CN108963245A - A kind of mesoporous cobaltosic oxide electrode material of lamellar and preparation method thereof - Google Patents
A kind of mesoporous cobaltosic oxide electrode material of lamellar and preparation method thereof Download PDFInfo
- Publication number
- CN108963245A CN108963245A CN201811099160.0A CN201811099160A CN108963245A CN 108963245 A CN108963245 A CN 108963245A CN 201811099160 A CN201811099160 A CN 201811099160A CN 108963245 A CN108963245 A CN 108963245A
- Authority
- CN
- China
- Prior art keywords
- electrode material
- lamellar
- cobaltosic oxide
- oxide electrode
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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 mesoporous cobaltosic oxide electrode materials of a kind of lamellar and its preparation method and application.The particle of the material has fine and close lamellar structure, is made of nanometer sheet accumulation；Nanometer sheet has meso-hole structure, is assembled by nano particle.Preparation method are as follows: use hydro-thermal method, prepare presoma using cobalt nitrate, urea mixed solution as raw material, then cobaltosic oxide powder material is made through calcining in air atmosphere.The material has high-tap density, for showing high reversible capacity, high initial coulomb efficiency and high circulation stability when lithium ion battery negative material.
Description
Technical field
The present invention relates to lithium ion battery electrode materials, and in particular to a kind of mesoporous cobaltosic oxide electrode material of lamellar
And its preparation method and application.
Background technique
Lithium ion battery has obtained very extensive quotient because having the advantages that high voltage, high capacity, high power, long-life
Industry application, it has also become the electric energy storage device of mainstream.With equipment performances such as electronic product, electric car and energy-accumulating power stations
It is constantly promoted, the requirement to the energy density of lithium ion battery is also higher and higher.However, existing commercialized lithium ion battery
Used graphite cathode material, through years development, technology is highly developed, and capacity has almost been exhibited to pole
Limit, it is difficult to realize the breakthrough of battery energy density.Therefore, it is badly in need of developing novel cheap high capacity lithium ion cells cathode material
Material.
Cobaltosic oxide is a kind of novel cathode material for high capacity lithium ion battery, and theoretical capacity is graphite material
2.5 again.It also has many advantages, such as that chemical property is stable, it is simple, low in cost to prepare.But it is in practical application, still deposit
The initial coulomb efficiency and not high cyclical stability the disadvantages of.So the practical chemical property of cobaltosic oxide material is improved,
It is its key scientific problems as lithium ion battery negative material application urgent need to resolve.
It is currently nano-structured to the conventional modified method of cobaltic-cobaltous oxide negative pole material, although to a certain extent can
It gives full play to material capacity, improve initial coulomb efficiency and cyclical stability, but nano structural material is mostly because superfine small
Particle size and loose microstructure and result in that its density is very low, this can seriously reduce the volume energy density of battery, no
Conducive to the practical application of material in the battery.
Therefore, the present invention provides a kind of mesoporous cobaltosic oxide materials of lamellar with high density, high electrochemical performance
Material is used for lithium ion battery negative material.
Summary of the invention
It is a kind of for negative electrode of lithium ion battery the invention aims to provide, with high density and high electrochemical performance
Mesoporous cobaltosic oxide material of lamellar and preparation method thereof.
The preparation method of the mesoporous cobaltic-cobaltous oxide negative pole material of lamellar, its step are as follows:
(1) hydro-thermal method is used, hydro-thermal reaction is carried out to cobalt nitrate and urea mixed solution and prepares presoma.Nitre in mixed solution
The concentration of sour cobalt is 0.02 ~ 0.08 mol/L, and the concentration of urea is 1.5 ~ 2.0 mol/L, the useful load of solution in reaction vessel
It is 80%；The temperature of hydro-thermal reaction is 150 ~ 200oC, reaction time are 8 ~ 16 h.
(2) step (1) resulting presoma is calcined in air atmosphere, calcination temperature is 300 ~ 400oC, when calcining
Between be 30 ~ 60 min, obtain cobaltosic oxide electrode material.
The beneficial effects of the present invention are:
(1) apparent density of cobaltosic oxide electrode material of the invention is 1.5 ~ 2.0 g/cm3, tap density is 2.5 ~ 3.2
g/cm3, when being used as lithium ion battery negative material, the volume and capacity ratio of electrode can be substantially improved.
