CN104966834A - Preparation method of squid-tentacle-shaped tricobalt tetraoxide lithium battery negative electrode material - Google Patents
Preparation method of squid-tentacle-shaped tricobalt tetraoxide lithium battery negative electrode material Download PDFInfo
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- CN104966834A CN104966834A CN201510414321.0A CN201510414321A CN104966834A CN 104966834 A CN104966834 A CN 104966834A CN 201510414321 A CN201510414321 A CN 201510414321A CN 104966834 A CN104966834 A CN 104966834A
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- squid
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- tentacle
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a preparation method of a squid-tentacle-shaped tricobalt tetraoxide lithium battery negative electrode material, belonging to the technical field of new material production and scientific research. The preparation method comprises the following steps: preparing SiO2@PS in a deposition way by a template method; then, performing a hydrothermal method in the presence of cobaltous nitrate hexahydrate, urea and ammonium fluoride; and carrying out high-temperature calcination. The squid-tentacle-shaped tricobalt tetraoxide nano materials different in size can be prepared according to the control over calcination temperature. According to the preparation method, the operation is simple, energy-saving and environment-friendly effects are achieved, and the conditions can be controlled easily. The prepared squid-tentacle-shaped tricobalt tetraoxide has extremely large specific surface area and nano intervals, the contact surface of squid-tentacle-shaped tricobalt tetraoxide and electrolyte is greatly increased, Li<+1> de-intercalation in the charging and discharging process is facilitated, and the battery performance is improved.
Description
Technical field
The invention belongs to manufacture of materials technical field, particularly there is the preparation method of regular nano gap and orderly novel nano metal oxide.
Background technology
Business-like lithium battery adopts carbon-based material as negative pole substantially at present, but the cycle performance of carbon-based material and high rate performance are good not and power is low own through becoming its technical bottleneck further developed of restriction.
Cobaltosic oxide has higher theoretical capacity (up to 890 mAh/g, much larger than graphite), is a kind of Carbon anode substitution material of great potential.Meanwhile, cobaltosic oxide is also a kind of well functional material, also has very wide application prospect in fields such as gas sensing, temperature sensing, chemical catalysis.In addition, cobaltosic oxide still synthesizes the raw material of positive pole material of lithium cobalt acid.Therefore, R and D cobaltosic oxide has very important practical value.But because cobaltosic oxide exists the shortcomings such as conductivity is bad, high rate performance is poor, what make its specific capacity in large current density electric process decline is very fast.Although by studying in recent years, prepare nano level cobaltosic oxide, its high rate performance and conductivity made moderate progress.
As everyone knows, the specific area of material is larger, and nano gap is larger, and the contact area of itself and electrolyte is larger, is beneficial to Li
+deintercalation, comparatively large and nano gap the is larger material structure of preparation specific area becomes direction and the difficult point of researcher's research.
Summary of the invention
The object of the invention is to propose one simple to operate, repeatable strong, there is the preparation method of the lithium cell cathode material of squid palpus shape feature.
The present invention includes following steps:
1) taken out after the mixed solution of the concentrated sulfuric acid and hydrogen peroxide soaks by the slide of cleaning, drying, obtains the slide matrix of hydrophilicity-imparting treatment;
2) slide of hydrophilicity-imparting treatment is vertically put into the mixed solution by tetraethyl orthosilicate and polyacrylonitrile, after ageing, take out slide, drying, must deposit SiO
2the slide of@PS;
3) SiO will be deposited
2the mixed liquor be made up of cabaltous nitrate hexahydrate, ammonium fluoride and urea vertically put into by the slide of@PS, after warm water thermal response, takes out slide, through high-temperature calcination, isolates skin-material from slide, and obtaining squid must shape structure C o
3o
4.
The advantage of present invention process is: invent a kind of new technology hydro thermal method first, and coordinate and adopt vertical deposition method, preparation cost is cheap, and equipment requirement is simple, and manufacturing cycle is short, and the present invention is that the material preparing nano gap large provides new direction.
The Co of the squid palpus shape made
3o
4, there is larger nano gap, regular in order, there is great specific area simultaneously.The present invention is simple to operate, energy-conserving and environment-protective, and condition is easily controlled.The squid of preparation shape cobaltosic oxide must have great specific area and nano gap, and the contact area of itself and electrolyte increases greatly, is beneficial to Li in charge and discharge process
+deintercalation, improve battery performance.
Further, in step 1) of the present invention, the mixed volume ratio of sulfuric acid and hydrogen peroxide is 3:1.Under this volume ratio, slide can be made to obtain best hydrophilicity-imparting treatment.
Soak time described in step 1) of the present invention is 24 ± 1 hours.Under this soak time, surface of glass slide can be made to cover with the oxide-film of one deck densification, thus fully must obtain hydrophilicity-imparting treatment.
