CN106654243A - Preparation method for bi-continuous phase mixed metal oxide by in-situ electrochemical method and application of mixed metal oxide - Google Patents
Preparation method for bi-continuous phase mixed metal oxide by in-situ electrochemical method and application of mixed metal oxide Download PDFInfo
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- CN106654243A CN106654243A CN201611103045.7A CN201611103045A CN106654243A CN 106654243 A CN106654243 A CN 106654243A CN 201611103045 A CN201611103045 A CN 201611103045A CN 106654243 A CN106654243 A CN 106654243A
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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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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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
- 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
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- H—ELECTRICITY
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- 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
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- 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 for bi-continuous phase mixed metal oxide by an in-situ electrochemical method and an application of the mixed metal oxide. A CoO/TiO<2> bi-continuous phase mixed metal nanometer provided by invention has capability of improving a battery cycling effect, and is an excellent negative electrode material of a lithium ion battery. The preparation method for the mixed nanometer is simple and creative, batch production can be realized and the raw materials are easily available, so that the preparation method is high in application prospect; more importantly, the problem existing in raw material mixing uniformity in a conventional mixture preparation process is avoided; instead, the bi-continuous phase mixed metal nanometer is directly formed through an in-situ electrochemical process; and when the CoO/TiO<2> bi-continuous phase mixed metal nanometer is used as the negative electrode material of the lithium ion battery, excellent rate capability and high-rate cycling performance are represented.
Description
Technical field
The invention belongs to nano material and technical field of lithium batteries, are related to a kind of original of two-arch tunnel mixed-metal oxides
The preparation method of position electrochemistry and its application in lithium ion battery negative material.
Background technology
Lithium ion battery the advantages of high-energy-density, safety and stability, green high-efficient, memory-less effect due to becoming
The high energy green energy-storing material of a new generation.At present, lithium ion battery has been widely used for all kinds of portable electric appts, electronic
The fields such as the vehicles, robot, energy storage device.It is negative with what Current commercialization was adopted for lithium ion battery negative material
Pole material graphite (theoretical capacity 372mA h g-1) compare, variable valency metal oxide material has higher theoretical specific capacity, rich
Degree is high, the advantages of.In order to meet the eager demand of current close to high-energy and stable long circulation life electrode material, research tool
There is the negative material of high theoretical specific capacity extremely urgent.But the universal shortcoming of metal oxide-type material is due to variable valency metal
The violent volumetric expansion in charge and discharge process of oxide material and contraction, faster capacity declines to cause metal oxide materials
Move back.The at present research with regard to the metal-oxide of battery cathode more is concentrated on variable valency metal oxide and stable insert-type
Metal-oxide mix homogeneously is solving capacity attenuation and stable circulation sex chromosome mosaicism, but its mixed-metal oxides for obtaining
All it is a simple physical mixed, and the result homogeneity for obtaining is uncontrollable.
Here, we by electrostatic spinning control nanostructured, designed and synthesized on pattern have it is mesoporous, excellent and
The three-dimensional CoTiO of high electrochemical activity3Nano-fiber material, then such a CoO/TiO is obtained by electrochemical in-situ process2
Two-arch tunnel hybrid metal nano material (two-arch tunnel metal refers to the biphase completely continuous of two kinds of different metal materials, wherein
CoO belongs to variable valency metal oxide material, TiO2Belong to deintercalation type metal oxide materials).There is the material excellent length to follow
Ring stability, high rate performance.
The content of the invention
The purpose of the present invention is to propose to a kind of electrochemical in-situ method obtains such a CoO/TiO2Two-arch tunnel is mixed
Alloy metal nanometer material and its application.
The CoO/TiO that the present invention is provided2Two-arch tunnel hybrid metal nano material, by CoTiO3(CoTiO3The size of granule
In 10nm or so) obtained by electrochemical in-situ method.
The inventive method is achieved through the following technical solutions：
A kind of CoO/TiO2The preparation method of two-arch tunnel hybrid metal nano material, its basic implementation process is as follows：
(1) butyl titanate is added to into stirring in acetic acid and forms homogeneous transparent solution.
(2) ethanol is added in the solution that step (1) is obtained, is stirred for lower addition Co salt and high polymer and continues stirring extremely
Peony clear solution.
(3) solution left standstill for obtaining (2) carries out afterwards for a period of time electrostatic spinning.
(4) presoma for obtaining step (3), in air atmosphere heat treatment is carried out, and what is obtained is CoTiO3Nanowire
Dimension material.
(5) CoTiO that will be prepared3Nano-fiber material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, with
NMP makes slurry for solvent, is coated uniformly on Copper Foil.After button cell being assembled into as negative material in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.That the discharge and recharge of first lap is obtained after terminating is exactly CoO/TiO2
Two-arch tunnel hybrid metal nano material.
