CN109950480A - Preparation method of carbon-coated tin sulfide nanobelt of lithium ion battery negative electrode material - Google Patents
Preparation method of carbon-coated tin sulfide nanobelt of lithium ion battery negative electrode material Download PDFInfo
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- CN109950480A CN109950480A CN201810112212.7A CN201810112212A CN109950480A CN 109950480 A CN109950480 A CN 109950480A CN 201810112212 A CN201810112212 A CN 201810112212A CN 109950480 A CN109950480 A CN 109950480A
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- nanobelt
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- artificial gold
- carbon
- tin sulfide
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- 239000002127 nanobelt Substances 0.000 title claims abstract description 58
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 12
- AFNRRBXCCXDRPS-UHFFFAOYSA-N tin(ii) sulfide Chemical compound [Sn]=S AFNRRBXCCXDRPS-UHFFFAOYSA-N 0.000 title abstract 8
- 239000007773 negative electrode material Substances 0.000 title description 8
- 238000000576 coating method Methods 0.000 claims abstract description 25
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000243 solution Substances 0.000 claims abstract description 13
- 229960003638 dopamine Drugs 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 10
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 239000007983 Tris buffer Substances 0.000 claims abstract description 8
- 229920001690 polydopamine Polymers 0.000 claims abstract description 8
- 238000001354 calcination Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 239000012298 atmosphere Substances 0.000 claims abstract description 3
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 3
- 238000001816 cooling Methods 0.000 claims abstract description 3
- 238000000967 suction filtration Methods 0.000 claims abstract description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 56
- 239000010931 gold Substances 0.000 claims description 56
- 229910052737 gold Inorganic materials 0.000 claims description 56
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 239000011248 coating agent Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 238000005253 cladding Methods 0.000 claims description 9
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 8
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- 239000004202 carbamide Substances 0.000 claims description 8
- 235000011150 stannous chloride Nutrition 0.000 claims description 8
- 239000001119 stannous chloride Substances 0.000 claims description 8
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 8
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012456 homogeneous solution Substances 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000000872 buffer Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 229910052754 neon Inorganic materials 0.000 claims description 2
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 8
- 238000006116 polymerization reaction Methods 0.000 abstract description 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000003763 carbonization Methods 0.000 abstract 1
- 239000010406 cathode material Substances 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 10
- 239000011889 copper foil Substances 0.000 description 10
- 229960000935 dehydrated alcohol Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000002242 deionisation method Methods 0.000 description 5
- 239000006230 acetylene black Substances 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000002002 slurry Substances 0.000 description 4
- 229910001290 LiPF6 Inorganic materials 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 239000011149 active material Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052976 metal sulfide Inorganic materials 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 1
- IMTNQIVQITYBJV-UHFFFAOYSA-N 4-(2-hydrazinylethyl)benzene-1,2-diol Chemical compound NNCCC1=CC=C(O)C(O)=C1 IMTNQIVQITYBJV-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WTDRDQBEARUVNC-UHFFFAOYSA-N L-Dopa Natural products OC(=O)C(N)CC1=CC=C(O)C(O)=C1 WTDRDQBEARUVNC-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- MHUWZNTUIIFHAS-CLFAGFIQSA-N dioleoyl phosphatidic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC(COP(O)(O)=O)OC(=O)CCCCCCC\C=C/CCCCCCCC MHUWZNTUIIFHAS-CLFAGFIQSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229960004756 ethanol Drugs 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 229960004502 levodopa Drugs 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 235000010413 sodium alginate Nutrition 0.000 description 1
- 239000000661 sodium alginate Substances 0.000 description 1
- 229940005550 sodium alginate Drugs 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- 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
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a preparation method of a carbon-coated tin sulfide nanobelt of a lithium ion battery cathode material, which comprises the following preparation processes: preparing a tin sulfide nanobelt; adding tin sulfide nanobelts into a tris buffer solution, and performing ultrasonic treatment to obtain a mixed solution; adding dopamine into the mixed solution, and stirring at room temperature for reaction; carrying out suction filtration, washing and drying on the reaction product to obtain a polydopamine-coated tin sulfide nanobelt; and calcining the polydopamine-coated tin sulfide nanobelt under the protection of inert atmosphere, and then cooling to room temperature to obtain the carbon-coated tin sulfide nanobelt. The method adopts a hydrothermal method to prepare the tin sulfide nanobelt, adopts dopamine as a carbon source, does not need a complex reaction process at a proper temperature and pH value, can almost generate self-polymerization on the surface of any object to generate a continuous high-strength polydopamine thin layer, has a simple coating process, and can form an ideal carbon layer after high-temperature carbonization.