Described step 2) described in the mixed volume of tetraethyl orthosilicate and polyacrylonitrile than being 1:0.02, the mass fraction of described tetraethyl orthosilicate is 0.15 ~ 0.45 wt%, and the mass fraction of polyacrylonitrile is 0.1 ~ 0.4 wt%.
The present invention is to prepare certain density polyacrylonitrile and tetraethyl orthosilicate emulsion, in the temperature of free energy optimum state, be allowed to condition at self assembly on slide that hydrophilicity-imparting treatment crosses and form intensive nanogel coating, natural drying, then by a certain proportion of cabaltous nitrate hexahydrate, ammonium fluoride, urea mixing, stir, vertically put into the SiO deposited
2the slide of@PS, puts into baking oven, hydro-thermal reaction, dries, then takes out slide, then the slide made is carried out high-temperature calcination, and then at air calcination removing PS ball, obtained squid must shape nano material.The squid of making must the cobaltosic oxide of shape have must shape structure and larger specific area and nano gap like squid.
Described step 2) described in Aging Temperature be 30 ~ 40 DEG C, digestion time is 2 ~ 3 days.In this temperature and time scope, the coating uniform that vertical deposition obtains, self assembly reaches optimum state.
In addition, in order to make the squid palpus shape Co3O4 nanometer material of preparation, pattern is homogeneous, and the mixing mol ratio of cabaltous nitrate hexahydrate of the present invention, ammonium fluoride and urea is 5 ~ 9:6 ~ 10:8 ~ 10.In this proportion, solution is the most easily prepared, utilization the most extensive.
In described step 3), during hydro-thermal reaction, the temperature of baking oven is 80 ~ 150 DEG C, and the hydro-thermal reaction time is 2 ~ 8 h.Under this hydrothermal condition, keep the growth that cobaltosic oxide precursor crystal is orderly, thus the obtained good precursor product of pattern.
In described step 3), calcining heat is 400 ~ 600 DEG C, and the time is 1 ~ 8 h.At this temperature range and calcination time, product form structure can be made better, and pattern change can not be there is because of calcining in product.If calcining heat is more than 600 DEG C, then the special squid of end product must shape structure not easily maintain.
In addition, when calcining in described step 3) with the heating rate of 1 ~ 5 DEG C/min by temperature to 400 ~ 600 DEG C.This heating rate makes material heat up with given pace in calcination process, keeps the regular slow growth of crystal formation, thus in order obtained and have the cobaltosic oxide material of nano gap.
Accompanying drawing explanation
fig. 1 is in example 1,2 method, in step 2) after the SiO that obtains
2the scanning electron microscope (SEM) photograph of@PS coating.
Fig. 2 is in example 1 method, adopts the inventive method and step 3), the Co of preparation
3o
4the scanning electron microscope (SEM) photograph of squid palpus structure.
Fig. 3 is the XRD figure of end product of the present invention.
Fig. 4 is the EDS figure of end product of the present invention.
Fig. 5 is in example 2 method, adopts the inventive method in step 3), the Co of preparation
3o
4the scanning electron microscope (SEM) photograph of squid palpus structure.
Fig. 6 is the charge-discharge performance figure of end product of the present invention.
Embodiment
preparation technology:
example 1:
One, preparation method:
1, slide matrix hydrophilicity-imparting treatment:
Slide is cut into the size of long 30 mm, wide 30 mm, is placed in the beaker of 50 mL, adds the water of 25 mL, ultrasonic 20 min, successively then with the ethanol of 10 mL, acetone ultrasonic 20 min respectively of 10 mL.Taking out slide cleans complete, and dustless oven dry is stand-by.
With volume ratio be 3:1 ratio by the concentrated sulfuric acid and hydrogen peroxide mixing, preparation obtains the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, clean slide is soaked wherein after 25 hours take out, natural airing, obtains the slide of hydrophilicity-imparting treatment.
2, vertical deposition prepares SiO
2@PS:
The preparation polyacrylonitrile aqueous solution of 0.1 ~ 0.4 wt% and the tetraethyl orthosilicate aqueous solution of 0.15 ~ 0.45 wt%.
The tetraethyl orthosilicate aqueous solution of the polyacrylonitrile aqueous solution and 0.2 mL of getting 10 mL, in container, after ultrasonic 30 min, makes solution fully mix, for obtaining the good SiO of pattern
2@PS nano coating, adopts vertical deposition method, vertically puts into the slide of hydrophilicity-imparting treatment, keeps horizontal plane and slide to be 90 ° as far as possible, reposefully container is put into the baking oven of 30 DEG C, and ageing, after 2 ~ 3 days, is taken out slide, then through natural drying, must be deposited SiO
2the slide of@PS.
