CN107146885A - CoP hollow tubular nano materials and its preparation method and application - Google Patents
CoP hollow tubular nano materials and its preparation method and application Download PDFInfo
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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
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
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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
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Abstract
The invention discloses a kind of CoP hollow tubulars nano material and its preparation method and application, the CoP nano materials are three-dimensional hollow tubular structure, and length is 1 5um, a diameter of 80 250nm.The preparation method includes：1) cobalt source and part are subjected to complexation reaction in water, then by reaction product drying with obtained purple powder presoma；2) three (methylol) aminomethanes are dissolved in purple precursor water solution, are subsequently added into hydrochloric acid, then added dopamine and carry out haptoreaction gray product is made；3) in the presence of protection gas, gray product is heat-treated black product is made；4) in the presence of protection gas, phosphorus source and black product are calcined CoP hollow tubular nano materials are made.The CoP hollow tubular nano materials have excellent chemical property can be as lithium ion battery electrode material, and the preparation method process is simple and raw material is easy to get.
Description
Technical field
The present invention relates to CoP nano materials, in particular it relates to CoP hollow tubular nano materials and preparation method thereof and should
With.
Background technology
Increasingly increase with social energy shortage and the mankind to energy demand, traditional energy is in reserves, energy efficiency, ring
Border pollute and cost in terms of constraint increasingly highlight, therefore active demand some high-energy, the energy storage material of high power density
To solve energy crisis, lithium ion battery arises at the historic moment as energy storage device.Lithium ion battery has voltage high, small volume, electricity
The advantages of capacity is big and pollution-free.In lithium ion battery, commercialization graphite negative electrodes material reaches 372mAh/g theoretical appearance
Limiting value is measured, the development of electrokinetic cell is seriously constrained.So finding higher capacity, the negative material of economic security substitutes graphite
Material has turned into current research problem urgently to be resolved hurrily.CoP materials have higher theoretical capacity (894mAh/g), low cost,
Superior security performance, the advantages of be easy to be made；Have in negative material as high power capacity high rate capability material and well should
Use prospect.
With the progress of recent nanometer technology, there are various synthetic methods to be used to synthesize Co2P and CoP nano materials.So
And, it has been reported that CoP anodes be also not carried out good lithium storage properties (for example stable cycle performance and excellent times it is forthright
Can).Therefore, the regulation and control of structure and composition are carried out to CoP materials, it is that this area is anxious to obtain the CoP materials with more excellent properties
The technical problem that need to be solved.
The content of the invention
It is an object of the invention to provide a kind of CoP hollow tubulars nano material and its preparation method and application, the CoP is hollow
Tubular nanometer material has excellent chemical property can be as lithium ion battery electrode material, and the preparation method
Process is simple and raw material is easy to get.
To achieve these goals, the invention provides a kind of CoP hollow tubulars nano material, the CoP nano materials are
Three-dimensional hollow tubular structure, length is 1-5um, a diameter of 80-250nm.
Present invention also offers a kind of preparation method of above-mentioned CoP hollow tubular nano materials, the preparation method includes：
1) cobalt source and part are subjected to complexation reaction in water, then by reaction product drying with obtained purple powder forerunner
Body；
2) three (methylol) aminomethanes are dissolved in purple precursor water solution, are subsequently added into hydrochloric acid, then add
Dopamine carries out haptoreaction gray product is made；
3) in the presence of protection gas, gray product is heat-treated black product is made；
4) in the presence of protection gas, phosphorus source and black product are calcined CoP hollow tubular nano materials are made.
Invention further provides a kind of application of above-mentioned CoP hollow tubular nano materials in lithium ion battery.
Pass through above-mentioned technical proposal, the present invention：The precursor powder of purple powder is prepared by solvent-thermal method first；Then will
Purple powder precursor powder carries out dopamine cladding；Gray product after dopamine is coated carbonize obtaining gray powder
End；The black product after charing is finally subjected to the phosphatization cobalt that phosphatization obtains hollow tubular structure.Obtained by electro-chemical test
Know that the nano material has outstanding chemical property, can be used as the electrode material of lithium ion battery.Meanwhile, the preparation
Method has the advantages that process is simple and raw material is easy to get.