Wherein, the concretely 0.1-1h of mixing time described in step (1).
It can be 2-8h to continue mixing time in step (2).Wherein, Co salt can be CoX2(X=F, Cl, Br), Co
(NO3)2, CoSO4, CoCO3Any one.High polymer can be PVP (polyvinylpyrrolidone), PVB (polyvinyl alcohol contracting fourths
Aldehyde), PAN (Peroxyacetyl nitrate), PMMA (polymethyl methacrylate), PI (polyimides)
The solution left standstill time can be 0.5-2h in step (3).
Step (4) heat treatment reaction temperature can be 400-600 DEG C, and the time can be 2-6h.
Description of the drawings
Fig. 1 is CoTiO in embodiment 53Nano material (a) X-ray diffraction (XRD), (b) x-ray photoelectron energy (XPS).
Fig. 2 is CoTiO in embodiment 33(a) of nano-fiber material is scanning electron microscope (SEM) photo, (b) is
Transmission electron microscope (TEM) photo.
Fig. 3 is to CoTiO in embodiment 53Material and its formation CoO/TiO2The one of two-arch tunnel hybrid metal nano material
Individual schematic diagram.
Fig. 4 is to CoTiO in embodiment 53CoO/TiO is obtained after nano material electrochemical treatments2Two-arch tunnel hybrid metal
The XPS analysis that nano material is done.
Fig. 5 is CoO/TiO in embodiment 52Two-arch tunnel hybrid metal nano material is used as lithium ion battery negative material
When (a) cyclic voltammetry curve, (b) charging and discharging curve figure.
Fig. 6 is CoO/TiO in embodiment 52Two-arch tunnel hybrid metal nano material is used as lithium ion battery negative material
When (a) high rate performance, (b) cycle performance
Fig. 7 is CoO/TiO in embodiment 52Two-arch tunnel hybrid metal nano material is used as lithium ion battery negative material
When high current density under long circulating performance map.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but the present invention is not limited to following examples.
Embodiment 1
Prepare CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 6ml ethanol and 0.20g cobalt nitrates and 0.4g PVP, stirring are added under stirring
4h, to stand and start electrostatic spinning after 1h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1's
Heating rate is warming up to 600 DEG C, at this temperature constant temperature 2h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 2
CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobaltous chlorides and 0.4g PVP, stirring are added under stirring
4h, to stand and start electrostatic spinning after 1h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1's
Heating rate is warming up to 600 DEG C, at this temperature constant temperature 2h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 3
Prepare CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobaltous sulfates and 0.3g PVP, stirring are added under stirring
4h, to stand and start electrostatic spinning after 1h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1's
Heating rate is warming up to 600 DEG C, at this temperature constant temperature 2h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 4
Prepare CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobalt nitrates and 0.2g PAN, stirring are added under stirring
4h, to stand and start electrostatic spinning after 1h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1's
Heating rate is warming up to 600 DEG C, at this temperature constant temperature 2h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 5
Prepare CCoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobalt nitrates and 0.2g PVP, stirring are added under stirring
4h, to stand and start electrostatic spinning after 0.5h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1
Heating rate be warming up to 600 DEG C, at this temperature constant temperature 2h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 6
Prepare CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobalt nitrates and 0.2g PVP, stirring are added under stirring
4h, to stand and start electrostatic spinning after 0.5h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1
Heating rate be warming up to 500 DEG C, at this temperature constant temperature 2h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 7
Prepare CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobalt nitrates and 0.2g PVP, stirring are added under stirring
6h, to stand and start electrostatic spinning after 0.5h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1
Heating rate be warming up to 500 DEG C, at this temperature constant temperature 3h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
Embodiment 8
Prepare CoO/TiO2Two-arch tunnel hybrid metal nano material
The butyl titanate of 0.15g is added in 3ml acetums, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethanol and 0.20g cobalt nitrates and 0.2g PVP, stirring are added under stirring
6h, to stand and start electrostatic spinning after 1h.Finally, under the conditions of air atmosphere, by this presoma with 5 DEG C of min in tube furnace-1's
Heating rate is warming up to 500 DEG C, at this temperature constant temperature 4h, is subsequently cooled to room temperature, you can obtain CoTiO3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethyl cellulose are with 6:3:1 ratio, solvent is made up of NMP
Slurry, is coated uniformly on Copper Foil.As working electrode, used as to electrode, electrolyte is the LiPF of 1M to lithium piece6, EC:DEC
(volume ratio is 1:1).Barrier film is glass fibre (W hatman 934-A H).After button cell being assembled in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.The discharge and recharge of first lap obtain after terminating for CoO/TiO2It is double
Continuous mixed phase metal nano material.
