CN103274474A - Rod-shaped zinc ferrite and its preparation method - Google Patents
Rod-shaped zinc ferrite and its preparation method Download PDFInfo
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- CN103274474A CN103274474A CN2013102232390A CN201310223239A CN103274474A CN 103274474 A CN103274474 A CN 103274474A CN 2013102232390 A CN2013102232390 A CN 2013102232390A CN 201310223239 A CN201310223239 A CN 201310223239A CN 103274474 A CN103274474 A CN 103274474A
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Abstract
The invention discloses rod-shaped zinc ferrite and its preparation method. The diameter of the rod-shaped zinc ferrite is 7.0-500 nanometers; length-diameter ratio is 3.0-20; the rod-shaped radial direction is composed of 1-20 nano-particles; and the size of a single nano-particle is 7.0-30 nanometers. The preparation method of the rod-shaped zinc ferrite comprises the following steps: selecting ferrous sulphate and zinc chloride as raw materials, using oxalic acid as a precipitating agent, carrying out precipitation at room temperature, carrying out a hybrid reaction, aging, centrifuging, washing, drying and carrying out heat treatment to obtain the rod-shaped zinc ferrite constructed by the nano-particles. By the adoption of the method, the rod-shaped zinc ferrite constructed by the nano-particles can be prepared, and morphological control of length-diameter ratio being 3.0-20 and structural regulation and control of radial-direction nano-particle distribution number being 1-20 can be realized. The rod-shaped zinc ferrite constructed by the nano-particles is applicable to be used as a lithium ion battery cathode material as well as a photocatalysis material.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic functional material, particularly relate to a kind of employing oxalic acid precipitation and prepare nano particle and construct shaft-like zinc ferrite, belong to inorganic advanced nano material preparation Technology field.
Background technology
Plurality of advantages such as lithium ion battery has the voltage height, and specific storage is big, and density is high and have extended cycle life have become one of focus of new type power battery research and development.Yet, want to satisfy lithium ion battery and bring into play bigger potentiality at electromobile and field of hybrid electric vehicles, just must have higher specific storage and high rate performance.At present, metal oxide and alloy have higher specific storage becomes electrode materials of new generation, and the one dimension rod-like structure has the good lithium ion passage that shuttles back and forth, and therefore has good electrochemical.
The zinc ferrite theoretical specific capacity surpasses 1000 MAH/grams, and has that starting material are extensive, manufacturing cost hangs down becomes desirable lithium ion battery negative material.But zinc ferrite is in the charge and discharge cycles process, and the expansion of volume and contraction cause the electrode materials internal stress to concentrate, and cause the electrode efflorescence, reduce its cycle life.In order to improve the chemical property of zinc ferrite, the investigator has carried out big quantity research, mainly concentrates on the structure and pattern, doping and the preparation matrix material etc. that change material.Nano particle has better electrochemical performance, but under high current density, still can descend fast, to trace it to its cause be that high surface energy causes the oneself in its charge and discharge process to reunite and electrolyte decomposition, reduced active substance with effective contact area of electrolytic solution and brought very big potential safety hazard.Than nano particle, the ultrafine grain metal oxide compound that assembling is built into not only can avoid reuniting and guaranteeing security by reducing surface energy, also by fully keeping nanometer size effect, improves its chemical property advantage.Therefore constructing the one dimension rod-like structure by nano particle becomes an a kind of good approach that improves the electrode materials chemical property.
Summary of the invention
The purpose of this invention is to provide a kind of shaft-like zinc ferrite and preparation method thereof, this preparation method's technology is simple, cost is low, controllable product shape, and the zinc ferrite of preparation has excellent electrochemical properties etc.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of shaft-like zinc ferrite, described shape zinc ferrite diameter is the 7.0-500 nanometer, and length-to-diameter ratio is 3.0 to 20, shaft-likely radially is made of 1 to 20 nano particle, and single nanoparticle is of a size of the 7.0-30 nanometer.
