CN107230782A - A kind of preparation method of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate - Google Patents
A kind of preparation method of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate Download PDFInfo
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- CN107230782A CN107230782A CN201710401536.8A CN201710401536A CN107230782A CN 107230782 A CN107230782 A CN 107230782A CN 201710401536 A CN201710401536 A CN 201710401536A CN 107230782 A CN107230782 A CN 107230782A
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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
- H01M4/362—Composites
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention belongs to battery preparation technology field, it is related to a kind of preparation method of sodium-ion battery negative plate, the preparation method of more particularly to a kind of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate, by having wrapped up one layer of class graphene transition metal molybdenum disulfide on natural black pigment nanosphere, carbon ball/molybdenum disulfide material of N doping is prepared, and is prepared into battery；Its preparation method is simple, environmental protection and effectively；The present invention extracts melanin from natural inkfish juice, molybdenum disulfide is wrapped up on its surface by hydro-thermal method, because the main component of melanin is poly-dopamine, it is changed into the carbon ball of N doping in water-heat process, molybdenum disulfide nano sheet is uniformly coated on Nano carbon balls, laod network is formed between nanometer sheet, good conductive network is served；By the CS/MoS of preparation2Material is used as the negative material of sodium-ion battery, improves the stability at negative pole structure and interface, is conducive to commercially producing and applies.
Description
Technical field：
The invention belongs to battery preparation technology field, it is related to a kind of preparation method of sodium-ion battery negative plate, especially relates to
And a kind of preparation method of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate, by natural black pigment nanometer
One layer of class graphene transition metal molybdenum disulfide has been wrapped up on ball, carbon ball/molybdenum disulfide (MoS of N doping is prepared2)
(carbon spheres,CS)(CS/MoS2) material, and it is prepared into battery.
Background technology：
Sodium-ion battery is because abundance, preparation technology are simple, pollution-free, cheap and are distributed in nature
Wide the advantages of, be considered as the preferable substitute of lithium ion battery always.More anode material of lithium-ion battery is studied at present
Mainly various carbon-based materials, such as graphite, carbonaceous mesophase spherules, hard carbon, the chemical property of carbon-based material have with its structure
Substantial connection, meanwhile, metal_based material, due to higher theoretical capacity, is also the preferable anode material of lithium-ion battery of a class,
It wherein common are metal alloy, metal oxide and metal sulfide etc..Two-dimentional transient metal sulfide have low cost and
The characteristics of high theoretical specific capacity, the study hotspot as sode cell negative material；Because interlamellar spacing is big, interlaminar action power compares
Weak, two-dimentional transient metal sulfide is easily achieved the reversible electrochemical deintercalation of sodium ion；Wherein, molybdenum disulfide is a kind of typical case
Two-dimentional transient metal sulfide, have the advantages that theoretical capacity is high, but its electric conductivity is poor, causes its high rate performance to be paid no attention to
Think.Therefore the present invention is intended to provide a kind of preparation method of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate, knot
Close the advantage of the high theoretical specific capacity of molybdenum disulfide and N doping carbon ball high conductivity, for prepare with high charge-discharge specific capacity,
The sodium-ion battery of good high rate performance and long circulation life, with good economic benefit and social benefit.
The content of the invention：
The present invention is in order to overcome the shortcomings of the prior art, seek to design a kind of nitrogen-doped carbon nanosphere/molybdenum disulfide
The preparation method of sodium-ion battery negative plate, by having wrapped up one layer of class graphene transition metal on natural black pigment nanosphere
Molybdenum disulfide, prepares the material of carbon ball/molybdenum disulfide of N doping, and is prepared into battery.