Other features and advantages of the present invention will be described in detail in subsequent embodiment part.
Brief description of the drawings
Accompanying drawing is, for providing a further understanding of the present invention, and to constitute a part for specification, with following tool
Body embodiment is used to explain the present invention together, but is not construed as limiting the invention.In the accompanying drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph for detecting the purple powder presoma in example 1 in embodiment 1；
Fig. 2 is the scanning electron microscope (SEM) photograph for detecting the black product in example 1 in embodiment 1；
Fig. 3 is the scanning electron microscope (SEM) photograph for detecting A1 in example 1；
Fig. 4 is the transmission electron microscope picture for detecting A1 in example 1；
Fig. 5 is the X-ray diffractogram for detecting A1 in example 1；
Fig. 6 is the discharge cycles curve map for detecting A1 in example 1.
Embodiment
The embodiment to the present invention is described in detail below.It should be appreciated that described herein specific
Embodiment is merely to illustrate and explain the present invention, and is not intended to limit the invention.
The end points and any value of disclosed scope are not limited to the accurate scope or value herein, these scopes or
Value should be understood to comprising the value close to these scopes or value.For number range, between the endpoint value of each scope, respectively
It can be combined with each other between the endpoint value of individual scope and single point value, and individually between point value and obtain one or more
New number range, these number ranges should be considered as specific open herein.
The invention provides a kind of CoP hollow tubulars nano material, the CoP nano materials are three-dimensional hollow tubular structure,
Length is 1-5um, a diameter of 80-250nm.
Present invention also offers a kind of preparation method of above-mentioned CoP hollow tubular nano materials, the preparation method includes：
1) cobalt source and part are subjected to complexation reaction in water, then by reaction product drying with obtained purple powder forerunner
Body；
2) three (methylol) aminomethanes are dissolved in purple precursor water solution, are subsequently added into hydrochloric acid, then add
Dopamine carries out haptoreaction gray product is made；
3) in the presence of protection gas, gray product is heat-treated black product is made；
4) in the presence of protection gas, phosphorus source and black product are calcined CoP hollow tubular nano materials are made.
In the step 1 of above-mentioned preparation method) in, the actual conditions of complexation reaction can be selected in wide scope, still
In order that obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that in step 1) in, coordination
Reaction at least meets following condition：Reaction temperature is 100-150 DEG C, and the reaction time is 10-15h.
In the step 1 of above-mentioned preparation method) in, the actual conditions of drying can be selected in wide scope, but in order to
Make obtained CoP hollow tubulars nano material that there is more excellent chemical property, it is preferable that in step 1) in, drying is at least
Meet following condition：Drying temperature is 60-80 DEG C, and drying time is 8-12h.
In the step 1 of above-mentioned preparation method) in, the consumption of each material can be selected in wide scope, but in order that
Obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that in step 1) in, cobalt source and part
Mol ratio be 1：1-1.5.It is highly preferred that the cobalt source relative to 5mmol, the consumption of water is 40-60mL.
In the step 1 of above-mentioned preparation method) in, the specific species of part can be selected in wide scope, but in order to
Make obtained CoP hollow tubulars nano material that there is more excellent chemical property, it is preferable that part is selected from urea, Wu Luotuo
At least one of product.
In the step 1 of above-mentioned preparation method) in, the specific species of cobalt source can be selected in wide scope, but in order to
Make obtained CoP hollow tubulars nano material that there is more excellent chemical property, it is preferable that cobalt source is selected from CoCl2﹒ 6H2O, nitre
At least one of sour cobalt and cobaltous sulfate.
In addition, step 1) filling order can be selected in wide scope, but in order that step 1) in each material
Fully reaction, step 1) filling order be：First cobalt source and water are stirred, part is then added and is reacted.Wherein, stirring
Condition can be selected in wide scope, in order to further improve reaction rate, it is highly preferred that stirring meets following condition：Stir
Temperature is mixed for 15-35 DEG C, mixing time is 8-15min.
