CN105478789A - Preparation method of spherical and spheroidal zinc powder - Google Patents

Preparation method of spherical and spheroidal zinc powder Download PDF

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Publication number
CN105478789A
CN105478789A CN201511024606.XA CN201511024606A CN105478789A CN 105478789 A CN105478789 A CN 105478789A CN 201511024606 A CN201511024606 A CN 201511024606A CN 105478789 A CN105478789 A CN 105478789A
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China
Prior art keywords
zinc
zinc powder
spherical
spheroidal
alloy liquid
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Pending
Application number
CN201511024606.XA
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Chinese (zh)
Inventor
乔涛
董烈寒
吴涛
李清湘
刘银
夏冬冬
王宏群
周少强
万良标
陈端云
吕新娟
向红印
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Shenzhen Nonfemet Technology Co ltd
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Shenzhen Nonfemet Technology Co ltd
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Priority to CN201511024606.XA priority Critical patent/CN105478789A/en
Publication of CN105478789A publication Critical patent/CN105478789A/en
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F9/00Making metallic powder or suspensions thereof
    • B22F9/02Making metallic powder or suspensions thereof using physical processes
    • B22F9/06Making metallic powder or suspensions thereof using physical processes starting from liquid material
    • B22F9/08Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying
    • B22F9/10Making metallic powder or suspensions thereof using physical processes starting from liquid material by casting, e.g. through sieves or in water, by atomising or spraying using centrifugal force
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B22CASTING; POWDER METALLURGY
    • B22FWORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/06Metallic powder characterised by the shape of the particles
    • B22F1/065Spherical particles

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)

Abstract

The invention provides a preparation method of spherical and spheroidal zinc powder. The centrifugal atomization powder making process of zinc powder mainly comprises the steps of pouring alloyed zinc alloy liquid into an intermediate heat preservation furnace, opening a flow control valve to enable the zinc alloy liquid to flow into a high-speed rotating disc through nozzle small holes, throwing the zinc alloy liquid out of the disc under the centrifugal force action of the high-speed rotating disc, and forming zinc powder particles in a centrifugal atomization barrel containing oxygen and inert gas in a certain proportion. The zinc powder is sieved and classified by a screen mesh to obtain spherical and spheroidal zinc powder, the prepared zinc powder can be used as a negative electrode material of an alkaline zinc-manganese dioxide battery, and the prepared battery has better comprehensive electrical properties such as high specific capacity, high power, long storage life and the like. The process flow for preparing the zinc powder by the centrifugal method is short, the interference factors are few, and the energy consumption is low.

