CN101451254A - One-step electrochemistry reduction method for preparing nano scale metal simple substance cobalt - Google Patents
One-step electrochemistry reduction method for preparing nano scale metal simple substance cobalt Download PDFInfo
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- CN101451254A CN101451254A CNA2008102447796A CN200810244779A CN101451254A CN 101451254 A CN101451254 A CN 101451254A CN A2008102447796 A CNA2008102447796 A CN A2008102447796A CN 200810244779 A CN200810244779 A CN 200810244779A CN 101451254 A CN101451254 A CN 101451254A
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Abstract
The invention provides a one-step electrochemistrical reduction method for preparing nanometer-class metal simple substance cobalt. The method is characterized in that metal lithium used as cathode material, micron-class cobalt oxide used as anode material, electrolytic solution and a separating membrane are assembled into an electrochemistrical reactor with lithium cell structure; and in the process of electrochemistrical discharge of the lithium cell, the metal lithium reduces the cobalt oxide to obtain the nanometer-class particle of the metal cobalt, and the nanometer-class particle is separated to obtain the nanometer-class cobalt particle. The method for preparing the nanometer-class metal cobalt has the advantages of simple process, convenient execution and easy operation, and can obtain the nanometer-class particle of the cobalt with good dispersivity, narrow particle size distribution and uniform appearance in high efficiency.
Description
Technical field
The present invention relates to the preparation method of metal nano material, a kind of electrochemical reduction method that in the electro-reduction process of lithium cell, prepares nano scale metal simple substance cobalt of more specifically saying so.
Background technology
Transition metal nanoparticles is owing to have surface effects, volume effect, quantum size effect and macroscopic quantum tunneling effect, and have peculiar electrically, magnetic, optical property and textural property, therefore obtained using widely in fields such as catalysis, luminescent material, magneticsubstance, semiconductor material and nano-devices.As a kind of magnetic element, nanometre metal cobalt powder can be used as high-performance magnetism recording materials, magnetic fluid, absorbing material, activated sintering additive, is widely used in industry such as Wimet, battery, catalytic material, permanent magnet, pottery.
Document in recent years and patent retrieval are as can be known, the method for preparing nano scale metal simple substance cobalt mainly contains aqueous solution reduction method, sol-gel method is emulsion method, vapour deposition process (CVD), evaporation-coacervation (contain plasma evaporation, excite evaporation and electron beam evaporation cohesion), though first three methods can be produced the nano scale metal simple substance cobalt of the equal Li Jing ≦ 100nm of Ping, production cost height and production efficiency is very low; The cobalt powder median size that vapour deposition process is produced is generally at 0.1～1.5 μ m, and the big production efficiency of facility investment is low, and evaporation-coacervation can be produced the simple substance cobalt of 0.1～3 μ m, and its production cost is low, and production efficiency is also very low.Wu Chengyi etc. propose to adopt air-flow ullrasonic spraying transformation approach to prepare the method that nanometer super-fine cobalt powder method and precipitation-reduction prepare nano-cobalt powder in the patent of the patent of publication number CN1586772A and publication number CN1686650A respectively, but technology is still comparatively complicated, the cost costliness.
Summary of the invention
The present invention is for avoiding above-mentioned existing in prior technology weak point, provide the one-step electrochemistry reduction method that a kind of method is simple, implement the preparation nano scale metal simple substance cobalt of convenience, easy handling, in the hope of obtaining good dispersity, narrow particle size distribution, the uniform cobalt nanometer particle of pattern efficiently.
Technical solution problem of the present invention adopts following technical scheme:
The characteristics that the present invention prepares an one-step electrochemistry reduction method of nano scale metal simple substance cobalt are that negative plate, positive plate, electrolytic solution and barrier film are assembled into the electrochemical reactor with lithium battery structure; Negative material is that the positive electrode material in metallic lithium, the described positive plate is the micron order cobalt/cobalt oxide in the described negative plate; In the electrochemical discharge process of described electrochemical reactor, by metallic lithium the reduction of cobalt/cobalt oxide is obtained the nanometer particle of cobalt metal, obtain the nanometre grade cobalt particle through separating.