(2) primary granule of the powder of cobaltosic oxide material of the invention has lamellar knot having a size of 20 ~ 50 μm
Structure, by being constituted with a thickness of the nanometer sheet Close stack of 10 ~ 30 nm；Nanometer sheet has meso-hole structure, by having a size of 10 ~ 30 nm's
Nano particle assembles, and the size of intermediary hole is 10 ~ 50 nm.The big primary granule Assurance of Size high density of material；
The lamellar structure of particle and the meso-hole structure of nanometer sheet can allow electrolyte permeability to inside, increase reaction interface, mitigate electrode
Polarization improves the dynamic performance that material participates in electrochemical reaction, improves the utilization rate of material, to ensure that the height electricity of material
Chemical property.
Figure of description
In order to illustrate more clearly of the technical solution that the present invention is implemented, letter will be made to attached drawing needed in the embodiment below
Singly introduce.
Fig. 1 is stereoscan photograph of the cobaltic-cobaltous oxide negative pole material under different multiples in embodiment；(a) 500 times；
(b) 3000 times；(c) 200000 times.
Specific embodiment
The present invention is made below by specific embodiment and further being illustrated, but the invention is not limited to following
Example.
Embodiment:
(1) hydro-thermal method is used, hydro-thermal reaction is carried out to the mixed solution of cobalt nitrate and urea and prepares presoma.In mixed solution
The concentration of cobalt nitrate is 0.05 mol/L, and the concentration of urea is 1.875 mol/L, and the useful load of solution is 80% in reaction vessel；
The temperature of hydro-thermal reaction is 160oC, reaction time are 12 h.After reaction, it is centrifugated gained sediment, uses deionization
Water washes and dries, and obtains precursor powder.
(2) presoma obtained by step (1) is calcined in air atmosphere, calcination temperature 350oC, calcination time 45
Min obtains cobaltosic oxide electrode material.
Gained cobaltosic oxide material, apparent density are 1.8 g/cm3, tap density is 3.0 g/cm3.Material is swept
Electromicroscopic photograph is retouched as shown in Figure 1, its primary granule is having a size of 20 ~ 50 μm, Close stack is constituted layer by layer by nanometer sheet, forming layer
Laminated structure；Nanometer sheet is assembled by the nano particle having a size of 20 nm, and the width of hole is 10 nm therebetween.
Electrochemical property test is carried out to material using CR2025 button cell.Working electrode is by cobaltosic oxide, acetylene
Black, polyvinylidene fluoride is mixed by the mass ratio of 85:7.5:7.5, adds N-Methyl pyrrolidone, and stirring is tuned into uniform sizing material,
It is coated in copper foil current collector, then is made through vacuum drying；Metal lithium sheet is used to electrode；Electrolyte is 1 mol/L LiPF6
DEC+EC (volume ratio DEC:EC=1:1) solution；Diaphragm is Celgard2400 polypropylene screen.Battery assembling process
It is completed in the glove box that water, oxygen concentration are below 1 ppm.After battery installs, 12 h are stood, using galvanostatic charge/discharge,
In the voltage range of 0.02 ~ 3.0 V, constant current charge-discharge is carried out to it using the multiplying power of 0.2 C, tests the reversible of electrode material
Capacity, initial coulomb efficiency and cyclical stability.
Cobaltic-cobaltous oxide negative pole material of the invention, with use solution identical with embodiment through 80oC hydro-thermal reaction 12
Conventional nano cobaltosic oxide powder obtained by h is compared, and is had the advantage that
1, the density of powder body material is improved significantly, and greatly improves the volume and capacity ratio of electrode.Cobaltosic oxide of the present invention
Negative electrode material, apparent density are up to 1.8 g/cm3, tap density is up to 3.0 g/cm3, prepared electrode volume specific capacity is
2500 mAh/cm3, these values are much higher than 0.5 g/cm of conventional nano cobaltosic oxide material3、1.0 g/cm3With 1000 mAh/
cm3。
2, the reversible capacity of material, initial coulomb efficiency and cycle performance be improved significantly.Cobaltosic oxide of the present invention
Negative electrode material, primary granule are made of nanometer sheet Close stack, and nanometer sheet is meso-hole structure, are assembled by nano particle.
This structure can allow electrolyte to penetrate into inside particle, and material is enable sufficiently to participate in electrochemical reaction, to effectively improve material
Reversible capacity and initial coulomb efficiency.Meanwhile this structure can with the volume change during padded coaming lithiumation, make its
There is better structural stability in cyclic process, therefore the cycle performance of material can be improved.The cobaltosic oxide of embodiment
The reversible capacity for the first time of material be 880 mAh/g, initial coulomb efficiency 85%, circulation 100 times after capacity retention ratio be
102%, hence it is evident that higher than 850 mAh/g, 70% and 65% of conventional nano cobaltosic oxide material.