Description

Preparation method of spherical and spheroidal zinc powder
Technical Field
The invention belongs to the technical field of electronic materials, and particularly relates to a preparation method of spherical and spheroidal zinc powder.
Background
At present, the atomization method is mainly adopted for preparing zinc powder. The medium for the atomization method includes high-pressure air, high-pressure inert gas and high-pressure water. Because the production cost of high-pressure inert gas and high-pressure water is relatively high, at present, high-pressure air is most commonly used as a medium for preparing zinc powder, cooling media of an atomization method are air cooling and water cooling, and at present, air cooling media are commonly used.
For example, CN1529369a in the prior art discloses a method for zinc powder for mercury-free alkaline manganese batteries, which is characterized in that aluminum and/or calcium with high melting points are placed at the bottom of a medium frequency induction furnace when melting is started, indium and bismuth are added at the furnace temperature of 550-640 ℃ after zinc ingots are completely melted, alloying is performed, the mixture is continuously and uniformly stirred for 3-4 minutes, the medium frequency induction furnace is rotated to 85KW and heated for 8-14 minutes, the temperature is controlled to be 650-720 ℃, then heating is stopped, the mixture is poured into a tundish for atomization while the mixture is hot, then particles with the particle size larger than 850 μm are removed by screening, and finally the particles are subjected to homogenization treatment to obtain a finished product.
CN103100709A discloses a method for producing zinc powder for alkaline zinc-manganese dioxide batteries of digital products, which is characterized by comprising the following steps: step A, heating a zinc ingot to 490-640 ℃, and adding at least two elements of indium, bismuth, aluminum and magnesium for alloying; and B: atomizing the alloy zinc liquid obtained in the step A to form zinc powder; and C: and D, grading the powder obtained in the step B by using a vibrating screen to obtain the zinc powder for the alkaline zinc-manganese battery.
The atomization method for preparing the zinc powder is influenced by the process, so that the technical problems and the defects of the atomization method have the following aspects:
1. the atomization powder preparation barrel process is generally a semi-open system and is easily influenced by external factors such as: the external temperature, the humidity, the wind power and the like, so the quality of the zinc powder prepared by the atomization method is relatively large under the external interference.
2. Most of the zinc powder prepared by the atomization method is in a random shape, mainly in a rod shape, a needle shape, a flake shape and the like, so that the zinc powder has relatively large specific surface area and relatively high chemical activity, and is not beneficial to long-time storage (10 years) of an alkaline battery.
3. The zinc powder prepared by the atomization method has relatively high oxidation degree which generally reaches over 0.2 percent because the atomization medium and the cooling medium are air, and the zinc powder is not beneficial to long-time storage.
4. The bulk density of the zinc powder prepared by the atomization method is generally 3g/cm 3 The specific capacity of the alkaline battery thus produced is difficult to be further improved.
Disclosure of Invention
In view of the technical problems in the prior art, the invention provides a preparation method of spherical and spheroidal zinc powder, which comprises the following steps:
(1) Preparing zinc alloy liquid, wherein the diameter range of the zinc alloy is, the solvent comprises, and the concentration range is;
(2) And (2) adding the zinc alloy liquid obtained in the step (1) into centrifugal atomization equipment, flowing into a rotating disc rotating at a high speed through small holes of a nozzle, throwing the zinc alloy liquid out by the rotating disc, and sieving and classifying to obtain spherical or near-spherical zinc powder in a centrifugal atomization barrel containing oxygen and inert gas in a certain proportion.
The particle size of the spherical or spheroidal zinc powder obtained by screening and grading is preferably distributed between 25 and 150 mu m, and the preferred apparent density is 3.0g/cm 3 ~5.0g/cm 3
The optimized parameters are selected through a large number of experiments by comprehensively considering the shape of the zinc powder of the centrifugal atomization powder preparation process, the requirement on the electrical property of the alkaline manganese battery and the characteristics of the centrifugal atomization equipment. The spherical and spheroidal zinc powder prepared by the parameters can meet the requirements of the market on various electrical properties of the alkaline manganese battery. And the direct yield of the method can reach more than 95 percent.
However, other centrifugal atomization methods and further particle size sieving can only be used to obtain a bulk density of 3g/cm 3 The following products; and most of them are rod-shaped, needle-shaped, flake-shaped, etc., and their specific surface area is relatively large, and their chemical activity is relatively high, so that they are not favourable for long-time storage of alkaline cell (10 years).
The zinc alloy liquid is alloyed zinc alloy liquid, and In and Bi are added In a certain proportion of 100-500 ppm at 450-600 ℃ after a zinc ingot is melted, or 1 or 2 of Al, ca and the like are added In a certain proportion of 0-300 ppm for alloying to form the zinc alloy liquid.
And (2) adding the zinc alloy liquid obtained in the step (1) into an intermediate heat preservation furnace of centrifugal atomization equipment, controlling the heat preservation temperature to be generally 450-700 ℃, opening a flow control valve, and passing through a nozzle small hole with the diameter of 1-5 mm.
The material of the turntable can be one or more of graphite, ceramic, iron, titanium alloy and the like.
The shape and the structure of the rotating disc can be a smooth disc without radian, a cup with certain radian or a bowl, and the diameter of the rotating disc is between 3 and 10cm.
The rotating speed range of the high-speed finger is 12000-30000 r/min.
The inert gas may be nitrogen or argon.
The volume ratio of the oxygen to the inert gas is less than or equal to 1/10 (V/V).