The preparation method of above-mentioned a kind of shaft-like zinc ferrite, selecting ferrous sulfate and zinc chloride for use is raw material, is precipitation agent with oxalic acid, carry out precipitation at room temperature, after the hybrid reaction, obtain the shaft-like zinc ferrite constructed by nano particle through ageing, centrifugal, washing, drying and thermal treatment, concrete preparation process is as follows:
(1) carries out secluding air in the deionized water of deoxidation treatment, adding the part hexanaphthene, add ferrous sulfate and zinc chloride then, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.01-5.0 mole/every liter, slowly stir after 30 minutes, add small amount of hydrochloric acid, obtain transparent ferrous sulfate and solder(ing)acid;
(2) configuration oxalic acid spirituous solution, concentration of oxalic acid is the 1.0-2.0 mol, the control stirring velocity is 100-2000 rev/min;
(3) under the condition of ferrous sulfate and solder(ing)acid secluding air, at the uniform velocity join the oxalic acid spirituous solution of whipped state with the speed of 0.5-4.0 ml/min;
(4) after reaction is finished, through ageing in 0-36 hour, centrifugal, washing for several times the back 50-100 ℃ dry 3-8 hour down, at last at 200-800 ℃ of following thermal treatment 0.5-4 hour, obtain the shaft-like zinc ferrite of being constructed by the particle that is of a size of the 7.0-30 nanometer.
Concentration is the ferrous sulfate of 0.01-5.0 mol described in the step (1), and solution condition is secluding air and deoxidation.
Ferrous sulfate and zinc chloride described in the step (1) replaced with ferrous sulfate or zinc chloride, and product becomes ferric oxide or zinc oxide, but appearance structure do not change, and namely still is built into rod-like structure for nano particle.
Alcohol water described in the step (2), ethylene glycol or add tensio-active agent in the solution and substitute; Described alcohol substitutes with alcohol and ethylene glycol solution; Described alcohol adds tensio-active agent with alcohol, ethylene glycol solution with in the solution and substitutes; Above-mentioned product still is built into rod-like structure for nano particle.
Add speed described in the step (3) and can regulate and control the product length-to-diameter ratio, when speed was the 0.1-2.0 ml/min, the product length-to-diameter ratio was 10-20, and when speed was the 5.0-10 ml/min, the product length-to-diameter ratio was 3.0-5.0.
Time of repose described in the step (4) is regulation and control product length-to-diameter ratio, and time of repose is 0-2 hour, and the product length-to-diameter ratio is 10-20, and time of repose is 24-36 hour, and the product length-to-diameter ratio is 3.0-5.0.
Thermal treatment temp described in the step (4) is 200-800 ℃, and heat treatment time is 0.5-4 hour.
The present invention has the following advantages:
1) reaction mechanism of the present invention is that oxalate presoma product decomposes formation nano particle is constructed rod-like structure, and the presoma pattern is genetic to the product zinc ferrite through form templating nucleation process.
2) zinc ferrite rod-like structure of the present invention is reunited by nanometer zinc ferrite and is formed the characteristics that exist orientation to overlap between the nano particle; The nanoparticle agglomerates rod-like structure has the big characteristic of nano particle specific surface area; And form mesoporously between the nano particle, be conducive to coordinate the volumetric expansion in the lithium ion battery charge and discharge process.
3) the present invention can effectively control the size of nanoparticle agglomerates by regulation and control adding speed and digestion time, length-to-diameter ratio and the distribution number of nano particle radially of control rod-like structure, can realize that nano particle distribution number radially is the structure regulating between 1 to 20, length-to-diameter ratio is by 3.0 to 20 pattern regulation and control.
4) precipitation process of the present invention is room temperature reaction, and subsequent heat treatment technology is simple, environmental protection, and finally reduced manufacturing cost and process complexity.
Description of drawings
Fig. 1 is the zinc ferrite X-ray diffraction analysis of the present invention's preparation.
Fig. 2 can find out clearly that for the zinc ferrite field emission morphology observation of the present invention's preparation zinc ferrite is rough, and shaft-like diameter is; A) 10-100 nanometer, b) 50-500 nanometer, c) 100-400 nanometer.