In the step 2 of above-mentioned preparation method) in, catalytic condition can be selected in wide scope, but in order to
Make obtained CoP hollow tubulars nano material that there is more excellent chemical property, it is preferable that in step 2) in, haptoreaction
At least meet following condition：Reaction temperature is 0-30 DEG C, and the reaction time is 24-48h.
In the step 2 of above-mentioned preparation method) in, the consumption of each material can be selected in wide scope, but in order that
Obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that in step 2) in, relative to 5mmol
Purple presoma made from cobalt source, the consumption of three (methylol) aminomethanes is 0.5-2.0g, and the consumption of dopamine is 50-
200mg, the consumption of hydrochloric acid is that the pH of 5-10 drops and hydrochloric acid is 6.5-10.5, and the volume of purple precursor water solution is 40-60mL.
In the step 3 of above-mentioned preparation method) in, the condition of heat treatment can be selected in wide scope, but in order that
Obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that in step 3) in, heat treatment is at least
Meet following condition：Treatment temperature is 300-600 DEG C, and processing time is 0.5-5h.
Meanwhile, in order that obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that
Before heat treatment, step 3) also include：Gray product is warming up to 300-600 from the 15-35 DEG C of speed with 1.5-2.5 DEG C/min
℃。
In the step 4 of above-mentioned preparation method) in, the condition of calcining can be selected in wide scope, but in order that system
The CoP hollow tubulars nano material obtained has more excellent chemical property, it is preferable that in step 4) in, calcining is at least met
Following condition：Calcining heat is 350-450 DEG C, and calcination time is 2-6h.
In addition, in order that obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that
Before calcining, step 4) also include：By the mixture of phosphorus source and black product from the 15-35 DEG C of speed with 1.5-2.5 DEG C/min
It is warming up to 300-600 DEG C.
In the step 4 of above-mentioned preparation method) in, the consumption of phosphorus source and black product can be selected in wide scope, but
It is in order that obtained CoP hollow tubulars nano material has more excellent chemical property, it is preferable that in step 4) in, phosphorus
The weight ratio of source and black product is 1：5-30.
In the step 4 of above-mentioned preparation method) in, the species of phosphorus source can be selected in wide scope, but in order that system
The CoP hollow tubulars nano material obtained has more excellent chemical property, it is preferable that phosphorus source is selected from sodium hypophosphite, di(2-ethylhexyl)phosphate
At least one of hydrogen ammonium and diammonium hydrogen phosphate.
Invention further provides a kind of application of above-mentioned CoP hollow tubular nano materials in lithium ion battery.
The present invention will be described in detail by way of examples below.
Embodiment 1
1) at 25 DEG C, 5mmol CoCl are taken respectively2﹒ 6H2O、5mmolCO(NH2)2Add in 50ml deionized waters, stirring
After 10min, it is transferred in reactor；React in an oven (reaction temperature is 120 DEG C, and the reaction time is 12h)；It is subsequently cooled to
25℃；Finally product is put in an oven, 12h is dried at 60 DEG C and obtains purple powder presoma.
2) resulting purple powder presoma is added in beaker, and 50ml deionized waters is added into beaker, it is ultrasonic
10min；1.2114g tri- (methylol) aminomethane is added in beaker again, stirring until completely dissolved, adds 8 and drips concentrated hydrochloric acid
After (PH is 8.5) is well mixed, 50mg dopamines are added, gray product is obtained in stirring 24h at 25 DEG C.
3) in N2Under atmosphere, above-mentioned gray product is warming up to 400 DEG C in tube furnace from 25 DEG C of speed with 2 DEG C/min
2h is calcined, black product is obtained.
4) in N2Under atmosphere, by 0.06g black products, 1.2g sodium hypophosphites (sodium hypophosphite is placed on porcelain boat upper end) in tubular type
400 DEG C of calcining 4h are warming up to from 25 DEG C of speed with 2 DEG C/min in stove, CoP hollow tubular nano materials A1 is obtained.