Description
Technical field
The present invention relates to lithium ion battery negative material fields, and in particular to a kind of lithium ion battery negative material carbon cladding
The preparation method of artificial gold nanobelt.
Background technique
Lithium ion battery has the features such as energy density is high, and the service life is long, voltage is high, self discharge is small, pollution is small, therefore quilt
It is widely used in the portable devices such as mobile phone, digital camera, notebook.Compared to materials such as traditional graphite (372mAh/g),
Transient metal sulfide, such as FeS, CoS, NiS, CuS have higher theoretical capacity, it is considered to be ideal lithium ion battery
Negative electrode material substitute.Wherein, artificial gold is due to having the characteristics that low price, abundance, theoretical capacity are high (780mAh/g),
And higher conductivity (120Scm), not only make artificial gold that there is better high rate performance, can be effectively reduced simultaneously
Fuel factor in charge and discharge process.But SnS is easy to produce volume expansion and causes battery when in lithium ion battery
It is destroyed or capacity declines.To overcome drawbacks described above, the porous SnS of 3D nano flower, 3D, nanosphere, the nucleocapsid knot of nanostructure
Structure, nanometer sheet, nanometer rods and nanobelt etc. are widely used for slowing down its volume expansion.In above-mentioned nanostructure, 1D SnS is often
Physically better or chemical property can be shown, but 1D structure is still not enough to eliminate negative shadow brought by volume expansion
It rings.And its volume expansion can then be effectively inhibited by wrapping up one layer of porous carbon layer with good conductivity in vulcanization tin surfaces, and be improved
The chemical property of raw material.In general, graphene and carbon nanotube are the most common carbon sources of carbon coating, but material cost compared with
It is high；And biomass carbon source, although such as glucose, chitosan, sodium alginate, cellulose price relative moderate, coat program
But seem relative complex.
Summary of the invention
It is being used as lithium ion battery negative material based on existing graphite carbon material and transient metal sulfide material
When the disadvantages of existing specific capacity is low, volume expansion, poor circulation, not ideal enough high rate performance, the present invention provides one kind
The preparation method of carbon coating artificial gold nanobelt lithium ion battery negative material.Cell negative electrode material capacity prepared by this method
Much higher than business carbon material, the volume expansion that artificial gold generates in charge and discharge process is can be effectively suppressed in carbon-coating, while can mention
The conductivity of high material, therefore have excellent cycle performance and high rate performance.
A kind of preparation method of lithium ion battery negative material carbon cladding artificial gold nanobelt, preparation process are as follows:
1) artificial gold nanobelt is prepared；
2) artificial gold nanobelt is added in trishydroxymethylaminomethane (Tris) buffer, ultrasound is at mixed liquor；
3) dopamine is added in mixed liquor, reaction is stirred at room temperature；
4) reaction product that step 3) obtains is obtained to the artificial gold nanobelt of poly-dopamine cladding after suction filtration, washing, drying；
5) under inert atmosphere protection, the artificial gold nanobelt that poly-dopamine coats is calcined, after then cooling to room temperature,
Obtain carbon coating artificial gold nanobelt.
Further scheme, artificial gold nanobelt as described in step (1) the preparation method is as follows: first by urea 0.1-10g,
Thioacetamide 0.1-10g, two hydrated stannous chloride 0.1-10g are added in the deionized water of 10-100mL, and stirring is configured to
Homogeneous solution；Then above-mentioned solution is transferred in water heating kettle and carries out hydro-thermal reaction, used after being then cooled to room temperature reactant
After deionized water and ethyl alcohol successively wash, drying obtains artificial gold nanobelt.
Stirring herein is magnetic agitation or mechanical stirring 30min.
Preferably, hydrothermal temperature is 100-200 DEG C in the step 2, and the hydro-thermal time is 1-24h, and it is cold to be cooled to nature
But.Cleaning solution is deionized water and dehydrated alcohol, and washing times are respectively 3 times.