CoTiO is obtained to example 53Nano material carries out powder x-ray diffraction (RigakuDmaxrB, CuK alpha ray) point
Analysis crystal structure.Fig. 1 (a) is the XRD of embodiment 5, as can be seen from the figure proves that we successfully synthesize CoTiO3Material.Figure
1 (b-d) is the XPS of embodiment 3.The SEM and TEM figure of embodiment 7 is respectively from Fig. 2 (a) and Fig. 2 (b).It can be seen that embodiment
3 CoTiO for obtaining3It is three-dimensional nano-fiber material, and from TEM figures it can be seen that every fiber CoTiO3Nanometer little particle heap
Product composition, CoTiO3Nanometer small particle diameters are about 10nm.Fig. 3 is to CoTiO in embodiment 53Material morphology and its formation
CoO/TiO2One schematic diagram of two-arch tunnel hybrid metal nano material.Fig. 4 is to CoTiO in embodiment 53Nano material electricity
CoO/TiO is obtained after chemical treatment2The XPS analysis that two-arch tunnel hybrid metal nano material is done, it was demonstrated that electrochemical treatments it
That what is obtained really afterwards is CoO/TiO2Two-arch tunnel hybrid metal nano material.Fig. 5 is CoO/TiO in embodiment 72Two-arch tunnel
Hybrid metal nano material is used as cyclic voltammetry curve during lithium ion battery negative material and its corresponding charging and discharging curve figure.
Fig. 6 is CoO/TiO in embodiment 72Nano material is used as cycle performance during lithium ion battery negative material and high rate performance figure.
Fig. 7 is CoO/TiO in embodiment 72Two-arch tunnel hybrid metal nano material is used as big electricity during lithium ion battery negative material
Long circulating performance map under current density, after 1200 circulations, capacity maintains always 617mA h g-1, show very
Stable cycle performance.Fig. 5, Fig. 6 and Fig. 7 show that the nano material shows excellent stability electrochemical energy and circulation energy
Power.
Claims (8)
1. class CoO/TiO2The preparation of two-arch tunnel hybrid metal nano material, it is characterised in that by electrochemical in-situ method
The two-arch tunnel metal mixed material (two kinds of different materials are biphase completely continuous) of preparation, realizes stable charge-discharge cycle
Energy.
2. according to claim 1, the CoO/TiO2The architectural feature of metal nano material is, by CoTiO3Material is obtained,
CoTiO3Overall pattern is rendered as threadiness, and the size of fiber is diameter 100-500nm, length 10-200 μm, preferred diameter
200nm, 100 μm of length.
3. a kind of CoO/TiO2The preparation method of two-arch tunnel hybrid metal nano material, its basic implementation process is as follows：
(1) stirring in acetum is added to form homogeneous transparent solution butyl titanate.
(2) ethanol is added in the solution that step (1) is obtained, is stirred for lower addition Co salt and high polymer and continues to stir to dark red
Color clear solution.
(3) solution left standstill for obtaining (2) carries out afterwards for a period of time electrostatic spinning.
(4) presoma for obtaining step (3), carries out air atmosphere heat treatment, and what is obtained is CoTiO3Nano material.
(5) to CoTiO3Nano material carries out smear, and discharge and recharge after packed battery obtains CoO/TiO2 two-arch tunnel hybrid metal nanometers
Material.
4. in preparation method according to claim 3, the concretely 0.1-1h of mixing time described in step (1).It is preferred that
0.2h。
5. in preparation method according to claim 3, it can be 2-8h that mixing time is continued in step (2).It is preferred that 6h, its
In, Co salt can be CoX2(X=F, Cl, Br), Co (NO3)2, CoSO4, CoCO3Any one, preferred Co (NO3)2, Gao Ju
Thing can be PVP (polyvinylpyrrolidone), PVB (polyvinyl butyral resin), PAN (Peroxyacetyl nitrate), PMMA (poly- first
Base acrylic acid methyl ester .), PI (polyimides), preferred PVP.
6. in preparation method according to claim 3, the solution left standstill time can be 0.5-2h in step (3).It is preferred that 0.5h.
7. in preparation method according to claim 3, step (4) heat treatment reaction temperature can be 400-600 DEG C, and the time can
For 2-6h.It is preferred that 4h.
8. in the preparation method according to claim 1-7, the CoO/TiO2Two-arch tunnel hybrid metal nano material lithium from
Application in sub- battery electrode material.
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| CN109904418A (en) * | 2019-01-31 | 2019-06-18 | 深圳大学 | A kind of lithium ion battery negative material and preparation method thereof |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107293724A (en) * | 2017-07-17 | 2017-10-24 | 中南大学 | A kind of cobalt titanate/titanium dioxide/cobalt@carbon composites and preparation method thereof and it is used as the application of sodium ion negative material |
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| CN109904418B (en) * | 2019-01-31 | 2021-09-21 | 深圳大学 | Lithium ion battery cathode material and preparation method thereof |
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| CN106654243B (en) | 2019-07-09 |
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