in the art without departing from the spirit and scope of the present invention as defined in the appended claims.
Claims (12)
1. A preparation method of zinc bismuth alloy powder adopts chemical dip plating, zinc powder is put into dip plating solution, and zinc bismuth alloy is prepared through chemical reaction, and is characterized in that the preparation method of the zinc bismuth alloy comprises the following specific processes:
(1) Zinc powder is subjected to oil removal, acid washing and activation;
(2) Plating bismuth by chemical dip plating solution;
(3) Filtering, cleaning and drying the alloy powder;
(4) Heating the alloy powder at high temperature in an inert gas atmosphere;
(5) And obtaining the zinc-bismuth alloy powder.
2. The preparation method of the zinc-bismuth alloy powder according to claim 1, wherein the chemical bismuth immersion plating solution comprises the following components: bismuth salt, complexing agent, auxiliary complexing agent, stabilizing agent, PH buffering agent, surfactant and solvent.
3. The method for preparing the zinc-bismuth alloy powder according to claim 2, wherein the bismuth salt is one or more of bismuth trioxide, bismuth nitrate, bismuth chloride, bismuth methanesulfonate and bismuth sulfamate; the bismuth salt content is 1-100g/L, preferably 5-50g/L, more preferably 20-40g/L, wherein when bismuth trioxide is selected, the bismuth trioxide is dissolved in one or more of nitric acid, hydrochloric acid, methanesulfonic acid or sulfamic acid during actual preparation.
4. The preparation method of the zinc-bismuth alloy powder according to claim 2, wherein the complexing agent is one or more of lactic acid, tartaric acid, malic acid and citric acid, and the content of the complexing agent is 10-200g/L, preferably 20-150g/L, and more preferably 30-100g/L.
5. The method for preparing the zinc-bismuth alloy powder according to claim 2, wherein the auxiliary complexing agent is one or more of salicylic acid, pyridine carboxylic acid, 2-piperazine carboxylic acid, 1, 6-pyridine dicarboxylic acid, 2, 3-pyridine dicarboxylic acid, 2, 5-pyridine dicarboxylic acid, 2, 3-piperazine dicarboxylic acid, nitrilotriacetic acid, thiourea and thiosemicarbazide; the content of the auxiliary complexing agent is 10-100g/L, preferably 20-80g/L, and more preferably 30-70g/L.
6. The method for preparing the zinc-bismuth alloy powder according to claim 2, wherein the stabilizer is one or more of glycerol, mannitol, ethylene glycol and triethanolamine; the content of the stabilizer is 10 to 50g/L, preferably 15 to 45g/L, and more preferably 20 to 40g/L.
7. The method for preparing the zinc-bismuth alloy powder according to claim 2, wherein the pH buffering agent is boric acid; the boric acid content is 10-50g/L, preferably 20-40g/L, more preferably 25-35g/L.
8. The method for preparing the zinc-bismuth alloy powder according to claim 2, wherein the surfactant is one or more of turkey red oil, sulfonated castor oil and tween 40; the content of the surfactant is 0.01-10g/L.
9. The method for preparing the zinc-bismuth alloy powder according to claim 2, wherein the solvent is a mixed solution of water and ethanol, and the ratio of the mixed solution is from 0 to 100, preferably from 20 to 80, and more preferably from 40 to 60.
10. The method for preparing the zinc-bismuth alloy powder as claimed in claim 1, wherein the zinc powder is dipped in the dipping solution in a manner that the zinc powder is added into a dipping solution container starting magnetic stirring or mechanical stirring, and the zinc powder and the dipping solution are stirred until reaching the time required for dipping.
11. The method for preparing the zinc-bismuth alloy powder according to claim 1, wherein the zinc powder chemically dip-plated with bismuth is cleaned, dried, laid flat, put into a high-temperature oven filled with argon or nitrogen for high-temperature alloying, heated to 300-400 ℃ at a rate of 10 ℃/min, kept for 6-12h, then closed and heated, and naturally cooled to obtain the new coin alloy powder.
12. The preparation method of the zinc-bismuth alloy powder according to claim 2, wherein the zinc-bismuth alloy powder is used for preparing zinc-manganese battery cathode slurry, and the specific preparation process comprises uniformly stirring the zinc-bismuth alloy powder, the organic corrosion inhibitor, the conductive agent, the high molecular binder, the curing agent, the stabilizer, the leveling agent, the dispersing agent, the defoaming agent, the solvent and the like through a stirring device.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113707854A (en) * | 2021-08-13 | 2021-11-26 | 张家港智电芳华蓄电研究所有限公司 | Preparation method of zinc powder coated with copper, tin, lead or alloy thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1332269A (en) * | 2001-07-10 | 2002-01-23 | 中山大学 | Chemical bismuth plating process |
| US6461768B1 (en) * | 1999-06-08 | 2002-10-08 | Dowa Mining Co., Ltd. | Negative electrode material containing bismuth-coated zinc powder particles for use in alkaline cell |
| CN103469184A (en) * | 2013-09-27 | 2013-12-25 | 武汉工程大学 | Preparation method of super-hydrophobic bismuth coating |
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2016
- 2016-12-30 CN CN201611260322.5A patent/CN108269991A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6461768B1 (en) * | 1999-06-08 | 2002-10-08 | Dowa Mining Co., Ltd. | Negative electrode material containing bismuth-coated zinc powder particles for use in alkaline cell |
| CN1332269A (en) * | 2001-07-10 | 2002-01-23 | 中山大学 | Chemical bismuth plating process |
| CN103469184A (en) * | 2013-09-27 | 2013-12-25 | 武汉工程大学 | Preparation method of super-hydrophobic bismuth coating |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113707854A (en) * | 2021-08-13 | 2021-11-26 | 张家港智电芳华蓄电研究所有限公司 | Preparation method of zinc powder coated with copper, tin, lead or alloy thereof |
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