The characteristics that the present invention prepares an one-step electrochemistry reduction method of nano scale metal simple substance cobalt also are:
Described is in the positive plate of positive electrode material with the micron order cobalt/cobalt oxide, is to be positive electrode current collector with the Copper Foil.
Described micron order cobalt/cobalt oxide is micron order Co
3O
4Or the powder body material of CoO.
The thickness of described positive plate is 200 μ m.
Electrolytic solution in the described electrochemical reactor is the lithium hexafluoro phosphate LiPF6 solution of 1mol/L, and solvent is that volume ratio is the diethyl carbonate DEC of 1:1 and the mixing solutions of NSC 11801 EC.
Described barrier film is polyethene microporous membrane Celgard 2400;
The discharge current density of described electrochemical discharge process is 0.03-0.5mA/cm
2, discharge temp is 0-70 ℃.
Sepn process for the nanometre grade cobalt particle is: peel off and remove through the Copper Foil in the positive plate of electrochemical reaction, obtain the electrochemical reaction product of micron order cobalt/cobalt oxide, electrochemical reaction product for described micron order cobalt/cobalt oxide is at first removed residual electrolytic solution with methylcarbonate DMC solution soaking, the dilute hydrochloric acid solution and the dehydrated alcohol that use N-methyl 2-Pyrrolidone NMP, concentration to be lower than 0.01mol/L more successively carry out eccentric cleaning, obtain the black solid product and are the nanometre grade cobalt particle.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the present invention as microreactor, prepares the cobalt nanometer particle with specific morphology with lithium cell conveniently, easy to operate, and cost is low;
2, the present invention can utilize electronic conduction speed difference under the different current densities, thereby causes electrochemical reducting reaction gained metal simple-substance change in particle size, reaches control synthetic purpose;
3, the cobalt nanometer particle of the present invention's preparation is a kind of special dispersion system, the reunion that can solve the magneticmetal particle.
Description of drawings
Fig. 1 is Co in the embodiment of the invention 1
3O
4The SEM figure of commodity powder.
Fig. 2 is Co in the embodiment of the invention 1
3O
4The TEM figure of commodity powder reduction after product.
Fig. 3 is Co in the embodiment of the invention 1
3O
4EDS (X-ray energy spectrum) figure of commodity powder reduzate.
Fig. 4 is commodity powder Co in the embodiment of the invention 1
3O
4The discharge curve of discharge first of/Li battery.
Fig. 5 is Co in the embodiment of the invention 2
3O
4The TEM figure of commodity powder reduction after product.
Fig. 6 is Co in the embodiment of the invention 3
3O
4The TEM figure of commodity powder reduction after product.
Below pass through embodiment, and the invention will be further described in conjunction with the accompanying drawings.
Embodiment
Embodiment 1;
Present embodiment prepares as follows:
The preparation of step 1, positive plate: get 1g micron order commodity powder cobalt oxide Co
3O
4, after fully grinding, with mass ratio Co
3O
4: PVDF=90:10 grinds to form slurry after mixing, and with scraper slurry is pulled into the film that thickness is 200 μ m on Copper Foil, oven dry system positive plate in 80 ℃ of vacuum drying ovens;
The preparation of step 2, negative plate and the assembling of battery: after the preparation diameter is the lithium anode sheet of 14mm, in vacuum drying oven, place for some time, then the button CR2032 battery of assembling two electrodes in glove box
Li/1M?LiPF6(EC:DEC＝1:1)/Co
3O
4
Select for use polyethene microporous membrane Celgard 2400 as barrier film;
Step 3, battery discharge: the battery with gained under the room temperature carries out the constant-current discharge experiment on multi-channel electrochemical tester NEWARE BTS-610, selecting current density for use is 0.032mA/cm
2Battery is discharged to 0V by open circuit voltage;
Step 4, extraction reduzate: after the battery after will discharging is sent into and taken apart in the glove box, positive plate is soaked in DMC, cleans to remove remaining electrolytic solution on the electrode surface, the electrode film that cleaned dries the back and takes out from glove box, clean except that the adhesive PVDF in the striping with NMP, use ethanol flush away electrode surface impurity and NMP again, clean to remove with dilute hydrochloric acid then not by complete reductive oxide compound and reduzate Li
2O cleans with dehydrated alcohol at last, centrifugal 2-3 time then, obtains the black solid product.
