CN103274474B - Rod-shaped zinc ferrite and its preparation method - Google Patents
Rod-shaped zinc ferrite and its preparation method Download PDFInfo
- Publication number
- CN103274474B CN103274474B CN201310223239.0A CN201310223239A CN103274474B CN 103274474 B CN103274474 B CN 103274474B CN 201310223239 A CN201310223239 A CN 201310223239A CN 103274474 B CN103274474 B CN 103274474B
- Authority
- CN
- China
- Prior art keywords
- shaft
- zinc ferrite
- ferrous sulfate
- oxalic acid
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses rod-shaped zinc ferrite and its preparation method. The diameter of the rod-shaped zinc ferrite is 7.0-500 nanometers; length-diameter ratio is 3.0-20; the rod-shaped radial direction is composed of 1-20 nano-particles; and the size of a single nano-particle is 7.0-30 nanometers. The preparation method of the rod-shaped zinc ferrite comprises the following steps: selecting ferrous sulphate and zinc chloride as raw materials, using oxalic acid as a precipitating agent, carrying out precipitation at room temperature, carrying out a hybrid reaction, aging, centrifuging, washing, drying and carrying out heat treatment to obtain the rod-shaped zinc ferrite constructed by the nano-particles. By the adoption of the method, the rod-shaped zinc ferrite constructed by the nano-particles can be prepared, and morphological control of length-diameter ratio being 3.0-20 and structural regulation and control of radial-direction nano-particle distribution number being 1-20 can be realized. The rod-shaped zinc ferrite constructed by the nano-particles is applicable to be used as a lithium ion battery cathode material as well as a photocatalysis material.
Description
Technical field
The present invention relates to a kind of preparation method of inorganic functional material, particularly relate to and a kind of adopt oxalic acid precipitation to prepare nano particle to construct shaft-like zinc ferrite, belong to inorganic advanced technical field of nano-composite material preparation technology.
Background technology
It is high that lithium ion battery has voltage, and specific storage is large, and the plurality of advantages such as density is high and have extended cycle life, become one of focus of Novel power battery research and development.But, want to meet lithium ion battery and play larger potentiality at electromobile and field of hybrid electric vehicles, just must have higher specific storage and high rate performance.At present, metal oxide and alloy have higher specific storage becomes electrode materials of new generation, and one dimension rod-like structure has good lithium ion and to shuttle back and forth passage, therefore has good chemical property.
Zinc ferrite theoretical specific capacity more than 1000 MAhs/g, and has that starting material are extensive, manufacturing cost is low becomes desirable lithium ion battery negative material.But zinc ferrite is in charge and discharge cycles process, and the expansion of volume and contraction cause electrode materials internal stress to concentrate, and cause electrode efflorescence, reduce its cycle life.In order to improve the chemical property of zinc ferrite, investigator has carried out large quantity research, mainly concentrates on structure and the pattern of change material, adulterates and prepare matrix material etc.Nano particle has good chemical property, but still can decline fast under high current density, to trace it to its cause be that high surface energy causes oneself in its charge and discharge process to reunite and electrolyte decomposition, reduces active substance with effective contact area of electrolytic solution and bring very large potential safety hazard.Compared to nano particle, assemble the ultrafine grain metal oxide compound be built into, not only by reducing surface energy, can avoiding reuniting and ensureing security, also by fully retaining nanometer size effect, improving its chemical property advantage.Therefore construct one dimension rod-like structure by nano particle and become a kind of good approach improving electrode materials chemical property.
Summary of the invention
The object of this invention is to provide a kind of shaft-like zinc ferrite and preparation method thereof, this preparation method's technique is simple, cost is low, product morphology is controlled, and the zinc ferrite of preparation has excellent chemical property etc.
Above-mentioned purpose of the present invention is achieved through the following technical solutions:
A kind of shaft-like zinc ferrite, described shape zinc ferrite diameter is 7.0-500 nanometer, and length-to-diameter ratio is 3.0 to 20, and shaft-like radial direction is made up of 1 to 20 nano particles, and single nanoparticle is of a size of 7.0-30 nanometer.