The zinc alloy is formed by adding 100-500 ppm of In and Bi elements at 450-600 ℃ after a zinc ingot is melted, or adding 1 or 2 elements of Al, ca and the like at 0-300 ppm In addition according to a certain proportion for alloying.
The spherical and spheroidal zinc powder prepared by the method is mainly used in the negative electrode material of the alkaline zinc-manganese battery. Such as alkaline batteries used in digital cameras, remote controls, toys, etc.
The beneficial effects of the invention compared with the prior art comprise:
the method mainly comprises the steps of producing zinc powder in a closed powder collecting barrel under the protection of inert gas containing certain oxygen, and solving the problems that the quality stability of the zinc powder prepared by an atomization method is relatively poor, the produced zinc powder has irregular appearance and high activity, the safety problem caused by self-discharge in the long-term storage process of a battery is caused, the loose packing density is difficult to improve, and the like. The spherical and spheroidal zinc powder prepared by the centrifugal method adjusts the particle size distribution and particle size of the zinc powder by adjusting the rotating speed, and adjusts the appearance, shape and apparent density of the zinc powder by adjusting the oxygen content of the powder collecting barrel. Thereby realizing the comprehensive performance of high capacity, high power and long storage life of the alkaline zinc-manganese dioxide battery.
The zinc powder can be used as a negative electrode material of an alkaline zinc-manganese battery, and the manufactured battery has good comprehensive electrical properties such as high specific capacity, high power, long storage life and the like. The process flow for preparing the zinc powder by the centrifugal method is short, the interference factors are few, and the energy consumption is low.
Drawings
The invention uses the centrifugal materialization equipment schematic diagram, wherein, 1-centrifugal atomization equipment; 2-zinc alloy liquid; 3, missing the package; 4-a turntable; 5-high speed motor, 6-zinc powder.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the invention are not limited thereto.
Example 1
The apparatus shown in fig. 1 was used. A preparation method of spherical and spheroidal zinc powder comprises the following steps:
(1) And preparing zinc alloy (the specific chemical components comprise In and Bi, and 1 or 2 of Al and Ca can be added if necessary).
(2) Adding the zinc alloy liquid obtained in the step (1) into an intermediate heat preservation furnace of centrifugal atomization equipment (the heat preservation temperature is 450-700 ℃), opening a flow control valve, flowing into a high-speed rotating turntable through a nozzle small hole (the aperture is 1-5 mm), then throwing the zinc alloy liquid out by the turntable, and screening and grading the zinc alloy liquid to obtain a zinc alloy liquid with the particle size distribution of 25-150 mu m and the apparent density of 3.0g/cm in a centrifugal atomization barrel with the volume ratio of oxygen to inert gas (nitrogen) being less than or equal to 1/10V/V 3 —5.0g/cm 3 Spherical or spheroidal zinc powder.
The turntable is made of graphite; the shape and structure of the rotary disk can be a smooth disk without radian, and the diameter of the rotary disk is 3-10 cm.
The rotating speed range of the high-speed finger is 12000-30000 r/min.
Example 2
The apparatus shown in fig. 1 was used. A preparation method of spherical and spheroidal zinc powder comprises the following steps:
(1) And preparing zinc alloy (the specific chemical components comprise In and Bi, and 1 or 2 of Al and Ca can be added if necessary) solution.
(2) Adding the zinc alloy liquid obtained in the step (1) into a middle heat preservation furnace of centrifugal atomization equipment (the heat preservation temperature is 450-700 ℃), opening a flow control valve, enabling the zinc alloy liquid to flow into a turntable rotating at a high speed through a nozzle small hole (the aperture is 1-5 mm), then throwing the zinc alloy liquid out by the turntable,and in a centrifugal atomization barrel with the volume ratio of oxygen to inert gas (argon) being less than or equal to 1/10V/V, the particles are classified by sieving to obtain particles with the particle size distribution of 25-150 mu m and the apparent density of 3.0g/cm 3 —5.0g/cm 3 Spherical or spheroidal zinc powder.
The turntable is made of ceramic; the shape and the structure of the turntable are cup-shaped with a certain radian (the radian is generally less than or equal to 25 degrees), and the diameter is 3-10 cm.
The rotating speed range of the high-speed finger is 12000-30000 r/min.
Example 3
The apparatus shown in fig. 1 was used. A preparation method of spherical and spheroidal zinc powder comprises the following steps:
(1) Preparing zinc alloy (the specific chemical components comprise In and Bi, and 1 or 2 of Al and Ca can be added when necessary) solution;
(2) Adding the zinc alloy liquid obtained in the step (1) into an intermediate heat preservation furnace of centrifugal atomization equipment (the heat preservation temperature is 450-700 ℃), opening a flow control valve, flowing into a high-speed rotating turntable through a nozzle small hole (the aperture is 1-5 mm), then throwing the zinc alloy liquid out by the turntable, and screening and grading the zinc alloy liquid to obtain a zinc alloy liquid with the particle size distribution of 25-150 mu m and the apparent density of 3.0g/cm in a centrifugal atomization barrel with the volume ratio of oxygen to inert gas being less than or equal to 1/10V/V (nitrogen gas) 3 —5.0g/cm 3 Spherical or spheroidal zinc powder.
The turntable is made of titanium alloy; the shape and the structure of the turntable are cup arc bowl-shaped with a certain radian (the radian is generally less than or equal to 25 degrees), and the diameter of the turntable is 3-10 cm.
The rotating speed range of the high-speed finger is 12000-30000 r/min.
The foregoing is a more detailed description of the present invention in connection with specific preferred embodiments thereof, and is not intended to limit the invention to the particular forms disclosed. For those skilled in the art to which the invention pertains, numerous simplifications or substitutions may be made without departing from the spirit of the invention, which shall be deemed to be within the scope of the invention.