Further scheme, the hydro-thermal reaction are that water heating kettle sealing is placed in air dry oven to be heated to 100-200
DEG C, react 1-24h.
Further scheme, the width of the artificial gold nanobelt is 50-500nm, length is 1-10 μm.
Further scheme, the pH value of TRIS buffer described in step (2) are 5-10.
Further scheme, it is 1-4mg/mL, stirring that dopamine described in step (3), which is added quality and accounts for the volume ratio of mixed liquor,
Reaction time is 1-48h.
Further scheme, inert gas described in step (5) are one of nitrogen, helium, neon, argon gas；It is described to forge
It is that 1-10 DEG C/min is warming up to 100-800 DEG C that burning, which is with heating rate, calcination time 1-10h.
Further scheme, coat in the carbon coating artificial gold nanobelt carbon-coating with a thickness of 10-30nm.
The present invention is that artificial gold nanobelt is prepared using hydro-thermal method, be a certain proportion of urea, thioacetamide,
Two hydration stannous sulfides are added to the water, and are added in water heating kettle after dissolution is sufficiently stirred and carry out hydro-thermal reaction.Hydro-thermal reaction mistake
The HS generated in journey-The Sn that ion and stannous chloride ionize out2+Ion directly forms SnS and H2S gas.Hydro-thermal reaction terminates
Afterwards, with the H of penetrating odor in water heating kettle2S gas confirms the generation of the reaction, and correlated response equation is as follows:
Sn2++2HS-→SnS+H2S↑
In reaction process, a large amount of SnS nucleus growths become SnS nano particle, due to Sn2+And HS-Ion is in the molten of different directions
Solution is different with growth rate, and the growth rate of SnS nano particle in one direction is caused to be significantly larger than other two direction
Growth rate ultimately forms the nanometer band structure of Bao Erchang.
Compared with the prior art, the advantages of the present invention are as follows:
This method prepares artificial gold nanobelt using hydro-thermal method, uses dopamine for carbon source, at temperature appropriate and pH, is not necessarily to
It is thin almost in any body surface the continuous high-intensitive poly-dopamine of one layer of auto polymerization generation can to occur for complex reaction process
Layer, cladding process is simple, and it can form one layer of ideal carbon-coating after high temperature cabonization.
Using dopamine as carbon source, one layer of uniform poly- DOPA is coated in nanometer belt surface using the auto polymerization behavior of dopamine
Amine coating obtains carbon coating artificial gold nanobelt after high temperature cabonization.It is modified due to the conduction and protective effect of carbon-coating
Active material high rate performance and cycle performance have increased significantly.Under the current density of 125mA/g, this kind of material
In the specific discharge capacity for being still able to maintain 1260.29mAh/g after 220 charge and discharge cycles, cycle life is much higher than without packet
The artificial gold covered.
So preparation method of the present invention is simple, expensive chemical reagent is not needed, it is low in cost；Without high temperature, wiper ring
It protects, safe operation is energy saving.
Using carbon coating artificial gold nanobelt prepared by the present invention as active material, and mixed with acetylene black, SBR/CMC
It is even, suitable quantity of water is added and is modulated into slurry, is coated uniformly on copper foil, electrode slice is made after drying.Half is assembled into glove box
Battery simultaneously tests its chemical property, and capacity is much higher than general battery, and good rate capability, has extended cycle life.
Detailed description of the invention
Fig. 1 is the cycle performance curve of battery made by the negative electrode material of the preparation of comparative example 1.
Fig. 2 is the scanning electron microscope (SEM) photograph and transmission electron microscope picture of artificial gold nanobelt made from comparative example 1.
Fig. 3 is the cycle performance curve of battery made by the negative electrode material of the preparation of embodiment 1.
Fig. 4 is the scanning electron microscope (SEM) photograph and transmission electron microscope picture of carbon coating artificial gold nanobelt made from embodiment 1.
Fig. 5 is the high rate performance curve of battery made by the negative electrode material of comparative example 1 and embodiment 2.