From the deposition SiO obtained
2the surface of glass slide of@PS takes off coating material, scans, and obtains Electronic Speculum figure, and as shown in Figure 1, multiplication factor: × 70000, visible obtained nano coating pattern is very homogeneous.
3, squid palpus shape cobaltosic oxide is prepared:
Be the ratio mixing of 5 ~ 9:6 ~ 10:8 ~ 10 by the mol ratio of cabaltous nitrate hexahydrate, ammonium fluoride and urea, after mechanical agitation 20 min, form the mixed liquor mixed.
The SiO of deposition is vertically put in mixed liquor
2the slide of@PS, and then be placed in baking oven and carry out hydro-thermal reaction (temperature of baking oven is 80 ~ 150 DEG C, and the reaction time is 2 ~ 8 h), takes out slide, dries at a certain temperature, then slide is carried out high-temperature calcination.Wherein calcining heat is 500 DEG C, and the time is 1 ~ 8 h, and heating rate is 1 ~ 5 DEG C/min, and obtained squid must shape Co3O4 nanometer material.
Fig. 2 is the scanning electron microscope (SEM) photograph of obtained squid palpus shape Co3O4 nanometer material, and multiplication factor: × 60000, the cobaltosic oxide material of squid palpus shape obtained as can be seen from Figure, pattern is very homogeneous.
Fig. 3 is the X-ray diffraction figure of squid palpus shape Co3O4 nanometer material prepared by the present invention, abscissa is the angle of diffraction of 2 times, ordinate is relative intensity, the diffraction maximum of the product marked in Fig. 3 and the standard spectrogram one_to_one corresponding of cobaltosic oxide, show that the composition of the nano material prepared is cobaltosic oxide.
Fig. 4 is the EDS figure of squid palpus shape Co3O4 nanometer material prepared by the present invention, has the elementary analysis contained by product morphology and material, show that the composition of the nano material prepared is cobaltosic oxide in Fig. 4.
example 2:
1, slide matrix hydrophilicity-imparting treatment:
Slide is cut into the size of 30 × 30 mm, is placed in the beaker of 50 mL, add the water of 25 mL, ultrasonic 20 min, successively then with the ethanol of 10 mL, acetone ultrasonic 20 min respectively of 10 mL.Clean and finish, dustless oven dry is stand-by.With volume ratio be 3:1 ratio by the concentrated sulfuric acid and hydrogen peroxide mixing, preparation obtains the mixed solution of the concentrated sulfuric acid and hydrogen peroxide, clean slide is soaked wherein after 23 hours take out, natural airing.
2, vertical deposition prepares SiO
2@PS:
The preparation polyacrylonitrile aqueous solution of 0.1 ~ 0.4 wt% and the tetraethyl orthosilicate aqueous solution of 0.15 ~ 0.45 wt%.
The tetraethyl orthosilicate aqueous solution of the polyacrylonitrile aqueous solution and 0.2 mL of getting 10 mL, in container, after ultrasonic 30 min, makes solution fully mix, for obtaining the good SiO of pattern
2@PS nano coating, adopts vertical deposition method, vertically puts into the slide of hydrophilicity-imparting treatment, keeps horizontal plane and slide to be 90 ° as far as possible, reposefully container is put into the baking oven of 40 DEG C, and ageing, after 2 ~ 3 days, is taken out slide, then through natural drying, must be deposited SiO
2the slide of@PS.
From the deposition SiO obtained
2the surface of glass slide of@PS takes off coating material, scans, and obtains Electronic Speculum figure, and also as shown in Figure 1, visible obtained nano coating pattern is very homogeneous.
3, squid palpus shape cobaltosic oxide is prepared:
Be the ratio mixing of 5 ~ 9:6 ~ 10:8 ~ 10 by the mol ratio of cabaltous nitrate hexahydrate, ammonium fluoride and urea, after mechanical agitation 20 min, form the mixed liquor mixed.
Deposition SiO is vertically put in mixed liquor
2the slide of@PS, and then be placed in baking oven and carry out hydro-thermal reaction (temperature of baking oven is 80 ~ 150 DEG C, and the reaction time is 2 ~ 8h), take out slide, dry at a certain temperature, then slide is carried out high-temperature calcination.Wherein calcining heat is 600 DEG C, and the time is 1 ~ 8h, and heating rate is 1 ~ 5 DEG C/min, and obtained squid must shape Co3O4 nanometer material.
Fig. 5 is the scanning electron microscope (SEM) photograph of obtained squid palpus shape Co3O4 nanometer material, and multiplication factor: × 60000, the cobaltosic oxide material of squid palpus shape obtained as can be seen from Figure, pattern is very homogeneous.