The result characterizes:
1, can determine commodity powder Co by accompanying drawing 1
3O
4Be micron particles;
2, can determine that by accompanying drawing 2 reduzate is a nanometer particle;
3, as can be seen by accompanying drawing 3, with contained element of the simple and easy quantitative analysis of film quantitative method and mass percent thereof be: carbon (5.93%), cobalt (65.74%), copper (28.34%) amount to (100%), wherein copper is substrate, can determine that the main component after reduzate is handled is simple substance Co;
4, can determine to have taken place electrochemical reducting reaction, i.e. Co by accompanying drawing 4
3O
4The commodity powder is reduced by the Li negative pole as positive pole, micron-sized Co in this process
3O
4Be reduced into nano level metallic cobalt particle.
Embodiment 2:
Step 1 is identical with embodiment 1 with step 2;
Step 3, battery discharge: the battery with gained under the room temperature carries out the constant-current discharge experiment on multi-channel electrochemical tester NEWARE BTS-610, selecting current density for use is 0.064mA/cm
2Battery is discharged to 0V by open circuit voltage;
Step 4, extraction reduzate: after the battery after will discharging is sent into and taken apart in the glove box, positive plate is soaked in DMC, cleans to remove remaining electrolytic solution on the electrode surface, the electrode film that cleaned dries the back and takes out from glove box, clean except that the adhesive PVDF in the striping with NMP, use ethanol flush away electrode surface impurity and NMP again, clean to remove with dilute hydrochloric acid then not by complete reductive oxide compound and reduzate Li
2O cleans with dehydrated alcohol at last, centrifugal 2-3 time then, obtains the black solid product.
Can determine that by accompanying drawing 5 reduzate is that granular size is the particle about 60 nanometers.As can be seen, all can obtain the cobalt metal ion of Nano grade with this method under different current densities, the current density difference has caused the difference of speed of response and electrons spread speed, so obtains the granular size difference of product.
Embodiment 3:
Step 1 is identical with embodiment 1 with step 2;
Step 3, battery discharge: the battery with gained in 50 ℃ of baking ovens carries out the constant-current discharge experiment on multi-channel electrochemical tester NEWAREBTS-610, selecting current density for use is 0.032mA/cm
2Battery is discharged to 0V by open circuit voltage;
Step 4, extraction reduzate: after the battery after will discharging is sent into and taken apart in the glove box, positive plate is soaked in DMC, cleans to remove remaining electrolytic solution on the electrode surface, the electrode film that cleaned dries the back and takes out from glove box, clean except that the adhesive PVDF in the striping with NMP, use ethanol flush away electrode surface impurity and NMP again, clean to remove with dilute hydrochloric acid then not by complete reductive oxide compound and reduzate Li
2O cleans with dehydrated alcohol at last, centrifugal 2-3 time then, obtains the black solid product.
Can determine that by accompanying drawing 6 reduzate is that granular size is the particle about 80 nanometers.As can be seen, all can obtain the cobalt metal ion of Nano grade with this method under different discharge temps, the discharge temp difference has caused the difference of speed of response and electrons spread speed, so obtains the granular size difference of product.
As seen, adopt this method, can realize the controlledly synthesis of cobalt metal nanoparticle.