The preparation method of above-mentioned a kind of shaft-like zinc ferrite, selects ferrous sulfate and zinc chloride to be raw material, take oxalic acid as precipitation agent, carry out precipitation at room temperature, after hybrid reaction, obtain the shaft-like zinc ferrite constructed by nano particle through ageing, centrifugal, washing, dry and thermal treatment, concrete preparation process is as follows:
(1) in the deionized water through deoxidation treatment, add part hexanaphthene and carry out isolated air, then ferrous sulfate and zinc chloride is added, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.01-5.0 mole/often liter, slow stirring is after 30 minutes, add a small amount of hydrochloric acid, obtain transparent ferrous sulfate and solder(ing)acid;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-2.0 mol/L, and control stirring velocity is 100-2000 rev/min;
(3), completely cut off the condition of air at ferrous sulfate and solder(ing)acid under, the oxalic acid spirituous solution of whipped state is at the uniform velocity joined with the speed of 0.5-4.0 ml/min;
(4) after having reacted, through ageing in 0-36 hour, after centrifugal, washing for several times at 50-100 DEG C dry 3-8 hour, finally thermal treatment 0.5-4 hour at 200-800 DEG C, obtain the shaft-like zinc ferrite constructed by the particle being of a size of 7.0-30 nanometer.
Concentration described in step (1) is the ferrous sulfate of 0.01-5.0 mol/L, and solution condition is isolated air and deoxidation.
Ferrous sulfate described in step (1) and zinc chloride, replace with ferrous sulfate or zinc chloride, product becomes ferric oxide or zinc oxide, but appearance structure does not change, namely still for nano particle is built into rod-like structure.
Alcohol water described in step (2), ethylene glycol or add in solution tensio-active agent substitute; Described alcohol alcohol and ethylene glycol solution substitute; Described alcohol alcohol, ethylene glycol solution and add in solution tensio-active agent substitute; Above-mentioned product is still for nano particle is built into rod-like structure.
Add speed described in step (3) and can regulate and control product length-to-diameter ratio, when speed is 0.1-2.0 ml/min, product length-to-diameter ratio is 10-20, and when speed is 5.0-10 ml/min, product length-to-diameter ratio is 3.0-5.0.
Time of repose described in step (4) is regulation and control product length-to-diameter ratio, and time of repose is 0-2 hour, and product length-to-diameter ratio is 10-20, and time of repose is 24-36 hour, and product length-to-diameter ratio is 3.0-5.0.
Thermal treatment temp described in step (4) is 200-800 DEG C, and heat treatment time is 0.5-4 hour.
The present invention has the following advantages:
1) reaction mechanism of the present invention is that oxalate precursor product decomposes formation nano particle constructs rod-like structure, and presoma pattern changes into nuclear process through morphological template and is genetic to product zinc ferrite.
2) zinc ferrite rod-like structure of the present invention is made up of nanometer zinc ferrite reunion, there is the feature of orientation overlap joint between nano particle; Nanoparticle agglomerates rod-like structure has the large characteristic of nano particle specific surface area; And formed mesoporous between nano particle, be conducive to coordinating the volumetric expansion in lithium ion battery charge and discharge process.
3) the present invention adds by regulation and control the size that speed and digestion time effectively can control nanoparticle agglomerates, control the length-to-diameter ratio of rod-like structure and the distribution number of radial nano particle, can realize radial nano particle distribution number is structure regulating between 1 to 20, length-to-diameter ratio by 3.0 to 20 Morphological control.
4) precipitation process of the present invention is room temperature reaction, and subsequent heat treatment technique is simple, environmental protection, and eventually reduces manufacturing cost and process complexity.
Accompanying drawing explanation
Fig. 1 is zinc ferrite X-ray diffraction analysis prepared by the present invention.