Specific embodiment
Comparative example 1
1) precise 1.05g urea, 1.32g thioacetamide, bis- hydrated stannous chloride of 0.24g are added to 70mL deionization
In water, stirring 30min is configured to homogeneous solution.
2) above-mentioned solution is transferred in 100mL water heating kettle, closed to be placed in air dry oven, hydro-thermal at 170 DEG C
10h.After being cooled to room temperature, after respectively being washed three times with deionized water and dehydrated alcohol, is dried at 70 DEG C, obtain artificial gold nanometer
Band.
3) it is sufficiently ground after mixing obtained active material and acetylene black, SBR/CMC according to the ratio of mass ratio 8:1:1
Mill, is added a certain amount of water, is configured to slurry, be coated uniformly on copper foil with automatic film applicator, and be dried in vacuo at 120 DEG C
12h.After the completion of drying, copper foil is cut into the disk of diameter 1.2cm.
4) using copper foil as working electrode, 1 M LiPF6EC:DEC=1:1(v:v) solution be electrolyte, lithium piece be to electricity
Pole is assembled into button half-cell in glove box.With new prestige battery test system, CHI660E electrochemical workstation tests battery
Chemical property.
As shown in Figure 1, being the cycle performance of battery curve, battery initial discharge specific capacity is up to 1215mAh/g, illustrates sulphur
Changing tin has very high energy density.But battery specific discharge capacity when by 47 charge and discharge cycles just has descended to
300mAh/g or less.This is because the volume expansion that artificial gold generates in cyclic process makes electrode material fall off, to make to put
Capacitance gradually decreases.
Fig. 2 be artificial gold nanobelt scanning electron microscope (SEM) photograph (on) and projection electron microscope (under), vulcanize as we can see from the figure
The shape of tin nanobelt is apparent strip-form structure.
Embodiment 1:
1) precise 1.05g urea, 1.32g thioacetamide, bis- hydrated stannous chloride of 0.24g are added to 70mL deionization
In water, stirring 30min is configured to homogeneous solution.
2) above-mentioned solution is transferred in 100mL water heating kettle, closed to be placed in air dry oven, 170 DEG C of hydro-thermal 10h.
After being cooled to room temperature, after respectively being washed three times with deionized water and dehydrated alcohol, is dried at 70 DEG C, obtain artificial gold nanobelt.
3) 264mg artificial gold nanobelt is taken, is added in 50mL Tris buffer (pH ~ 8.5), after ultrasonic 30min, adds
Enter 50mg dopamine and is stirred to react 24 h at 30 DEG C.Be washed with deionized water 3 times after reaction, 50 DEG C be dried to it is completely dry
It is dry.
4) under nitrogen atmosphere, 150 DEG C, constant temperature 1h are warming up to the rate of 3 DEG C/min, then with the heating speed of 2 DEG C/min
After rate rises to 500 DEG C, constant temperature 4 hours, cooled to room temperature obtains carbon coating artificial gold nanobelt.
5) using obtained carbon coating artificial gold nanobelt as negative electrode active material and acetylene black, SBR/CMC according to quality
It is fully ground after ratio mixing than 8:1:1, a certain amount of water is added, is configured to slurry, is coated uniformly on automatic film applicator
On copper foil, and 12h is dried in vacuo at 120 DEG C.After the completion of drying, copper foil is cut into the disk of diameter 1.2cm.It is with copper foil
Working electrode, 1M LiPF6EC:DEC=1:1(v:v) solution be electrolyte, lithium piece be to electrode, be assembled into glove box
Button half-cell.With new prestige battery test system, CHI660E electrochemical workstation tests the chemical property of battery.
The cycle performance curve for the battery that the present embodiment 1 as shown in Figure 3 assembles.As can be seen from Figure 3, the initial of battery is put
Electric specific capacity is 920.7mAh/g, since the presence of carbon makes the specific discharge capacity of composite material be slightly below pure artificial gold
Capacity.During circulating battery, due to the activation of electrode material, so that discharge capacity gradually rises, 220 are eventually passed through
Battery still has the specific discharge capacity of 1260.29mAh/g after secondary circulation.This is because carbon shell protects internal artificial gold not broken
It is bad, the significant increase cycle life of battery.