Claims (4)
1. a kind of mesoporous cobaltosic oxide electrode material of lamellar, which is characterized in that the primary granule of material is having a size of 20 ~ 50 μ
M is made of for fine and close lamellar structure the meso-porous nano piece densification stacking with a thickness of 10 ~ 30 nm, nanometer sheet by having a size of 10 ~
The particle of 30 nm assembles, and the size of intermediary hole is 10 ~ 50 nm；Material has highly dense because of its fine and close lamellar structure
Degree, apparent density are 1.5 ~ 2.0 g/cm3, tap density is 2.5 ~ 3.2 g/cm3。
2. the mesoporous cobaltosic oxide electrode material of lamellar according to claim 1, which is characterized in that the electrode material
There is excellent chemical property because of the synergistic effect between its fine and close lamellar structure and meso-hole structure, the electrode material exists
Reversible capacity for the first time under 0.2 C is 850 ~ 950 mAh/g, and initial coulomb efficiency is 80% ~ 90%, the capacity after 100 circulations
Conservation rate is 95% ~ 105%, 2200 ~ 2600 mAh/cm of volume and capacity ratio of prepared electrode3。
3. the mesoporous cobaltosic oxide electrode material of lamellar according to claim 1 is as lithium ion battery electrode material
Using.
4. the preparation method of the mesoporous cobaltosic oxide electrode material of lamellar according to claim 1, it is characterised in that packet
Include following steps:
(1) hydro-thermal reaction is carried out to the mixed solution of cobalt nitrate and urea and prepares presoma, the concentration of cobalt nitrate in mixed solution
For 0.02 ~ 0.08 mol/L, the concentration of urea is 1.5 ~ 2.0 mol/L, and the temperature of hydro-thermal reaction is 150 ~ 200oC, when reaction
Between be 8 ~ 16 h；
(2) step (1) resulting precursor powder is calcined in air atmosphere, calcination temperature is 300 ~ 400oC obtains four
Co 3 O electrode material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811099160.0A CN108963245A (en) | 2018-09-20 | 2018-09-20 | A kind of mesoporous cobaltosic oxide electrode material of lamellar and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811099160.0A CN108963245A (en) | 2018-09-20 | 2018-09-20 | A kind of mesoporous cobaltosic oxide electrode material of lamellar and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108963245A true CN108963245A (en) | 2018-12-07 |
Family
ID=64471736
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811099160.0A Pending CN108963245A (en) | 2018-09-20 | 2018-09-20 | A kind of mesoporous cobaltosic oxide electrode material of lamellar and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108963245A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109850850A (en) * | 2019-01-23 | 2019-06-07 | 复旦大学 | A kind of general preparative methods of carbon, nitrogen co-doped metal oxide nano-sheet |
| CN113707861A (en) * | 2021-08-26 | 2021-11-26 | 合肥工业大学 | Nitrogen-doped carbon layer-coated cobalt oxide nanosheet and preparation method and energy storage application thereof |
| CN115745014A (en) * | 2022-11-24 | 2023-03-07 | 科立鑫(珠海)新能源有限公司 | Nanometer grade high-compactness cobaltosic oxide particle and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568833A (en) * | 2010-12-24 | 2012-07-11 | 同济大学 | Hybrid electrochemical capacitor with mesoporous cobaltosic oxide as positive pole |
| CN104478006A (en) * | 2015-01-06 | 2015-04-01 | 南京工业大学 | Preparation method of tricobalt tetraoxide mesoporous nanosheets |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105198007A (en) * | 2015-09-08 | 2015-12-30 | 哈尔滨工程大学 | Preparation and stripping methods of mesoporous cobaltosic oxide nanosheet |
| CN106315690A (en) * | 2016-08-12 | 2017-01-11 | 浙江美都墨烯科技有限公司 | Porous cobalt tetroxide nanosheet and preparation method thereof |
-
2018
- 2018-09-20 CN CN201811099160.0A patent/CN108963245A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102568833A (en) * | 2010-12-24 | 2012-07-11 | 同济大学 | Hybrid electrochemical capacitor with mesoporous cobaltosic oxide as positive pole |
| CN104478006A (en) * | 2015-01-06 | 2015-04-01 | 南京工业大学 | Preparation method of tricobalt tetraoxide mesoporous nanosheets |
| CN104986807A (en) * | 2015-04-23 | 2015-10-21 | 金川集团股份有限公司 | Spherical tricobalt tetraoxide preparation method |
| CN105198007A (en) * | 2015-09-08 | 2015-12-30 | 哈尔滨工程大学 | Preparation and stripping methods of mesoporous cobaltosic oxide nanosheet |