Fig. 2 is zinc ferrite Flied emission morphology observation prepared by the present invention, and can find out that zinc ferrite is rough clearly, shaft-like diameter is; A) 10-100 nanometer, b) 50-500 nanometer, c) 100-400 nanometer.
Fig. 3 is zinc ferrite transmission morphology observation prepared by the present invention, and can find out that zinc ferrite is the meso-hole structure that nano particle constructs between formation and particle clearly, length-to-diameter ratio 18-20, radial particle is 4-5.
Fig. 4 is the charging and discharging curve figure of the zinc ferrite prepared of the present invention as lithium ion battery negative material, and capacity is more than 1200 MAhs/g first.
Fig. 5 is the charge-discharge performance of the zinc ferrite prepared of the present invention as lithium ion battery negative material, and after 50 times, capacity is kept at more than 1000 MAhs/g.
Embodiment
Embodiment one
(1) in the deionized water through deoxidation treatment, add part hexanaphthene and completely cut off air, then ferrous sulfate and zinc chloride is added, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.1-0.25 mol/L, slow stirring is after 30 minutes, add a small amount of hydrochloric acid, obtain transparent ferrous sulfate and solder(ing)acid;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.3-1.7 mole/milliliter, controls to stir for 500-600 rev/min;
(3), completely cut off the condition of air at ferrous sulfate and solder(ing)acid under, the oxalic acid spirituous solution of whipped state is at the uniform velocity joined with the speed of 1.0-2.0 ml/min;
(4) after having reacted, through ageing in 0 hour, after centrifugal, washing for several times at 60 DEG C dry 8 hours, finally thermal treatment 2-3 hour at 400-800 DEG C, the diameter obtaining shaft-like zinc ferrite is 7.0-20 nanometer, length-to-diameter ratio is 18 to 20, and shaft-like radial direction is made up of 1 to 3 nano particles, and single nanoparticle is of a size of 7.0-15 nanometer.
Embodiment two
(1) in the deionized water through deoxygenation process, add part hexanaphthene and completely cut off air, then ferrous sulfate and zinc chloride is added, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.2-1.0 mole/often liter, slow stirring is after 30 minutes, add a small amount of hydrochloric acid, obtain homogeneous transparent ferrous sulfate and solder(ing)acid;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, controls to stir for 1000-2000 rev/min;
(3), completely cut off the condition of air at ferrous sulfate and solder(ing)acid under, the oxalic acid spirituous solution in whipped state is at the uniform velocity joined with the speed of 2.0-3.0 ml/min;
(4) after having reacted, left standstill through 6 hours, after centrifugation, alcohol and water washing for several times at 60 DEG C dry 8 hours, last at 500-700 degree Celsius of lower thermal treatment 3-4 hour, the diameter obtaining shaft-like zinc ferrite is 10-100 nanometer, length-to-diameter ratio is 10 to 15, and shaft-like radial direction is made up of 3 to 5 nano particles, and single nanoparticle is of a size of 10-20 nanometer.
Embodiment three
(1) in the deionized water through deoxygenation process, add part hexanaphthene and completely cut off air, then ferrous sulfate and zinc chloride is added, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.1-1.0 mole/often liter, slow stirring is after 30 minutes, add a small amount of hydrochloric acid, obtain homogeneous transparent ferrous sulfate and solder(ing)acid;
(2) configure oxalic acid alcohol and ethylene glycol mixing solutions, concentration of oxalic acid is 1.0-1.7 mole/milliliter, controls to stir for 100-200 rev/min;
(3), completely cut off the condition of air at ferrous sulfate and solder(ing)acid under, the oxalic acid spirituous solution in whipped state is at the uniform velocity joined with the speed of 0.5-1.0 ml/min;
(4) after having reacted, left standstill through 6 hours, after centrifugation, alcohol and water washing for several times at 60 DEG C dry 7 hours, finally thermal treatment 3-4 hour at 400-600 DEG C, the diameter obtaining shaft-like zinc ferrite is 50-200 nanometer, length-to-diameter ratio is 15 to 18, and shaft-like radial direction is made up of 5 to 8 nano particles, and single nanoparticle is of a size of 7.0-15 nanometer.