Fig. 4 be carbon coating artificial gold nanobelt made from the present embodiment 1 scanning electron microscope (SEM) photograph (on) and transmission electron microscope picture
(under).Itself and Fig. 2 are compared, can be clearly seen that, the surface of smooth artificial gold nanobelt coated one layer it is relatively crude
Rough carbon-coating, thickness are about 21nm.
Embodiment 2:
1) precise 1.05g urea, 1.32g thioacetamide, bis- hydrated stannous chloride of 0.24g are added to 70mL deionization
In water, stirring 30min is configured to homogeneous solution.
2) above-mentioned solution is transferred in 100mL water heating kettle, closed to be placed in air dry oven, 170 DEG C of hydro-thermal 10h.
After being cooled to room temperature, after respectively being washed three times with deionized water and dehydrated alcohol, is dried at 70 DEG C, obtain artificial gold nanobelt.
3) 264mg artificial gold nanobelt is taken, is added in 50mL Tris buffer (pH ~ 8.5), after ultrasonic 30min, adds
Enter 100mg dopamine to be stirred to react for 24 hours at 30 DEG C.Be washed with deionized water 3 times after reaction, 50 DEG C be dried to it is completely dry
It is dry.
4) under nitrogen atmosphere, 150 DEG C, constant temperature 1h are warming up to the rate of 3 DEG C/min, then with the heating speed of 2 DEG C/min
After rate rises to 500 DEG C, constant temperature 4 hours, cooled to room temperature obtains carbon coating artificial gold nanobelt.
5) using obtained carbon coating artificial gold nanobelt as negative electrode active material and acetylene black, SBR/CMC according to quality
It is fully ground after ratio mixing than 8:1:1, a certain amount of water is added, is configured to slurry, is coated uniformly on automatic film applicator
On copper foil, and 12h is dried in vacuo at 120 DEG C.After the completion of drying, copper foil is cut into the disk of diameter 1.2cm.It is with copper foil
Working electrode, 1 M LiPF6EC:DEC=1:1(v:v) solution be electrolyte, lithium piece be to electrode, be assembled into glove box
Button half-cell.With new prestige battery test system, CHI660E electrochemical workstation tests the chemical property of battery.
Fig. 5 is the high rate performance curve of the button battery of comparative example 1 and the organized shape of embodiment 2.From the figure, it can be seen that without
The high rate performance of the artificial gold nanobelt of cladding is very poor, and when current density rises to 5A/g, specific capacity is had already decreased to
100mAh/g or less.And the high rate performance of carbon coating artificial gold nanobelt is excellent in the present invention, when current density rises to 5A/g,
Material remains to play the capacity of 500mAh/g, and when current density falls back to 0.2A/g, specific discharge capacity can go up immediately.
Embodiment 3:
1) precise 1.05g urea, 1.32g thioacetamide, bis- hydrated stannous chloride of 0.24g are added to 70 mL deionizations
In water, stirring 30min is configured to homogeneous solution.
2) above-mentioned solution is transferred in 100mL water heating kettle, closed to be placed in air dry oven, 170 DEG C of hydro-thermal 10h.
After being cooled to room temperature, after respectively being washed three times with deionized water and dehydrated alcohol, is dried at 70 DEG C, obtain artificial gold nanobelt.
3) 264mg artificial gold nanobelt is taken, is added in 50mL Tris buffer (pH ~ 8.5), after ultrasonic 30min, adds
Enter 50mg dopamine and is stirred to react 48h at 30 DEG C.It is washed with deionized water 3 times after reaction, 50 DEG C are dried to and are completely dried.
4) under nitrogen atmosphere, 150 DEG C, constant temperature 1h are warming up to the rate of 3 DEG C/min, then with the heating speed of 2 DEG C/min
After rate rises to 500 DEG C, constant temperature 4 hours, cooled to room temperature obtains carbon coating artificial gold nanobelt.
Embodiment 4:
1) precise 1.05g urea, 1.32g thioacetamide, bis- hydrated stannous chloride of 0.24g are added to 70mL deionization
In water, stirring 30min is configured to homogeneous solution.
2) above-mentioned solution is transferred in 100mL water heating kettle, closed to be placed in air dry oven, 170 DEG C of hydro-thermal 10h.
After being cooled to room temperature, after respectively being washed three times with deionized water and dehydrated alcohol, is dried at 70 DEG C, obtain artificial gold nanobelt.