Claims (10)

1. A preparation method of spherical and spheroidal zinc powder is characterized by comprising the following steps:
(1) Preparing zinc alloy liquid, wherein the diameter range of the zinc alloy is, the solvent comprises, and the concentration range is;
(2) And (2) adding the zinc alloy liquid obtained in the step (1) into centrifugal atomization equipment, flowing into a rotating disc rotating at a high speed through a nozzle small hole, throwing the zinc alloy liquid out by the rotating disc, and sieving and classifying spherical or spheroidal zinc powder in a centrifugal atomization barrel containing oxygen and inert gas in a certain proportion.
2. The method of claim 1, wherein the alloyed zinc alloy solution is formed by adding 100-500 ppm of In and Bi elements at 450-600 ℃ after melting the ingot, or by adding 1 or 2 elements of Al and Ca at 0-300 ppm.
3. The method for preparing spherical and spheroidal zinc powder according to claim 1, wherein the zinc alloy solution obtained in step (1) is added into an intermediate holding furnace of a centrifugal atomization device, the holding temperature is generally controlled to be 450-700 ℃, and a flow control valve is opened to pass through a nozzle orifice, wherein the diameter of the nozzle orifice is 1-5 mm.
4. The method as claimed in claim 1, wherein the material of the turntable is one or more of graphite, ceramic, iron, titanium alloy, etc.
5. A process for the production of spherical and spheroidal zinc powders according to claim 1 or 2, wherein the shape and configuration of the rotating disk is a smooth disk without curvature, a cup with curvature or a bowl with a diameter of 3-10 cm.
6. The method for preparing spherical and spheroidal zinc powder according to claim 5, wherein the high-speed finger has a rotation speed ranging from 12000 to 30000 rpm.
7. The process for preparing spherical and spheroidal zinc powders according to claim 1, wherein the inert gas is selected from the group consisting of nitrogen and argon.
8. The process for producing spherical, spheroidal zinc powder according to claim 1, wherein the volume ratio V/V of the oxygen gas to the inert gas is not more than 1/10.
9. The process for producing a spherical or spheroidal zinc powder according to claim 1, wherein the spherical or spheroidal zinc powder obtained by classifying by sieving has a particle size distribution of 25 to 150 μm and a bulk density of 3.0g/cm 3 ~5.0g/cm 3
10. A negative electrode material mainly used for alkaline zinc-manganese dioxide batteries, which is characterized by comprising spherical and spheroidal zinc powder prepared by the preparation method of any one of claims 1 to 9.
CN201511024606.XA 2015-12-29 2015-12-29 Preparation method of spherical and spheroidal zinc powder Pending CN105478789A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106925788A (en) * 2017-04-28 2017-07-07 攀钢集团研究院有限公司 Prepare the device of spherical Titanium Powder
CN113579240A (en) * 2021-07-30 2021-11-02 深圳市中金岭南科技有限公司 Centrifugal atomization preparation device for metal alloy and preparation method for zinc alloy

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1657203A (en) * 2004-12-31 2005-08-24 云南锡业集团有限责任公司 Nonferrous metal powder
WO2006045470A1 (en) * 2004-10-20 2006-05-04 Umicore Alloyed zinc powders for alkaline batteries with high pyknometer density
CN101143386A (en) * 2007-10-30 2008-03-19 林路峰 One-way throwing type centrifugal atomizing method and powder making machine
US7374840B1 (en) * 1999-02-09 2008-05-20 Umicore Centrifugally atomized zinc alloy powder for alkaline batteries
CN101898249A (en) * 2009-06-01 2010-12-01 北京有色金属研究总院 Method for preparing flaky metal powder
CN102248173A (en) * 2010-05-19 2011-11-23 浙江亚通焊材有限公司 Method and equipment for preparing spherical low-oxygen aluminum-based solder powder
CN103100718A (en) * 2012-12-28 2013-05-15 深圳市中金岭南科技有限公司 Preparation method for flake zinc powder containing indium and bismuth and aluminum and calcium

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7374840B1 (en) * 1999-02-09 2008-05-20 Umicore Centrifugally atomized zinc alloy powder for alkaline batteries
WO2006045470A1 (en) * 2004-10-20 2006-05-04 Umicore Alloyed zinc powders for alkaline batteries with high pyknometer density
CN1657203A (en) * 2004-12-31 2005-08-24 云南锡业集团有限责任公司 Nonferrous metal powder
CN101143386A (en) * 2007-10-30 2008-03-19 林路峰 One-way throwing type centrifugal atomizing method and powder making machine
CN101898249A (en) * 2009-06-01 2010-12-01 北京有色金属研究总院 Method for preparing flaky metal powder
CN102248173A (en) * 2010-05-19 2011-11-23 浙江亚通焊材有限公司 Method and equipment for preparing spherical low-oxygen aluminum-based solder powder
CN103100718A (en) * 2012-12-28 2013-05-15 深圳市中金岭南科技有限公司 Preparation method for flake zinc powder containing indium and bismuth and aluminum and calcium

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106925788A (en) * 2017-04-28 2017-07-07 攀钢集团研究院有限公司 Prepare the device of spherical Titanium Powder
CN113579240A (en) * 2021-07-30 2021-11-02 深圳市中金岭南科技有限公司 Centrifugal atomization preparation device for metal alloy and preparation method for zinc alloy

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