Embodiment four
(1) in the deionized water through deoxygenation process, add part hexanaphthene and completely cut off air, then add ferrous sulfate, concentration is 0.1-1.0 mole/often liter, slowly stirs after 30 minutes, adds a small amount of hydrochloric acid, obtain homogeneous transparent ferrous sulfate aqueous solution;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, controls to stir for 1000-2000 rev/min;
(3), completely cut off the condition of air at ferrous sulfate aqueous solution under, the oxalic acid spirituous solution in whipped state is at the uniform velocity joined with the speed of 0.5-1.0 ml/min;
(4) after having reacted, left standstill through 12 hours, after centrifugation, alcohol and water washing for several times at 60 DEG C dry 7 hours, last at 400-600 degree Celsius of lower thermal treatment 3-4 hour, the diameter obtaining shaft-like ferric oxide is 50-500 nanometer, length-to-diameter ratio is 8 to 13, and shaft-like radial direction is made up of 8 to 15 nano particles, and single nanoparticle is of a size of 7.0-15 nanometer.
Embodiment five
(1) in the deionized water through deoxygenation process, add part hexanaphthene and completely cut off air, then add zinc chloride, concentration is 0.1-1.0 mole/often liter, slowly stirs after 30 minutes, adds a small amount of hydrochloric acid, obtain homogeneous transparent solder(ing)acid;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, controls to stir for 300-400 rev/min;
(3), completely cut off the condition of air at solder(ing)acid under, the oxalic acid spirituous solution in whipped state is at the uniform velocity joined with the speed of 0.5-1.0 ml/min;
(4) after having reacted, left standstill through 12 hours, after centrifugation, alcohol and water washing for several times at 60 DEG C dry 7 hours, finally thermal treatment 3-4 hour at 400-600 DEG C, the diameter obtaining shaft-like zinc oxide is 200-900 nanometer, length-to-diameter ratio is 3.0 to 5.0, and shaft-like radial direction is made up of 10 to 20 nano particles, and single nanoparticle is of a size of 7.0-15 nanometer.
Claims (7)
1. a preparation method for shaft-like zinc ferrite, is characterized in that:
The diameter of described shaft-like zinc ferrite is 7.0-500 nanometer, and length-to-diameter ratio is 3.0 to 20, and shaft-like radial direction is made up of 1 to 20 nano particles, and single nanoparticle is of a size of 7.0-30 nanometer, and the preparation method of described shaft-like zinc ferrite is:
Select ferrous sulfate and zinc chloride to be raw material, take oxalic acid as precipitation agent, carry out precipitation at room temperature, after hybrid reaction, obtain the shaft-like zinc ferrite constructed by nano particle through ageing, centrifugal, washing, dry and thermal treatment, concrete preparation process is as follows:
(1) in the deionized water through deoxidation treatment, add part hexanaphthene and carry out isolated air, then ferrous sulfate and zinc chloride is added, ferrous sulfate and zinc chloride mol ratio are 2.0, wherein ferrous sulfate concentration is 0.01-5.0 mol/L, slow stirring is after 30 minutes, add a small amount of hydrochloric acid, obtain transparent ferrous sulfate and solder(ing)acid;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-2.0 mol/L, and control stirring velocity is 100-2000 rev/min;
(3), completely cut off the condition of air at ferrous sulfate and solder(ing)acid under, the oxalic acid spirituous solution of whipped state is at the uniform velocity joined with the speed of 0.5-4.0 ml/min;
(4) after having reacted, through ageing in 0-36 hour, after centrifugal, washing for several times at 50-100 DEG C dry 3-8 hour, finally thermal treatment 0.5-4 hour at 200-800 DEG C, obtain the shaft-like zinc ferrite constructed by the particle being of a size of 7.0-30 nanometer.