To achieve these goals, nitrogen-doped carbon nanosphere of the present invention/molybdenum disulfide sodium-ion battery negative plate
Preparation technology, specifically include：
(1) the inkfish capsule of select is broken and is taken out black liquor, be then added in ultra-pure water and centrifuged
Washing 2-10 time after, then by the melanin after centrifugation be put into bag filter progress dialysis purification, then the melanin after purification is entered
Row freeze-drying obtains natural black pigment powder standby to powder；
(2) according to weight proportion take natural black pigment powder be distributed to 25-35 times of weight than ultra-pure water in, carry out ultrasound
The finely dispersed natural black pigment aqueous solution is prepared after 10 minutes；
(3) take sodium molybdate and thioacetamide to be added in the ultra-pure water of 20-30 times of weight ratio according to weight proportion, carry out
Ultrasonic disperse is added to after 10-60 minutes in the natural black pigment aqueous solution of step (2) preparation, continues 10-60 points of magnetic agitation
Mixed dispersion liquid is obtained after clock；
(4) mixed dispersion liquid for obtaining step (3) is placed in ptfe autoclave, is entered at 150-200 DEG C
Water-filling thermal response 24-36 hours, then carries out washing and is dried to obtain nitrogen-doped carbon nanosphere/molybdenum disulfide sodium ion composite Nano
Material powder；
(5) CS/MoS for preparing step (4)2Composite nano materials powder and Super P (conductive black) and PVDF are (molten
In NMP) according to weight ratio be 15:5:2 ratio, which is put into mortar, grinds to form uniform slurry, and slurry then is coated on into copper foil
On, copper foil is placed under the infrared baking lamp that temperature is 60 DEG C and baked to dry tack free, then copper foil of the lamp after roasting is placed on vacuum
8-10h is toasted at 100-120 DEG C in baking oven, then by the copper foil roll-in after baking and a diameter of 12mm electrode slice is cut to and produces
Finished product.
The present invention relates to a kind of primary raw material parts by weight of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate
For：1-5 parts of natural black pigment, 1-20 parts of sodium molybdate, 8-40 parts of thioacetamide, 5-20 parts of conductive black, PVDF (polyvinylidene fluorides
Alkene) 0.001-0.1 parts, 1-2 parts of NMP (1-METHYLPYRROLIDONE), 20-200 parts of copper foil；Wherein natural black pigment is derived from inkfish capsule
In, remaining is commercially available prod.
Compared with prior art, its preparation method is simple, environmental protection and effectively by the present invention；Extracted from natural inkfish juice
Melanin, molybdenum disulfide is wrapped up by hydro-thermal method on its surface, because the main component of melanin is poly-dopamine, water-heat process
In be changed into the carbon ball of N doping, molybdenum disulfide nano sheet is uniformly coated on Nano carbon balls, and loaded webs are formed between nanometer sheet
Network, serves good conductive network；By the CS/MoS of preparation2Material is used as the negative material of sodium-ion battery, improves negative
Pole structure and the stability at interface, improve the cyclical stability of negative pole, are conducive to commercially producing and apply；It is prepared by the present invention
CS/MoS2Sodium-ion battery, in 80mA g-1First discharge specific capacity under current density is up to 794mAh g-1；In 1000mA
g-1Under high current density, 343mAh g are remained at-1。
Brief description of the drawings：
The CS/MoS that Fig. 1 is prepared for the present invention2Composite nano materials scanning electron microscope (SEM) photograph.
The transmission electron microscope picture for the natural black pigment that Fig. 2 extracts for the present invention.
The CS/MoS that Fig. 3 is prepared for the present invention2Sodium-ion battery is in 80mA g-1Current density under cycle performance and storehouse
Human relations efficiency chart.
Fig. 4 is CS/MoS prepared by the embodiment of the present invention2The high rate performance of sodium-ion battery.
Embodiment：
It is described further below by embodiment and with reference to accompanying drawing.