From above two examples and figure: the present invention prepares the Co3O4 nanometer material of squid palpus shape, its special squid palpus shape structure is relevant with calcining heat.Calcining heat is larger, and the special squid of end product must shape structure more not easily maintain.
the effect checking of product of the present invention:
By the charge-discharge performance of end product of the present invention as shown in Figure 6, as seen from Figure 6: squid must remain at 630 mAhg in 100 circles by shape cobaltosic oxide under 0.5C
-1left and right, stable performance, efficiency for charge-discharge maintains 100% all the time, has excellent battery performance.
Claims (9)
1. the preparation method of squid palpus shape cobaltosic oxide lithium cell cathode material, is characterized in that comprising the steps:
1) taken out after the mixed solution of the concentrated sulfuric acid and hydrogen peroxide soaks by the slide of cleaning, drying, obtains the slide matrix of hydrophilicity-imparting treatment;
2) slide of hydrophilicity-imparting treatment is vertically put into the mixed solution by tetraethyl orthosilicate and polyacrylonitrile, after ageing, take out slide, drying, must deposit SiO
2the slide of@PS;
3) SiO will be deposited
2the mixed liquor be made up of cabaltous nitrate hexahydrate, ammonium fluoride and urea vertically put into by the slide of@PS, after warm water thermal response, takes out slide, through high-temperature calcination, isolates skin-material from slide, and obtaining squid must shape structure C o
3o
4.
2. preparation method according to claim 1, is characterized in that the mixed volume of sulfuric acid and hydrogen peroxide in described step 1) than being 3:1.
3. preparation method according to claim 1, is characterized in that soak time described in described step 1) is 24 ± 1 hours.
4. preparation method according to claim 1, it is characterized in that described step 2) described in the mixed volume of tetraethyl orthosilicate and polyacrylonitrile than being 1:0.02, the mass fraction of described tetraethyl orthosilicate is 0.15 ~ 0.45 wt%, and the mass fraction of polyacrylonitrile is 0.1 ~ 0.4 wt%.
5. preparation method according to claim 1, is characterized in that described step 2) described in Aging Temperature be 30 ~ 40 DEG C, digestion time is 2 ~ 3 days.
6. preparation method according to claim 1, is characterized in that the mixing mol ratio of cabaltous nitrate hexahydrate, ammonium fluoride and urea in described step 3) is 5 ~ 9:6 ~ 10:8 ~ 10.
7. preparation method according to claim 1, it is characterized in that the temperature of baking oven during hydro-thermal reaction in described step 3) is 80 ~ 150 DEG C, the hydro-thermal reaction time is 2 ~ 8 h.
8. preparation method according to claim 1, it is characterized in that in described step 3), calcining heat is 400 ~ 600 DEG C, the time is 1 ~ 8 h.
9. preparation method according to claim 8, when it is characterized in that calcining in described step 3) with the heating rate of 1 ~ 5 DEG C/min by temperature to 400 ~ 600 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739058A (en) * | 2017-11-02 | 2018-02-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of self assembly rhombus flowers Co3O4 nanometer material and products thereof and application |
| CN110316768A (en) * | 2019-08-14 | 2019-10-11 | 中国科学院青海盐湖研究所 | A kind of spinel structure cobalt/cobalt oxide, preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040234859A1 (en) * | 2003-05-21 | 2004-11-25 | Samsung Sdi Co., Ltd | Negative active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery comprising same |
| CN104003454A (en) * | 2014-05-22 | 2014-08-27 | 中国科学院化学研究所 | Porous cobalt oxide nanowire, and preparation method and application thereof |
| CN104681299A (en) * | 2015-03-27 | 2015-06-03 | 吉林化工学院 | Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof |
-
2015
- 2015-07-15 CN CN201510414321.0A patent/CN104966834A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040234859A1 (en) * | 2003-05-21 | 2004-11-25 | Samsung Sdi Co., Ltd | Negative active material for rechargeable lithium battery, method of preparing same, and rechargeable lithium battery comprising same |
| CN104003454A (en) * | 2014-05-22 | 2014-08-27 | 中国科学院化学研究所 | Porous cobalt oxide nanowire, and preparation method and application thereof |
| CN104681299A (en) * | 2015-03-27 | 2015-06-03 | 吉林化工学院 | Supercapacitor electrode material of cobaltosic oxide porous nanowire array, and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107739058A (en) * | 2017-11-02 | 2018-02-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of self assembly rhombus flowers Co3O4 nanometer material and products thereof and application |
| CN110316768A (en) * | 2019-08-14 | 2019-10-11 | 中国科学院青海盐湖研究所 | A kind of spinel structure cobalt/cobalt oxide, preparation method and application |
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Application publication date: 20151007 |