2. the preparation method of a kind of shaft-like zinc ferrite according to claim 1, is characterized in that:
Concentration described in step (1) is the ferrous sulfate of 0.01-5.0 mol/L, and solution condition is isolated air and deoxidation.
3. the preparation method of a kind of shaft-like zinc ferrite according to claim 1, is characterized in that:
Alcohol water described in step (2), ethylene glycol or add in solution tensio-active agent substitute; Described alcohol alcohol and ethylene glycol solution substitute; Described alcohol alcohol, ethylene glycol solution and add in solution tensio-active agent substitute; Above-mentioned product is still for nano particle is built into rod-like structure.
4. the preparation method of a kind of shaft-like zinc ferrite according to claim 1, is characterized in that:
Add speed described in step (3) and can regulate and control product length-to-diameter ratio, when speed is 0.1-2.0 ml/min, product length-to-diameter ratio is 10-20, and when speed is 5.0-10 ml/min, product length-to-diameter ratio is 3.0-5.0.
5. the preparation method of a kind of shaft-like zinc ferrite according to claim 1, is characterized in that;
Time of repose described in step (4) is regulation and control product length-to-diameter ratio, and time of repose is 0-2 hour, and product length-to-diameter ratio is 10-20, and time of repose is 24-36 hour, and product length-to-diameter ratio is 3.0-5.0.
6. a preparation method for shaft-like ferric oxide, concrete preparation process is as follows:
(1) in the deionized water through deoxygenation process, add part hexanaphthene and completely cut off air, then add ferrous sulfate, concentration is 0.1-1.0 mol/L, slowly stirs after 30 minutes, adds a small amount of hydrochloric acid, obtain homogeneous transparent ferrous sulfate aqueous solution;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, controls to stir for 1000-2000 rev/min;
(3), completely cut off the condition of air at ferrous sulfate aqueous solution under, the oxalic acid spirituous solution in whipped state is at the uniform velocity joined with the speed of 0.5-1.0 ml/min;
(4) after having reacted, left standstill through 12 hours, after centrifugation, alcohol and water washing for several times at 60 DEG C dry 7 hours, last at 400-600 degree Celsius of lower thermal treatment 3-4 hour, the diameter obtaining shaft-like ferric oxide is 50-500 nanometer, length-to-diameter ratio is 8 to 13, and shaft-like radial direction is made up of 8 to 15 nano particles, and single nanoparticle is of a size of 7.0-15 nanometer.
7. a preparation method for shaft-like zinc oxide, concrete preparation process is as follows:
(1) in the deionized water through deoxygenation process, add part hexanaphthene and completely cut off air, then add zinc chloride, concentration is 0.1-1.0 mol/L, slowly stirs after 30 minutes, adds a small amount of hydrochloric acid, obtain homogeneous transparent solder(ing)acid;
(2) configure oxalic acid spirituous solution, concentration of oxalic acid is 1.0-1.7 mole/milliliter, controls to stir for 300-400 rev/min;
(3), completely cut off the condition of air at solder(ing)acid under, the oxalic acid spirituous solution in whipped state is at the uniform velocity joined with the speed of 0.5-1.0 ml/min;
(4) after having reacted, left standstill through 12 hours, after centrifugation, alcohol and water washing for several times at 60 DEG C dry 7 hours, finally thermal treatment 3-4 hour at 400-600 DEG C, the diameter obtaining shaft-like zinc oxide is 200-900 nanometer, length-to-diameter ratio is 3.0 to 5.0, and shaft-like radial direction is made up of 10 to 20 nano particles, and single nanoparticle is of a size of 7.0-15 nanometer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310223239.0A CN103274474B (en) | 2013-06-06 | 2013-06-06 | Rod-shaped zinc ferrite and its preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310223239.0A CN103274474B (en) | 2013-06-06 | 2013-06-06 | Rod-shaped zinc ferrite and its preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103274474A CN103274474A (en) | 2013-09-04 |
| CN103274474B true CN103274474B (en) | 2015-03-11 |
Family
ID=49057135