Claims (8)
1, an one-step electrochemistry reduction method of preparation nano scale metal simple substance cobalt is characterized in that negative plate, positive plate, electrolytic solution and barrier film are assembled into the electrochemical reactor with lithium battery structure; Negative material is that the positive electrode material in metallic lithium, the described positive plate is the micron order cobalt/cobalt oxide in the described negative plate; In the electrochemical discharge process of described electrochemical reactor, by metallic lithium the reduction of cobalt/cobalt oxide is obtained the nanometer particle of cobalt metal, obtain the nanometre grade cobalt particle through separating.
2, an one-step electrochemistry reduction method of preparation nano scale metal simple substance cobalt according to claim 1, it is characterized in that described be in the positive plate of positive electrode material with the micron order cobalt/cobalt oxide, be to be positive electrode current collector with the Copper Foil.
3, an one-step electrochemistry reduction method of preparation nano scale metal simple substance cobalt according to claim 1 is characterized in that described micron order cobalt/cobalt oxide is micron order Co
3O
4Or the powder body material of CoO.
4, an one-step electrochemistry reduction method of preparation nano scale metal simple substance cobalt according to claim 1, the thickness that it is characterized in that described positive plate are 200 μ m.
5, according to an one-step electrochemistry reduction method of the described preparation nano scale metal simple substance cobalt of claim 1, it is characterized in that the electrolytic solution in the described electrochemical reactor is the lithium hexafluoro phosphate LiPF6 solution of 1mol/L, solvent is that volume ratio is the diethyl carbonate DEC of 1:1 and the mixing solutions of NSC 11801 EC.
6,, it is characterized in that described barrier film is polyethene microporous membrane Celgard 2400 according to an one-step electrochemistry reduction method of the described preparation nano scale metal simple substance cobalt of claim 1.
7, according to an one-step electrochemistry reduction method of the described preparation nano scale metal simple substance cobalt of claim 1, the discharge current density that it is characterized in that described electrochemical discharge process is 0.03-0.5mA/cm
2, discharge temp is 0-70 ℃.
8, one-step electrochemistry reduction method according to the described preparation nano scale metal simple substance cobalt of claim 1, it is characterized in that for the sepn process of nanometre grade cobalt particle being: peel off and remove through the Copper Foil in the positive plate of electrochemical reaction, obtain the electrochemical reaction product of micron order cobalt/cobalt oxide, electrochemical reaction product for described micron order cobalt/cobalt oxide is at first removed residual electrolytic solution with methylcarbonate DMC solution soaking, use N-methyl 2-Pyrrolidone NMP more successively, dilute hydrochloric acid solution and dehydrated alcohol that concentration is lower than 0.01mol/L carry out eccentric cleaning, obtain the black solid product and are the nanometre grade cobalt particle.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9938628B2 (en) | 2015-05-19 | 2018-04-10 | General Electric Company | Composite nanoparticles containing rare earth metal and methods of preparation thereof |
| CN114682786A (en) * | 2022-04-06 | 2022-07-01 | 合肥学院 | Preparation method of micro-nano metal powder |
| CN114797843A (en) * | 2022-03-29 | 2022-07-29 | 杭州未名信科科技有限公司 | Carbon-supported metal nanocluster catalyst and preparation method and application thereof |
-
2008
- 2008-12-04 CN CNA2008102447796A patent/CN101451254A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9938628B2 (en) | 2015-05-19 | 2018-04-10 | General Electric Company | Composite nanoparticles containing rare earth metal and methods of preparation thereof |
| CN114797843A (en) * | 2022-03-29 | 2022-07-29 | 杭州未名信科科技有限公司 | Carbon-supported metal nanocluster catalyst and preparation method and application thereof |
| CN114682786A (en) * | 2022-04-06 | 2022-07-01 | 合肥学院 | Preparation method of micro-nano metal powder |
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Open date: 20090610 |