Fig. 3 is the zinc ferrite transmission morphology observation of the present invention's preparation, can find out clearly that zinc ferrite is that nano particle is constructed the meso-hole structure between formation and the particle, length-to-diameter ratio 18-20, and radially particle is 4-5.
Fig. 4 is the zinc ferrite of the present invention preparation charging and discharging curve figure as lithium ion battery negative material, and capacity surpasses 1200 MAH/grams first.
Fig. 5 is the zinc ferrite of the present invention preparation charge-discharge performance as lithium ion battery negative material, and capacity is kept at 1000 MAHs/more than the gram after 50 times.
Embodiment
Embodiment one
(1) in the deionized water of deoxidation treatment, adding part hexanaphthene secluding air, add ferrous sulfate and zinc chloride then, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is the 0.1-0.25 mol, slowly stir after 30 minutes, add small amount of hydrochloric acid, obtain transparent ferrous sulfate and solder(ing)acid;
(2) configuration oxalic acid spirituous solution, concentration of oxalic acid is 1.3-1.7 mole/milliliter, control is stirred to 500-600 rev/min;
(3) under the condition of ferrous sulfate and solder(ing)acid secluding air, at the uniform velocity join the oxalic acid spirituous solution of whipped state with the speed of 1.0-2.0 ml/min;
(4) after reaction is finished, through ageing in 0 hour, centrifugal, washing for several times the back 60 ℃ dry 8 hours down, at last at 400-800 ℃ of following thermal treatment 2-3 hour, the diameter that obtains shaft-like zinc ferrite is the 7.0-20 nanometer, length-to-diameter ratio is 18 to 20, shaft-likely radially is made of 1 to 3 nano particle, and single nanoparticle is of a size of the 7.0-15 nanometer.
Embodiment two
(1) in the deionized water of handling through deoxygenation, adds part hexanaphthene secluding air, add ferrous sulfate and zinc chloride then, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.2-1.0 mole/every liter, slowly stir after 30 minutes, add small amount of hydrochloric acid, obtain homogeneous transparent ferrous sulfate and solder(ing)acid;
(2) configuration oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, control is stirred to 1000-2000 rev/min;
(3) under the condition of ferrous sulfate and solder(ing)acid secluding air, at the uniform velocity join oxalic acid spirituous solution in the whipped state with the speed of 2.0-3.0 ml/min;
(4) after reaction is finished, left standstill through 6 hours, centrifugation, alcohol and water washing are back following dry 8 hours at 60 ℃ for several times, at last at 500-700 degree centigrade of following thermal treatment 3-4 hour, the diameter that obtains shaft-like zinc ferrite is the 10-100 nanometer, length-to-diameter ratio is 10 to 15, shaft-likely radially is made of 3 to 5 nano particles, and single nanoparticle is of a size of the 10-20 nanometer.
Embodiment three
(1) in the deionized water of handling through deoxygenation, adds part hexanaphthene secluding air, add ferrous sulfate and zinc chloride then, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.1-1.0 mole/every liter, slowly stir after 30 minutes, add small amount of hydrochloric acid, obtain homogeneous transparent ferrous sulfate and solder(ing)acid;
(2) configuration oxalic acid alcohol and ethylene glycol mixing solutions, concentration of oxalic acid is 1.0-1.7 mole/milliliter, control is stirred to 100-200 rev/min;
(3) under the condition of ferrous sulfate and solder(ing)acid secluding air, at the uniform velocity join oxalic acid spirituous solution in the whipped state with the speed of 0.5-1.0 ml/min;
(4) after reaction is finished, left standstill through 6 hours, centrifugation, alcohol and water washing are back following dry 7 hours at 60 ℃ for several times, at last at 400-600 ℃ of following thermal treatment 3-4 hour, the diameter that obtains shaft-like zinc ferrite is the 50-200 nanometer, length-to-diameter ratio is 15 to 18, shaft-likely radially is made of 5 to 8 nano particles, and single nanoparticle is of a size of the 7.0-15 nanometer.