Embodiment 2
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A2, is not both：Step 1) middle stirring
Time is 20min.
Embodiment 3
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A3, is not both：Step 1) middle drying
Temperature is 80 DEG C.
Embodiment 4
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A4, is not both：Step 1) middle drying
Time is 8h.
Embodiment 5
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A5, is not both：Step 2) ultrasound
Time is 20min.
Embodiment 6
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A6, is not both：Step 2) in three (hydroxyls
Methyl) aminomethane consumption be 2g.
Embodiment 7
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A7, is not both：Step 2) in DOPA
The consumption of amine is 200mg.
Embodiment 8
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A8, is not both：Step 2) middle stirring
Time is 48h.
Embodiment 9
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A9, is not both：Step 3) middle reaction
500 DEG C of temperature.
Embodiment 10
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A10, is not both：Step 3) middle reaction
Time is 4h.
Embodiment 11
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A11, is not both：Step 3) middle heating
Speed is 1 DEG C/min.
Embodiment 12
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A12, is not both：Step 4) in black
The weight ratio of product and sodium hypophosphite is 1：5.
Embodiment 13
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A13, is not both：Step 4) in black
The weight ratio of product and sodium hypophosphite is 1：10.
Embodiment 14
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A14, is not both：Step 4) in black
The weight ratio of product and sodium hypophosphite is 1：30.
Embodiment 15
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A15, is not both：Step 4) middle reaction
Time is 6h.
Embodiment 16
Method according to embodiment 1 carries out preparing CoP hollow tubular nano material A16, is not both：Step 4) middle heating
Speed is 1 DEG C/min.
Detect example 1
1) by Hitachi/ Hitachis s-4800 SEM (SEM) to the purple powder presoma in embodiment 1
Electronic Speculum detection is scanned, testing result is shown in Fig. 1, and the presoma pattern is nano wire as seen from the figure, and length is 1-5um, diameter
For 80-250nm.
2) black product in embodiment 1 is carried out by Hitachi/ Hitachis s-4800 SEM (SEM)
ESEM detects that testing result is shown in Fig. 2, and the black product pattern is nanometer rods as seen from the figure, and length is 1-5um, a diameter of
80-250nm。
3) it is scanned Electronic Speculum to A1 by Hitachi/ Hitachis s-4800 SEM (SEM) to detect, detection
As a result Fig. 3 is seen, the product morphology is nanometer rods as seen from the figure, and length is 1-5um, a diameter of 80-250nm.
4) transmission electron microscope inspection is carried out to A1 by Hitachi/ Hitachis HT-7700120KV transmission electron microscopes (TEM)
Survey, testing result is shown in Fig. 4, and the nanometer rods are hollow structures as seen from the figure, and length is 1-5um, a diameter of 80-250nm.
5) Shimadzu XRD-6000X-ray diffractometer, Cu targets K (radiation is passed through ) right
A1 carries out X-ray diffraction detection, and testing result is shown in Fig. 5, and the product is CoP as seen from the figure.
6) discharge cycles curve detection is carried out to A1 by new prestige tester, testing result is shown in Fig. 6, as seen from the figure the material
Better performances.
A2-A16 is detected in the same manner, testing result is basically identical with A1.
The preferred embodiment of the present invention described in detail above, still, the present invention are not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, a variety of simple variants can be carried out to technical scheme, this
A little simple variants belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to it is various can
The combination of energy no longer separately illustrates.
In addition, various embodiments of the present invention can be combined randomly, as long as it is without prejudice to originally
The thought of invention, it should equally be considered as content disclosed in this invention.
Claims (10)
1. a kind of CoP hollow tubulars nano material, it is characterised in that the CoP nano materials are three-dimensional hollow tubular structure, long
Spend for 1-5um, a diameter of 80-250nm.