Embodiment 1：
The preparation technology of the nitrogen-doped carbon nanosphere that the present embodiment is related to/molybdenum disulfide sodium-ion battery negative plate, specifically
Including：
(1) the inkfish capsule of select is broken and is taken out black liquor, be then added in ultra-pure water and centrifuged
Washing 2-10 time after, then by the melanin after centrifugation be put into bag filter progress dialysis purification, then the melanin after purification is entered
Row freeze-drying obtains natural black pigment powder standby to powder；
(2) according to weight proportion take natural black pigment powder be distributed to 25-35 times of weight than ultra-pure water in, carry out ultrasound
The finely dispersed natural black pigment aqueous solution is prepared after 10 minutes；
(3) take sodium molybdate and thioacetamide to be added in the ultra-pure water of 20-30 times of weight ratio according to weight proportion, carry out
Ultrasonic disperse is added to after 10-60 minutes in the natural black pigment aqueous solution of step (2) preparation, continues 10-60 points of magnetic agitation
Mixed dispersion liquid is obtained after clock；
(4) mixed dispersion liquid for obtaining step (3) is placed in ptfe autoclave, is entered at 150-200 DEG C
Water-filling thermal response 24-36 hours, then carries out washing and is dried to obtain nitrogen-doped carbon nanosphere/molybdenum disulfide sodium ion composite Nano
Material powder；
(5) CS/MoS for preparing step (4)2Composite nano materials powder and Super P (conductive black) and PVDF are (molten
In NMP) according to weight ratio be 15:5:2 ratio, which is put into mortar, grinds to form uniform slurry, and slurry then is coated on into copper foil
On, copper foil is placed under the infrared baking lamp that temperature is 60 DEG C and baked to dry tack free, then copper foil of the lamp after roasting is placed on vacuum
8-10h is toasted at 100-120 DEG C in baking oven, then by the copper foil roll-in after baking and a diameter of 12mm electrode slice is cut to and produces
Finished product.
The present embodiment is related to a kind of primary raw material weight of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate
Part it is：1-5 parts of natural black pigment, 1-20 parts of sodium molybdate, 8-40 parts of thioacetamide, 5-20 parts of conductive black, PVDF (gathers inclined fluorine
Ethene) 0.001-0.1 parts, 1-2 parts of NMP (1-METHYLPYRROLIDONE), 20-200 parts of copper foil；Wherein natural black pigment is derived from inkfish
In capsule, remaining is commercially available prod.
Sodium-ion battery negative plate made from the present embodiment and metallic sodium piece and electrolyte are assembled into sodium-ion battery, used
In carrying out constant current charge-discharge test, electrolyte is NaClO4It is 1 to be dissolved in volume ratio:1 ethylene carbonate (EC) and propylene carbonate
In ester (PC), and add 5vol% fluorinated ethylene carbonate (FEC)；Cyclic voltammetric (CV) test voltage range be
0.01V-3V, sweep speed is 0.1mVs-1, tester is CHI610E electrochemical workstations, and test result is as follows：
As shown in figure 3, CS/MoS2The 80mA g in sodium-ion battery-1Current density under cycle performance.Discharge first
Specific capacity is 794mAh g-1, initial charge specific capacity is 535mAh g-1, preceding 34 circle specific capacity is always growth state, to 34
Circle specific discharge capacity reaches 600mAh g-1, then there is downward trend, 80 circle specific discharge capacities remain at 288mAh g-1It is left
It is right.Fig. 4 is CS/MoS2High rate performance, in 20,40,80,320,640,1000mA g-1Current density under its discharge specific volume
Amount is respectively 468,465,439,397,369,342mAh g-1.Illustrate that material has good high rate performance, this may be with biology
There is provided good electric charge transmission channel is relevant for the good electric conductivity of matter carbon ball.