Embodiment four
(1) to add part hexanaphthene secluding air in the deionized water that deoxygenation is handled, add ferrous sulfate then, concentration is 0.1-1.0 mole/every liter, slowly stir 30 minutes after, add small amount of hydrochloric acid, obtain the homogeneous transparent ferrous sulfate aqueous solution;
(2) configuration oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, control is stirred to 1000-2000 rev/min;
(3) under the condition of ferrous sulfate aqueous solution secluding air, at the uniform velocity join oxalic acid spirituous solution in the whipped state with the speed of 0.5-1.0 ml/min;
(4) after reaction is finished, left standstill through 12 hours, centrifugation, alcohol and water washing are back following dry 7 hours at 60 ℃ for several times, at last at 400-600 degree centigrade of following thermal treatment 3-4 hour, the diameter that obtains shaft-like ferric oxide is the 50-500 nanometer, length-to-diameter ratio is 8 to 13, shaft-likely radially is made of 8 to 15 nano particles, and single nanoparticle is of a size of the 7.0-15 nanometer.
Embodiment five
(1) to add part hexanaphthene secluding air in the deionized water that deoxygenation is handled, add zinc chloride then, concentration is 0.1-1.0 mole/every liter, slowly stir 30 minutes after, add small amount of hydrochloric acid, obtain the homogeneous transparent solder(ing)acid;
(2) configuration oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, control is stirred to 300-400 rev/min;
(3) under the condition of solder(ing)acid secluding air, at the uniform velocity join oxalic acid spirituous solution in the whipped state with the speed of 0.5-1.0 ml/min;
(4) after reaction is finished, left standstill through 12 hours, centrifugation, alcohol and water washing are back following dry 7 hours at 60 ℃ for several times, at last at 400-600 ℃ of following thermal treatment 3-4 hour, the diameter that obtains shaft-like zinc oxide is the 200-900 nanometer, length-to-diameter ratio is 3.0 to 5.0, shaft-likely radially is made of 10 to 20 nano particles, and single nanoparticle is of a size of the 7.0-15 nanometer.
Claims (8)
1. shaft-like zinc ferrite is characterized in that:
Described shape zinc ferrite diameter is the 7.0-500 nanometer, and length-to-diameter ratio is 3.0 to 20, shaft-likely radially is made of 1 to 20 nano particle, and single nanoparticle is of a size of the 7.0-30 nanometer.
2. the preparation method of a kind of shaft-like zinc ferrite according to claim 1 is characterized in that:
Selecting ferrous sulfate and zinc chloride for use is raw material, is precipitation agent with oxalic acid, carries out precipitation at room temperature, after the hybrid reaction, obtains the shaft-like zinc ferrite constructed by nano particle through ageing, centrifugal, washing, drying and thermal treatment, and concrete preparation process is as follows:
(1) carries out secluding air in the deionized water of deoxidation treatment, adding the part hexanaphthene, add ferrous sulfate and zinc chloride then, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.01-5.0 mole/every liter, slowly stir after 30 minutes, add small amount of hydrochloric acid, obtain transparent ferrous sulfate and solder(ing)acid;
(2) configuration oxalic acid spirituous solution, concentration of oxalic acid is the 1.0-2.0 mol, the control stirring velocity is 100-2000 rev/min;
(3) under the condition of ferrous sulfate and solder(ing)acid secluding air, at the uniform velocity join the oxalic acid spirituous solution of whipped state with the speed of 0.5-4.0 ml/min;
(4) after reaction is finished, through ageing in 0-36 hour, centrifugal, washing for several times the back 50-100 ℃ dry 3-8 hour down, at last at 200-800 ℃ of following thermal treatment 0.5-4 hour, obtain the shaft-like zinc ferrite of being constructed by the particle that is of a size of the 7.0-30 nanometer.
3. the preparation method of a kind of shaft-like zinc ferrite according to claim 2 is characterized in that:
Concentration is the ferrous sulfate of 0.01-5.0 mol described in the step (1), and solution condition is secluding air and deoxidation.
