CN106654243B - A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed-metal oxides - Google Patents
A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed-metal oxides Download PDFInfo
- Publication number
- CN106654243B CN106654243B CN201611103045.7A CN201611103045A CN106654243B CN 106654243 B CN106654243 B CN 106654243B CN 201611103045 A CN201611103045 A CN 201611103045A CN 106654243 B CN106654243 B CN 106654243B
- Authority
- CN
- China
- Prior art keywords
- nano material
- arch tunnel
- coo
- tio
- 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.)
- Expired - Fee Related
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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
-
- 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
-
- 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
-
- 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
-
- 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
- H01M4/362—Composites
- H01M4/364—Composites as mixtures
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses the preparation method and applications that a kind of electrochemical in-situ method prepares two-arch tunnel mixed-metal oxides.CoO/TiO provided by the present invention2Two-arch tunnel mixed metal nano material has the ability for improving circulating battery effect, is an excellent lithium ion battery negative material.It is simple and novel for the preparation method of the mixing nano material, it can be mass, raw material is easy to get, and shows good application prospect.Importantly, this method avoid in conventional hybrid object preparation process the problem of raw material mixing uniformity, but the one two-arch tunnel mixed metal nano material directly formed by electrochemical in-situ process.The CoO/TiO2Two-arch tunnel mixed metal nano material illustrates the cycle performance under outstanding high rate performance and high magnification when being used as lithium ion battery negative material.
Description
Technical field
The invention belongs to nano materials 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 technique
Lithium ion battery the advantages that green high-efficient, memory-less effect and becomes due to high-energy density, safety and stability
The high energy green energy-storing material of a new generation.Currently, lithium ion battery has been widely used for all kinds of portable electronic devices, electronic
The fields such as the vehicles, robot, energy storage device.For lithium ion battery negative material, used with Current commercialization negative
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 that.In order to meet the eager demand of long circulation life electrode material currently close to high-energy and stable, research tool
There is the negative electrode material of high theoretical specific capacity extremely urgent.But the universal disadvantage of metal oxide-type material is due to variable valency metal
Oxide material volume expansion and contraction violent in charge and discharge process, cause the faster capacity of metal oxide materials to decline
It moves back.It concentrates at present by variable valency metal oxide and stable insert-type about the research of the metal oxide of battery cathode is more
Metal oxide is uniformly mixed to solve the problems, such as capacity attenuation and cyclical stability, but its obtained mixed-metal oxides
It is all a simple physical mixed, and obtained result homogeneity is uncontrollable.
Herein, we by electrostatic spinning control nanostructure, 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 mixed metal nano material (two-arch tunnel metal refers to that the two-phase of two kinds of different metal materials is completely continuous, 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.
Summary of the invention
The purpose of the present invention is to propose to a kind of electrochemical in-situ methods to obtain such a CoO/TiO2Two-arch tunnel is mixed
Alloy metal nanometer material and its application.
CoO/TiO provided by the invention2Two-arch tunnel mixed metal nano material, by CoTiO3(CoTiO3The size of particle
In 10nm or so) it is obtained by electrochemical in-situ method.
The method of the present invention is achieved through the following technical solutions:
A kind of CoO/TiO2The preparation method of two-arch tunnel mixed metal nano material, basic implementation process are as follows:
(1) butyl titanate is added to stirring in acetic acid and forms homogeneous transparent solution.
(2) ethyl alcohol is added in the solution that step (1) obtains, 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 electrostatic spinning afterwards for a period of time.
(4) presoma for obtaining step (3), is heat-treated in air atmosphere, and that obtain is CoTiO3Nanowire
Tie up material.
(5) by the CoTiO of preparation3Nano-fiber material, acetylene black, sodium carboxymethylcellulose with the ratio of 6:3:1, with
NMP is that slurry is made in solvent, is coated uniformly on copper foil.After being assembled into button cell in glove box as negative electrode material,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.That obtain after the charge and discharge of first lap is exactly CoO/TiO2
Two-arch tunnel mixed metal nano material.