3) 264mg artificial gold nanobelt is taken, is added in 50mL Tris buffer (pH ~ 8.5), after ultrasonic 30min, adds
Enter 50mg dopamine to be stirred to react for 24 hours at 30 DEG C.It is washed with deionized water 3 times after reaction, 50 DEG C are dried to and are completely dried.
4) under nitrogen atmosphere, after being warming up to 500 DEG C, constant temperature 4 hours with the rate of 5 DEG C/min, cooled to room temperature is obtained
Carbon coating artificial gold nanobelt.
It is described above that respective description only made to the preferable specific embodiment of the present invention, but the invention is not limited to
Upper embodiment, any those skilled in the art in the technical scope disclosed by the present invention, technology according to the present invention
Scheme and its inventive concept are subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (8)
1. a kind of preparation method of lithium ion battery negative material carbon cladding artificial gold nanobelt, it is characterised in that: preparation process
It is as follows:
1) artificial gold nanobelt is prepared；
2) artificial gold nanobelt is added in TRIS buffer, ultrasound is at mixed liquor；
3) dopamine is added in mixed liquor, reaction is stirred at room temperature；
4) reaction product that step 3) obtains is obtained to the artificial gold nanobelt of poly-dopamine cladding after suction filtration, washing, drying；
5) under inert atmosphere protection, the artificial gold nanobelt that poly-dopamine coats is calcined, after then cooling to room temperature,
Obtain carbon coating artificial gold nanobelt.
2. preparation method according to claim 1, it is characterised in that: the system of artificial gold nanobelt as described in step (1)
Preparation Method is as follows: urea 0.1-10g, thioacetamide 0.1-10g, two hydrated stannous chloride 0.1-10g being first added to 10-
In the deionized water of 100mL, stirring is configured to homogeneous solution；Then it is anti-above-mentioned solution to be transferred to progress hydro-thermal in water heating kettle
It answers, after successively being washed after being then cooled to room temperature reactant with deionized water and ethyl alcohol, drying obtains artificial gold nanobelt.
3. preparation method according to claim 2, it is characterised in that: the hydro-thermal reaction is to be placed on water heating kettle sealing
It is heated to 100-200 DEG C in air dry oven, reacts 1-24h.
4. preparation method according to claim 2, it is characterised in that: the width of the artificial gold nanobelt is 50-500
Nm, length are 1-10 μm.
5. preparation method according to claim 1, it is characterised in that: trishydroxymethylaminomethane described in step (2)
The pH value of buffer is 5-10.
6. preparation method according to claim 1, it is characterised in that: the addition of dopamine described in step (3) quality accounts for mixed
The volume ratio for closing liquid is 1-4mg/mL, and being stirred to react the time is 1-48h.
7. preparation method according to claim 1, it is characterised in that: inert gas described in step (5) is nitrogen, helium
One of gas, neon, argon gas；It is that 1-10 DEG C/min is warming up to 100-800 DEG C that the calcining, which is with heating rate, calcination time
For 1-10h.
8. preparation method according to claim 1, it is characterised in that: carbon coating artificial gold nanobelt described in step (5)
It is middle cladding carbon-coating with a thickness of 10-30nm.
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| CN111900346A (en) * | 2020-07-13 | 2020-11-06 | 滁州学院 | Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery |
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| CN111900346B (en) * | 2020-07-13 | 2022-05-13 | 滁州学院 | Carbon-coated tin dioxide/zinc sulfide hollow cubic nano composite material, preparation method thereof, lithium ion battery cathode and battery |
| CN112582185A (en) * | 2020-11-06 | 2021-03-30 | 广东工业大学 | Flexible self-supporting titanium nitride/stannous sulfide/carbon electrode material with triple core-shell structure and preparation method and application thereof |
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| CN113036121A (en) * | 2021-03-05 | 2021-06-25 | 大连理工大学 | Carbon-coated transition metal sulfide nanoflower structure, preparation method and application thereof |
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| CN114023953A (en) * | 2021-11-03 | 2022-02-08 | 惠州亿纬锂能股份有限公司 | Modified lithium iron manganese phosphate cathode material and preparation method and application thereof |
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