4. the preparation method of a kind of shaft-like zinc ferrite according to claim 2 is characterized in that:
Ferrous sulfate and zinc chloride described in the step (1) replaced with ferrous sulfate or zinc chloride, and product becomes ferric oxide or zinc oxide, but appearance structure do not change, and namely still is built into rod-like structure for nano particle.
5. the preparation method of a kind of shaft-like zinc ferrite according to claim 2 is characterized in that:
Alcohol water described in the step (2), ethylene glycol or add tensio-active agent in the solution and substitute; Described alcohol substitutes with alcohol and ethylene glycol solution; Described alcohol adds tensio-active agent with alcohol, ethylene glycol solution with in the solution and substitutes; Above-mentioned product still is built into rod-like structure for nano particle.
6. the preparation method of a kind of shaft-like zinc ferrite according to claim 2 is characterized in that:
Add speed described in the step (3) and can regulate and control the product length-to-diameter ratio, when speed was the 0.1-2.0 ml/min, the product length-to-diameter ratio was 10-20, and when speed was the 5.0-10 ml/min, the product length-to-diameter ratio was 3.0-5.0.
7. the preparation method of a kind of shaft-like zinc ferrite according to claim 2 is characterized in that;
Time of repose described in the step (4) is regulation and control product length-to-diameter ratio, and time of repose is 0-2 hour, and the product length-to-diameter ratio is 10-20, and time of repose is 24-36 hour, and the product length-to-diameter ratio is 3.0-5.0.
8. the preparation method of a kind of shaft-like zinc ferrite according to claim 2 is characterized in that:
Thermal treatment temp described in the step (4) is 200-800 ℃, and heat treatment time is 0.5-4 hour.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085930A (en) * | 2014-06-30 | 2014-10-08 | 陕西师范大学 | Method for preparing porous flake zinc ferrite with large specific surface area |
| CN109399725A (en) * | 2017-08-15 | 2019-03-01 | 中国石油化工股份有限公司 | A kind of preparation method and applications of the nano-structure array of dregs containing zinc |
| CN109455766A (en) * | 2018-12-14 | 2019-03-12 | 中国科学院合肥物质科学研究院 | A kind of ultra-fine ferrous acid zinc nanoparticles and preparation method thereof and air-sensitive application |
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| CN102531067A (en) * | 2012-03-20 | 2012-07-04 | 新疆大学 | Solid state method for preparing zinc ferrite nanorods |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102531067A (en) * | 2012-03-20 | 2012-07-04 | 新疆大学 | Solid state method for preparing zinc ferrite nanorods |
Non-Patent Citations (2)
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| HONGLIANG ZHU ET AL.: "Microemulsion-based synthesis of porous zinc ferrite nanorods and its application in a room-temperature ethanol sensor", 《NANOTECHNOLOGY》 * |
| 庄稼等: "ZnFe2O4 前驱物固相合成反应的热化学", 《应用化学》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085930A (en) * | 2014-06-30 | 2014-10-08 | 陕西师范大学 | Method for preparing porous flake zinc ferrite with large specific surface area |
| CN104085930B (en) * | 2014-06-30 | 2015-11-18 | 陕西师范大学 | A kind of preparation method of bigger serface porous flake zinc ferrite |
| CN109399725A (en) * | 2017-08-15 | 2019-03-01 | 中国石油化工股份有限公司 | A kind of preparation method and applications of the nano-structure array of dregs containing zinc |
| CN109399725B (en) * | 2017-08-15 | 2021-04-13 | 中国石油化工股份有限公司 | Preparation method and application of zinc ferrite-containing nano-structure array |
| CN109455766A (en) * | 2018-12-14 | 2019-03-12 | 中国科学院合肥物质科学研究院 | A kind of ultra-fine ferrous acid zinc nanoparticles and preparation method thereof and air-sensitive application |
| CN109455766B (en) * | 2018-12-14 | 2021-02-05 | 中国科学院合肥物质科学研究院 | Superfine zinc ferrite nano-particles, preparation method and gas-sensitive application thereof |
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