2. a kind of preparation method of CoP hollow tubulars nano material as claimed in claim 1, it is characterised in that the preparation
Method includes：
1) cobalt source and part are subjected to complexation reaction in water, then by reaction product drying with obtained purple powder presoma；
2) three (methylol) aminomethanes are dissolved in purple precursor water solution, are subsequently added into hydrochloric acid, then add DOPA
Amine carries out haptoreaction gray product is made；
3) in the presence of protection gas, the gray product is heat-treated black product is made；
4) in the presence of protection gas, phosphorus source and the black product are calcined the CoP hollow tubulars nanometer is made
Material.
3. preparation method according to claim 2, wherein, in step 1) in, the complexation reaction at least meets following bar
Part：Reaction temperature is 100-150 DEG C, and the reaction time is 10-15h；
Preferably, in step 1) in, the drying at least meets following condition：Drying temperature is 60-80 DEG C, and drying time is 8-
12h。
4. the preparation method according to Claims 2 or 3, wherein, in step 1) in, the mol ratio of the cobalt source and part is
1：1-1.5；
Preferably, the part is selected from least one of urea, methenamine；
It is highly preferred that the cobalt source is selected from CoCl2﹒ 6H2At least one of O, cobalt nitrate and cobaltous sulfate.
5. preparation method according to claim 4, wherein, in step 2) in, the haptoreaction at least meets following bar
Part：Reaction temperature is 0-30 DEG C, and the reaction time is 24-48h.
6. preparation method according to claim 4, wherein, in step 2) in, relative to the purple made from 5mmol cobalt sources
Color presoma, the consumption of described three (methylol) aminomethane is 0.5-2.0g, and the consumption of the dopamine is 50-200mg, institute
The consumption for stating hydrochloric acid is that the pH of 5-10 drops and hydrochloric acid is 6.5-10.5, and the volume of the purple precursor water solution is 40-60mL.
7. the preparation method according to claim 5 or 6, wherein, in step 3) in, the heat treatment at least meets following bar
Part：Treatment temperature is 300-600 DEG C, and processing time is 0.5-5h；
Preferably, before the heat treatment, step 3) also include：By the gray product from 15-35 DEG C with 1.5-2.5 DEG C/
Min speed is warming up to 300-600 DEG C.
8. preparation method according to claim 7, wherein, in step 4) in, the calcining at least meets following condition：Forge
It is 350-450 DEG C to burn temperature, and calcination time is 2-6h；
Preferably, before the calcining, step 4) also include：By the mixture of phosphorus source and black product from 15-35 DEG C
300-600 DEG C is warming up to 1.5-2.5 DEG C/min speed.
9. preparation method according to claim 8, wherein, in step 4) in, the weight ratio of phosphorus source and black product
For 1：5-30；
Preferably, phosphorus source is selected from least one of sodium hypophosphite, ammonium dihydrogen phosphate and diammonium hydrogen phosphate.
10. a kind of application of CoP hollow tubulars nano material as claimed in claim 1 in lithium ion battery.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242538A (en) * | 2017-12-27 | 2018-07-03 | 轻工业化学电源研究所 | A kind of preparation method of hollow sandwich type iron-based negative material |
| CN109518216A (en) * | 2018-11-15 | 2019-03-26 | 同济大学 | A kind of phosphatization cobalt nanometer frame and its preparation and application |
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| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105803580A (en) * | 2016-04-15 | 2016-07-27 | 东华大学 | Preparation method of cobalt phosphide hollow nano-fiber material |
Non-Patent Citations (1)
| Title |
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| XU, XIJUN，等: "Self-Supported CoP Nanorod Arrays Grafted on Stainless Steel as an Advanced Integrated Anode for Stable and Long-Life LithiumIon Batteries", 《CHEMISTRY-A EUROPEAN JOURNAL》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108242538A (en) * | 2017-12-27 | 2018-07-03 | 轻工业化学电源研究所 | A kind of preparation method of hollow sandwich type iron-based negative material |
| CN109518216A (en) * | 2018-11-15 | 2019-03-26 | 同济大学 | A kind of phosphatization cobalt nanometer frame and its preparation and application |
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