Wherein, the concretely 0.1-1h of mixing time described in step (1).
Continuing mixing time in step (2) can be 2-8h.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 fourth
Aldehyde), PAN (Peroxyacetyl nitrate), PMMA (polymethyl methacrylate), PI (polyimides)
The solution left standstill time can be 0.5-2h in step (3).
It can be 400-600 DEG C that step (4), which is heat-treated reaction temperature, and the time can be 2-6h.
Detailed description of the invention
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 mixed metal nano material
A schematic diagram.
Fig. 4 is in embodiment 5 to CoTiO3CoO/TiO is obtained after nano material electrochemical treatments2Two-arch tunnel mixed metal
The XPS analysis that nano material is done.
Fig. 5 is CoO/TiO in embodiment 52Two-arch tunnel mixed metal nano material is 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 mixed metal nano material is as lithium ion battery negative material
When (a) high rate performance, (b) cycle performance
Fig. 7 is CoO/TiO in embodiment 52Two-arch tunnel mixed metal nano material is as lithium ion battery negative material
When high current density under long circulating performance map.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
Prepare CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 6ml ethyl alcohol and 0.20g cobalt nitrate and 0.4g PVP are added under stirring, stirring
4h starts electrostatic spinning after standing 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, then cools to room temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 2
CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobalt chloride and 0.4g PVP are added under stirring, stirring
4h starts electrostatic spinning after standing 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, then cools to room temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 3
Prepare CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobaltous sulfate and 0.3g PVP are added under stirring, stirring
4h starts electrostatic spinning after standing 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, then cools to room temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 4
Prepare CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobalt nitrate and 0.2g PAN are added under stirring, stirring
4h starts electrostatic spinning after standing 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, then cools to room temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 5
Prepare CCoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobalt nitrate and 0.2g PVP are added under stirring, stirring
4h starts electrostatic spinning after standing 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, constant temperature 2h, then cools to room temperature at this temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 6
Prepare CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobalt nitrate and 0.2g PVP are added under stirring, stirring
4h starts electrostatic spinning after standing 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, constant temperature 2h, then cools to room temperature at this temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 7
Prepare CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobalt nitrate and 0.2g PVP are added under stirring, stirring
6h starts electrostatic spinning after standing 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, constant temperature 3h, then cools to room temperature at this temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It is double
Continuous mixed phase metal nano material.
Embodiment 8
Prepare CoO/TiO2Two-arch tunnel mixed metal nano material
The butyl titanate of 0.15g is added in 3ml acetum, after 20min is stirred at room temperature, solution becomes colourless uniform
Butyl titanate/acetum, then 4ml ethyl alcohol and 0.20g cobalt nitrate and 0.2g PVP are added under stirring, stirring
6h starts electrostatic spinning after standing 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, then cools to room temperature, and CoTiO can be obtained3Nano material.
The CoTiO of preparation3Nano material, acetylene black, sodium carboxymethylcellulose are made with the ratio of 6:3:1, solvent of NMP
Slurry is coated uniformly on copper foil.As working electrode, lithium piece is used as to electrode, and electrolyte is the LiPF of 1M6, EC:DEC
(volume ratio 1:1).Diaphragm is glass fibre (W hatman 934-A H).After being assembled into button cell in glove box,
Constant current charge-discharge is carried out on LAND.Voltage range is 0.01-3V.It obtains being CoO/TiO after the charge and discharge of first lap2It 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
Analyse 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.It is respectively SEM and the TEM figure of embodiment 7 from Fig. 2 (a) and Fig. 2 (b).It can be seen that embodiment
3 obtained CoTiO3It is three-dimensional nano-fiber material, and from TEM figure 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 mixed metal nano material.Fig. 4 is in embodiment 5 to CoTiO3Nano material electricity
CoO/TiO is obtained after chemical treatment2The XPS analysis that two-arch tunnel mixed metal nano material is done, it was demonstrated that electrochemical treatments it
That obtain really afterwards is CoO/TiO2Two-arch tunnel mixed metal nano material.Fig. 5 is CoO/TiO in embodiment 72Two-arch tunnel
Cyclic voltammetry curve and its corresponding charging and discharging curve figure when mixed metal nano material is as lithium ion battery negative material.