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310223239.0A Expired - Fee Related CN103274474B (en) | 2013-06-06 | 2013-06-06 | Rod-shaped zinc ferrite and its preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103274474B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104085930B (en) * | 2014-06-30 | 2015-11-18 | 陕西师范大学 | A kind of preparation method of bigger serface porous flake zinc ferrite |
| CN109399725B (en) * | 2017-08-15 | 2021-04-13 | 中国石油化工股份有限公司 | Preparation method and application of zinc ferrite-containing nano-structure array |
| CN109455766B (en) * | 2018-12-14 | 2021-02-05 | 中国科学院合肥物质科学研究院 | Superfine zinc ferrite nano-particles, preparation method and gas-sensitive application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102531067B (en) * | 2012-03-20 | 2014-04-09 | 新疆大学 | Solid state method for preparing zinc ferrite nanorods |
-
2013
- 2013-06-06 CN CN201310223239.0A patent/CN103274474B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN103274474A (en) | 2013-09-04 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105244501B (en) | A kind of active material of lithium ion battery electrode presoma manganese carbonate nickel | |
| CN106784686A (en) | A kind of doped lithium ion battery class monocrystalline multicomponent material and preparation method thereof | |
| CN100544081C (en) | A kind of nano lithium titanate and with the preparation method of the compound of titanium dioxide | |
| CN106784815B (en) | A kind of iron-based sulfide electrode material, preparation method and the application in solid state battery | |
| CN104810509A (en) | Ferroferric oxide/graphene three-dimensional composite structure as well as preparation method and application thereof | |
| CN106207138A (en) | A kind of method for preparing anode material of lithium-ion battery and application thereof | |
| CN111029572A (en) | Prussian-like blue derivative and preparation method and application thereof | |
| CN105514421B (en) | A kind of modified oxidized nickel negative electrode material and preparation method thereof | |
| CN106698527A (en) | Hydrothermal method for preparing nanometer nickel cobaltate by taking ethylene glycol and water as solvent system | |
| CN107935059A (en) | A kind of nickel cobalt aluminium ternary material precursor and preparation method thereof | |
| CN106410149A (en) | Preparation method of sulfur-doped carbon-coating high-content transition metal sulfide and lithium storage application | |
| CN110707301A (en) | Vanadium trioxide/carbon composite material with nanosphere structure and preparation method and application thereof | |
| CN109817960A (en) | A kind of anode material of lithium-ion battery, sodium-ion battery and preparation method thereof | |
| CN103274474B (en) | Rod-shaped zinc ferrite and its preparation method | |
| CN103387268A (en) | Preparation method of nano-nickel oxide for electrode material of supercapacitor, and nano-nickel oxide prepared by method | |
| CN103435104A (en) | Preparation method for lithium ion battery negative electrode material-nano zinc ferrite | |
| CN106450193A (en) | Nickel sulfide/graphene composite material and preparation method and application thereof | |
| CN104332629A (en) | Preparation method of hollow lithium manganese phosphate nano balls and product | |
| CN107039649A (en) | A kind of multistage hollow microsphere of copper based composite metal oxidate, preparation method and the usage | |
| CN107381656B (en) | Preparation method of lithium ion battery negative electrode material | |
| CN109742340A (en) | A kind of iron manganese phosphate for lithium composite material and preparation method, application | |
| CN103531789A (en) | Iron oxide-carbon nanotube ternary composite material and preparation method thereof | |
| CN105417589A (en) | Preparation method for shuttle-shaped ferroferric oxide-cobaltosic oxide self-assembly structure compound | |
| CN109671937A (en) | A kind of in-situ synthetic method of transiens metal oxide/graphene composite material | |
| CN106409520A (en) | Method for preparing electrode material of lithium-ion-mixed capacitor and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150311 Termination date: 20190606 |