| CN106315690A (en) * | 2016-08-12 | 2017-01-11 | 浙江美都墨烯科技有限公司 | Porous cobalt tetroxide nanosheet and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| XIAOHUA HUANG ET AL.: "Aligned nickelecobalt oxide nanosheet arrays for lithium ion battery applications", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》 * |
| 黄小华等: "片状介孔Co3O4的制备及其储锂性能", 《材料科学与工程学报》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109850850A (en) * | 2019-01-23 | 2019-06-07 | 复旦大学 | A kind of general preparative methods of carbon, nitrogen co-doped metal oxide nano-sheet |
| CN109850850B (en) * | 2019-01-23 | 2022-08-19 | 复旦大学 | Universal preparation method of carbon and nitrogen co-doped metal oxide nanosheet |
| CN113707861A (en) * | 2021-08-26 | 2021-11-26 | 合肥工业大学 | Nitrogen-doped carbon layer-coated cobalt oxide nanosheet and preparation method and energy storage application thereof |
| CN115745014A (en) * | 2022-11-24 | 2023-03-07 | 科立鑫(珠海)新能源有限公司 | Nanometer grade high-compactness cobaltosic oxide particle and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108807931B (en) | High-nickel material with surface coated with lithium aluminum silicate and surface layer doped with fluorine and preparation method | |
| CN108539141B (en) | Preparation method of ternary layered positive electrode material for sodium-ion battery | |
| CN108123128A (en) | Adulterate Al in a kind of surface layer3+NCM tertiary cathode materials preparation method | |
| WO2015021789A1 (en) | High-magnification anode material of aqueous alkali metal electrochemical cell, and preparation method thereof | |
| CN109659511B (en) | SiO (silicon dioxide)2Coated ternary positive electrode material and preparation method thereof | |
| WO2015054974A1 (en) | Tungsten-based material super battery and supercapacitor | |
| CN108899530B (en) | Silicon-carbon composite material and preparation method and application thereof | |
| CN103560019B (en) | A kind of zinc ion hybrid super capacitor | |
| CN107601579B (en) | The preparation method and its resulting materials of a kind of high-performance porous C o-Mn-O nanometer sheet material and application | |
| CN109301207A (en) | A kind of surface layer doping Ce3+And surface layer coats CeO2NCM tertiary cathode material and preparation method thereof | |
| CN106207161A (en) | Negative material and preparation method and with the lithium rechargeable battery of this negative material | |
| CN108963245A (en) | A kind of mesoporous cobaltosic oxide electrode material of lamellar and preparation method thereof | |
| CN107946564B (en) | Rich in Na4Mn2O5/Na0.7MnO2Composite material and preparation method and application thereof | |
| CN112968173A (en) | Porous carbon-coated sulfur vacancy composite electrode material, preparation method thereof and circular electrode adopting material | |
| Qiao et al. | Nanoneedle-assembled hollow α-Fe2O3 microflowers as Li-ion battery anode with high capacity and good temperature tolerance | |
| Jia et al. | In-situ formation of ultrafine ZnMn2O4-MnOOH composite nanoparticles embedded into porous carbon nanospheres for stable aqueous zinc-ion batteries | |
| JP2015088343A (en) | Method for manufacturing positive electrode active material for nonaqueous electrolyte secondary batteries | |
| CN108598463A (en) | A kind of preparation method of nano-sheet lithium-rich manganese-based anode material | |
| CN109449440B (en) | Microporous ultrathin soft carbon nanosheet and preparation method and application thereof | |
| CN107195884A (en) | A kind of lithium metasilicate doped graphene lithium ion battery negative material and preparation method thereof | |
| CN107994184B (en) | Diaphragm for improving sulfur content of lithium-sulfur battery anode, preparation method and application thereof | |
| CN115172710A (en) | Iron oxide graphite composite material for lithium ion battery and preparation method thereof | |
| CN105514415B (en) | A kind of polynary lithium-rich anode material of lithium ion battery and preparation method and application | |
| CN109742341B (en) | Method for preparing Fe-doped two-dimensional porous NiO electrode material with high lithium storage performance under assistance of glucose | |
| CN106972171A (en) | A kind of three-dimensional net structure material, preparation method and its usage |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20181207 |
|
| WD01 | Invention patent application deemed withdrawn after publication |