Fig. 6 is CoO/TiO in embodiment 72Cycle performance and high rate performance figure when nano material is as lithium ion battery negative material.
Fig. 7 is CoO/TiO in embodiment 72Big electricity when two-arch tunnel mixed metal nano material is as 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 (6)
1. a kind of lithium ion battery negative material CoO/TiO2The preparation method of two-arch tunnel mixed metal nano material, feature
It is, the CoO/TiO prepared by electrochemical in-situ method2Two-arch tunnel mixed-metal materials realize stable charge and discharge
Cycle performance；
The CoO/TiO2Two-arch tunnel mixed metal nano material, is to pass through CoTiO3Material is made, the CoTiO3Material is
Threadiness, the size of fiber are diameter 100-500nm, and length is 100-200 μm.
2. preparation method according to claim 1, implementation process are as follows:
(1) stirring in acetum is added in butyl titanate and forms homogeneous transparent solution；
(2) ethyl alcohol is added in the solution that step (1) obtains, 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 electrostatic spinning afterwards for a period of time；
(4) presoma for obtaining step (3) carries out air atmosphere heat treatment, and that obtain is CoTiO3Nano material；
(5) to CoTiO3Nano material carries out smear, and charge and discharge obtain CoO/TiO after packed battery2Two-arch tunnel mixed metal nanometer
Material.
3. preparation method according to claim 2, mixing time described in step (1) is specially 0.1-1h.
4. preparation method according to claim 2, the middle mixing time that continues of step (2) is 2-8h；Wherein, Co salt is CoF2,
CoCl2, CoBr2, Co (NO3)2, CoSO4, CoCO3In any one, high polymer be polyvinylpyrrolidone PVP, polyvinyl alcohol
Butyral PVB, Peroxyacetyl nitrate PAN, polymetylmethacrylate, any one in polyimides PI.
5. preparation method according to claim 2, the solution left standstill time can be 0.5-2h in step (3).
6. preparation method according to claim 2, it is 400-600 DEG C that step (4), which is heat-treated reaction temperature, time 2-
6h。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611103045.7A CN106654243B (en) | 2016-12-05 | 2016-12-05 | A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed-metal oxides |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611103045.7A CN106654243B (en) | 2016-12-05 | 2016-12-05 | A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed-metal oxides |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106654243A CN106654243A (en) | 2017-05-10 |
| CN106654243B true CN106654243B (en) | 2019-07-09 |
Family
ID=58819394
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201611103045.7A Expired - Fee Related CN106654243B (en) | 2016-12-05 | 2016-12-05 | A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed-metal oxides |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106654243B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107293724B (en) * | 2017-07-17 | 2019-11-12 | 中南大学 | A kind of cobalt titanate/titanium dioxide/cobalt@carbon composite and preparation method thereof and application as sodium ion negative electrode material |
| CN108649201B (en) * | 2018-05-08 | 2021-01-01 | 宁波大学 | LaTi21O38·CoO·CuLaO2Preparation method of composite nanowire |
| CN109904418B (en) * | 2019-01-31 | 2021-09-21 | 深圳大学 | Lithium ion battery cathode material and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844816A (en) * | 2010-05-25 | 2010-09-29 | 陕西科技大学 | Method for preparing nano cobalt acetate powder |
| CN102683710A (en) * | 2012-05-21 | 2012-09-19 | 北京化工大学 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
| CN105047904A (en) * | 2015-06-17 | 2015-11-11 | 中国矿业大学 | Preparation method and application of titanium-cobalt spinel |
-
2016
- 2016-12-05 CN CN201611103045.7A patent/CN106654243B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101844816A (en) * | 2010-05-25 | 2010-09-29 | 陕西科技大学 | Method for preparing nano cobalt acetate powder |