Claims (2)
1. the preparation method of a kind of nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate, it is characterised in that it is prepared
Technique is specifically included：
(1) the inkfish capsule of select is broken and is taken out black liquor, be then added in ultra-pure water and carry out centrifuge washing
After 2-10 times, then by the melanin after centrifugation be put into bag filter carry out dialysis purification, then by after purification melanin carry out it is cold
It is lyophilized dry to powder, obtain natural black pigment powder standby；
(2) according to weight proportion take natural black pigment powder be distributed to 25-35 times of weight than ultra-pure water in, carry out ultrasound 10 points
The finely dispersed natural black pigment aqueous solution is prepared after clock；
(3) take sodium molybdate and thioacetamide to be added in the ultra-pure water of 20-30 times of weight ratio according to weight proportion, carry out ultrasound
In the natural black pigment aqueous solution that step (2) preparation is added to after scattered 10-60 minutes, continue magnetic agitation after 10-60 minutes
Obtain mixed dispersion liquid；
(4) mixed dispersion liquid for obtaining step (3) is placed in ptfe autoclave, and water-filling is entered at 150-200 DEG C
Thermal response 24-36 hours, then carries out washing and is dried to obtain nitrogen-doped carbon nanosphere/molybdenum disulfide sodium ion composite nano materials
Powder；
(5) CS/MoS for preparing step (4)2Composite nano materials powder (is dissolved in Super P (conductive black) and PVDF
NMP it is) 15 according to weight ratio:5:2 ratio, which is put into mortar, grinds to form uniform slurry, and slurry then is coated on into copper foil
On, copper foil is placed under the infrared baking lamp that temperature is 60 DEG C and baked to dry tack free, then copper foil of the lamp after roasting is placed on vacuum
8-10h is toasted at 100-120 DEG C in baking oven, then by the copper foil roll-in after baking and a diameter of 12mm electrode slice is cut to and produces
Nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate finished product.
2. the preparation method of nitrogen-doped carbon nanosphere according to claim 1/molybdenum disulfide sodium-ion battery negative plate, its
It is characterised by that described nitrogen-doped carbon nanosphere/molybdenum disulfide sodium-ion battery negative plate primary raw material parts by weight are：Natural black
1-5 parts of pigment, 1-20 parts of sodium molybdate, 8-40 parts of thioacetamide, 5-20 parts of conductive black, PVDF (Kynoar) 0.001-
0.1 part, 1-2 parts of NMP (1-METHYLPYRROLIDONE), 20-200 parts of copper foil；Wherein natural black pigment is derived from inkfish capsule, and remaining is equal
For commercially available prod.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273691A (en) * | 2018-09-25 | 2019-01-25 | 岭南师范学院 | A kind of molybdenum disulfide/nitrogen-doped carbon composite material and preparation method and application |
| CN110787823A (en) * | 2019-09-30 | 2020-02-14 | 温州大学 | Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle, and preparation method and application thereof |
-
2017
- 2017-05-31 CN CN201710401536.8A patent/CN107230782A/en active Pending
Non-Patent Citations (2)
| Title |
|---|
| DONG XIE等: "" Nitrogen-Doped Carbon Embedded MoS2 Microspheres as Advanced Anodes for Lithium- and Sodium-Ion Batteries"", 《CHEMISTRY A EUROPEAN JOURNAL》 * |
| 风炎之雁等: ""乌贼墨"", 《百度百科网》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109273691A (en) * | 2018-09-25 | 2019-01-25 | 岭南师范学院 | A kind of molybdenum disulfide/nitrogen-doped carbon composite material and preparation method and application |
| CN109273691B (en) * | 2018-09-25 | 2020-12-15 | 岭南师范学院 | Molybdenum disulfide/nitrogen-doped carbon composite material and preparation method and application thereof |
| CN110787823A (en) * | 2019-09-30 | 2020-02-14 | 温州大学 | Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle, and preparation method and application thereof |
| CN110787823B (en) * | 2019-09-30 | 2022-08-12 | 温州大学 | Three-dimensional nitrogen-doped flower-shaped carbon sphere loaded superfine nitrogen-doped molybdenum carbide nano particle as well as preparation method and application thereof |
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Application publication date: 20171003 |