| CN102683710A (en) * | 2012-05-21 | 2012-09-19 | 北京化工大学 | Carbon nanofiber load titanium dioxide thin film anode material and preparation method thereof |
| CN105047904A (en) * | 2015-06-17 | 2015-11-11 | 中国矿业大学 | Preparation method and application of titanium-cobalt spinel |
Non-Patent Citations (2)
| Title |
|---|
| "Fabrication and characterization of CoTiO3 nanofibers by sol-gel assisted electrospinning";Guorui Yang et al.;《Materials Letters》;20140207;第122卷;摘要、实验部分、结果与讨论部分和结论部分 |
| "Mixed Transition Metal Titanate and Vanadate Negative Electrode Materials for Na-Ion Batteries";Z.L Brown et al.;《Journal of The Electrochemical Society》;20141107;第162卷;摘要、实验部分、结果与讨论部分和结论部分 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106654243A (en) | 2017-05-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106450205B (en) | Two-dimensional transition group metal carbon/nitride and nano sulfur particle composite material and preparation and application thereof | |
| CN106374099B (en) | A kind of lithium ion battery flexible self-supporting lithium-rich manganese-based anode and preparation method thereof | |
| CN100544081C (en) | A kind of nano lithium titanate and with the preparation method of the compound of titanium dioxide | |
| CN102891299B (en) | High-rate lithium ion battery cathode material and preparation method and application thereof | |
| CN108574089B (en) | Preparation method of hollow tubular lithium-rich manganese-based positive electrode material | |
| CN109167035A (en) | Carbon-coated ferrous sulfide negative electrode material, preparation method and its sodium-ion battery of preparation | |
| CN104466102B (en) | A kind of porous V2O5/C complex microspheres of positive electrode material of lithium secondary cell and preparation method thereof | |
| WO2014153957A1 (en) | Water-based alkali metal ion energy storage device | |
| CN108493458B (en) | High-performance echinoid nickel oxide/nickel cobaltate microsphere lithium oxygen battery positive electrode catalytic material and preparation method thereof | |
| CN105731409A (en) | Molybdenum-base positive pole material and preparation method thereof | |
| CN109904441A (en) | A kind of lithium ion battery negative material, lithium ion battery with nonaqueous electrolyte and preparation method thereof | |
| CN105161711A (en) | Lithium manganate cathode material, preparation method and use | |
| CN109148859A (en) | A kind of preparation method of double carbon-coating coated manganese oxide composite materials | |
| CN110416489A (en) | The nanofiber storage sodium positive electrode preparation of nano particle assembling and application method | |
| CN106654243B (en) | A kind of electrochemical in-situ method prepares the method and its application of two-arch tunnel mixed-metal oxides | |
| CN106299344B (en) | A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof | |
| CN110233261A (en) | A kind of preparation method and lithium ion battery of monocrystalline ternary anode material of lithium battery | |
| CN110817967A (en) | Method for synthesizing graphene coated MnO nano material by microwave-assisted method and application | |
| CN110165190A (en) | A kind of nanocarbon/metal sulfide composite material and preparation method and application | |
| CN106340621A (en) | Ferric negative electrode material for lithium battery and preparation method thereof | |
| CN113571681B (en) | Hollow titanium dioxide/nickel/carbon composite material and preparation method and application thereof | |
| CN106960947A (en) | Composite, its preparation method and application | |
| CN108110250A (en) | Zinc manganate/lithium iron oxide ion battery cathode material and preparation method thereof | |
| CN111384389A (en) | Precursor of ternary material | |
| CN110518216B (en) | Negative electrode composite material of sodium ion battery and preparation method thereof |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190709 Termination date: 20191205 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |