CN108493425A - A kind of preparation method of the Sn4P3 nano particle anode material of lithium-ion batteries of mesoporous carbon nanotube cladding - Google Patents
A kind of preparation method of the Sn4P3 nano particle anode material of lithium-ion batteries of mesoporous carbon nanotube cladding Download PDFInfo
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- CN108493425A CN108493425A CN201810324155.9A CN201810324155A CN108493425A CN 108493425 A CN108493425 A CN 108493425A CN 201810324155 A CN201810324155 A CN 201810324155A CN 108493425 A CN108493425 A CN 108493425A
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 16
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000005253 cladding Methods 0.000 title claims abstract description 13
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 13
- 239000010405 anode material Substances 0.000 title claims abstract description 12
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 10
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 229910016978 MnOx Inorganic materials 0.000 claims description 17
- 235000019441 ethanol Nutrition 0.000 claims description 16
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 16
- 239000002070 nanowire Substances 0.000 claims description 16
- 239000011159 matrix material Substances 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 238000001556 precipitation Methods 0.000 claims description 9
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000012286 potassium permanganate Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 239000003643 water by type Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000002474 experimental method Methods 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910001887 tin oxide Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 17
- 239000000047 product Substances 0.000 description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 6
- 229910001415 sodium ion Inorganic materials 0.000 description 6
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 5
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 235000014676 Phragmites communis Nutrition 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of Sn of mesoporous carbon nanotube cladding4P3The preparation method of nano particle anode material of lithium-ion battery is with mesoporous carbon-coated SnO2It is that raw material is prepared by heating phosphating reaction with sodium hypophosphite.Due to material specific surface area height, good conductivity and Sn4P3The presence of nano particle, when with Sn4P3@mC are as anode material of lithium-ion battery in use, gained battery material has preferable stable circulation stability and high cycle specific capacity, battery performance excellent；And product preparation method is simple and yield is high, and it is raw materials used cheap and easy to get, be conducive to commercial applications.
Description
Technical field
The present invention relates to a kind of anode material of lithium-ion battery, specifically a kind of Sn of mesoporous carbon nanotube cladding4P3
The preparation method of nano particle anode material of lithium-ion battery.
Background technology
The secondary cell energy storage technology of development efficient stable is the weight of the current increasingly urgent energy and environment problem of reply
Want means, and under conditions of lithium ion battery reserves are not abundant, sodium-ion battery due to abundant reserves become lithium from
The substitute of sub- battery is possibly realized.Fast-developing high-end consumption electronic product (such as smart mobile phone, wearable device) is urgently
It need to be with the secondary cell of high-energy-density.
Mesoporous carbon-coated Sn4P3Sodium ion negative material can still keep higher under the density of high current cycle
Specific capacity and cycle performance, therefore demand of the contemporary people to high energy density cells can be satisfied with.Phosphorization tin is conductive
The shortcomings of difference, volume expansion is big when charge and discharge, to solve these disadvantages, presently mainly phosphorization tin mixing carbon material etc. so that
The performance of product is restricted.Low output is not suitable for large-scale production and seriously hinders its practical application.
Invention content
To avoid the problems of above-mentioned prior art, the present invention provides a kind of Sn of mesoporous carbon nanotube cladding4P3
The preparation method of nano particle anode material of lithium-ion battery, it is intended to further increase the gentle solution volume expansion of electric conductivity of material
To improve Sn4P3The performance of sodium-ion battery as negative material.
The Sn of the mesoporous carbon nanotube cladding of the present invention4P3The preparation method of nano particle anode material of lithium-ion battery, including
Following steps：
Step 1：By 1.8-2.5g'sF-127 powder is dispersed in the burning equipped with 30ml deionized water solvents
In cup；Step 2：By 1.0-1.8g phenol, the sodium hydroxide solution of 3.8-4.8ml formaldehyde and a concentration of 0.01mol/L of 20-40ml
It sequentially adds in conical flask, 20-50min is stirred at 60-80 DEG C；
Step 3：The solution that step 1 is prepared is added in the reaction solution of step 2, and 4 DEG C are reduced on the basis of original temperature,
1.5-3h is stirred with 280-400rpm；
Step 4：80-120ml deionized waters are added in conical flask, original temperature and the stirring of original mixing speed are kept
15-24h after stirring, and observes bottom whether there is or not precipitation, the failure of an experiment if having precipitation, if being dropped with cold water without precipitation
Temperature is cooled to room temperature to obtain mesoporous carbon matrix precursor F127Solution, it is spare；
Step 5：Potassium permanganate is added in deionized water, PVP is stirring evenly and then adding into and stirs evenly, hydro-thermal reaction knot
Beam postcooling is centrifuged, is washed and obtain MnO after drying to room temperaturexLine presoma；
Step 6：By MnO made from step 5xLine presoma is added in water and alcohol mixed solution, stirs evenly, then according to
Secondary addition urea and KSnO3·H2O is simultaneously stirred evenly, and is cooled to room temperature after hydro-thermal reaction, and products therefrom centrifugation, washing are simultaneously
It is dry, obtain MnOx@SnO2Nano wire, granules of stannic oxide are evenly distributed on manganese oxide surface；
Step 7：By MnOx@SnO2Nano wire and CTAB are added in deionized water, and ultrasonic disperse is uniform, and step 4 is then added
The mesoporous carbon matrix precursor F obtained127Solution ＆ stir is uniform, is cooled to room temperature after hydro-thermal reaction, is centrifuged by water and ethyl alcohol
Washing obtains the MnO of mesoporous carbon matrix precursor claddingx@SnO2Nano wire is abbreviated as MnOx@SnO2@CF127Nano wire；
Step 8：The unseasoned MnO that step 7 is obtainedx@SnO2@CF127Nano wire, which immerses in oxalic acid solution, removes presoma
MnOxLine is converted into hollow SnO2@CF127Pipe；
Step 9：By hollow SnO2@CF127Pipe is placed in inert atmosphere and roasts, and is converted into SnO2@mC；
Step 10：By SnO2@mC are mixed with sodium hypophosphite, carry out phosphating reaction in an inert atmosphere, after reaction with
0.05mol/L HCl solutions and ethyl alcohol washing obtain the Sn of mesoporous carbon nanotube cladding after vacuum drying4P3Nano particle sodium from
Sub- cell negative electrode material, is abbreviated as Sn4P3@mC anode material of lithium-ion batteries.
In step 5, the mass ratio of potassium permanganate and PVP are 85：40-60, preferably 76:45；Potassium permanganate and solvent matter
Amount volume ratio is 85mg：35-45ml, preferably 85mg：40mL；Hydrothermal temperature is 160 DEG C, reaction time 8-10h, preferably
9h。
In step 6, MnOx、urea、KSnO3·H2O, the mass volume ratio of water and alcohol mixed solution is 90-110mg：
700-1000mg：100-164mg：25-35ml, preferred mass volume ratio are 100mg：900mg：144mg：30ml.Water and ethyl alcohol
The volume content of ethyl alcohol is 37.5% in mixed solution；Hydrothermal temperature is 170 DEG C, reaction time 1-3h, preferably 1h.
In step 7, MnOx@SnO2Nano wire, CTAB and mesoporous carbon matrix precursor F127The mass volume ratio of solution is 100mg:
70-120mg：1.0-3.5ml preferably 100mg：100mg：1.5ml；Wait for MnOx@SnO2After nano wire and CTAB are uniformly dispersed,
Mesoporous carbon matrix precursor F is added127Solution stirs 2-8h after adding；Hydrothermal temperature is 120-130 DEG C, preferably hydro-thermal reaction temperature
Degree is 130 DEG C, and the hydro-thermal reaction time is for 24 hours.
In step 8, a concentration of 0.4-0.6M of oxalic acid solution, preferably 0.5M.
In step 9, the inert atmosphere is nitrogen；Calcination temperature is 500-700 DEG C, and preferably 500 DEG C, roasting time is
40-80min, preferably 50min.
In step 10, SnO2The molar ratio of@mC and sodium hypophosphite is 1：4-6；The inert atmosphere is nitrogen；Phosphating reaction
Temperature be 260-300 DEG C, preferably 280 DEG C, reaction time 15-60min, preferably 50min.
Beneficial effects of the present invention are embodied in：
1, the present invention is with nanotube-shaped mesoporous carbon-coated Sn4P3Nano particle compares table as anode material of lithium-ion battery
Area is high, and gained battery has preferable stable circulation stability and high cycle specific capacity, battery performance excellent.
2, the nanotube-shaped mesoporous carbon-coated Sn of the present invention4P3The preparation method of nano particle is simple, raw materials used cheap easy
, be conducive to commercial applications.
Description of the drawings
Fig. 1 is 1 gained nanometer threadiness MnO of embodimentxSEM photograph.
Fig. 2 is 1 gained nanometer threadiness MnO of embodimentxTEM photos.
Fig. 3 is 1 gained nanometer threadiness MnO of embodimentx@SnO2SEM photograph.
Fig. 4 is 1 gained nanometer threadiness MnO of embodimentx@SnO2TEM photos.
Fig. 5 is 1 gained nanometer threadiness MnO of embodimentx@SnO2@CF127SEM photograph.
Fig. 6 is the 1 nanotube-shaped SnO of gained of embodiment2@CF127TEM photos.
Fig. 7 is the 1 nanotube-shaped SnO of gained of embodiment2The TEM photos of@mC.
Fig. 8 is the 1 nanotube-shaped Sn of gained of embodiment4P3The SEM photograph of@mC.
Fig. 9 is the 1 nanotube-shaped Sn of gained of embodiment4P3The TEM photos of@mC.
Figure 10 is the 1 nanotube-shaped Sn of gained of embodiment4P3The XRD diagram of@mC.
Figure 11 is the 1 nanotube-shaped Sn of gained of embodiment4P3The EDS of@mC schemes.
Figure 12 is the 1 nanotube-shaped Sn of gained of embodiment4P3The BET of@mC schemes.
Figure 13 is the 1 nanotube-shaped Sn of gained of embodiment4P3The battery performance figure of@mC.
Specific implementation mode
Below by attached drawing and specific embodiment, the present invention is described in detail.
Experimental method used in following embodiments is conventional method unless otherwise specified.It is used in the following example
Reagent, material etc. unless otherwise specified, commercially obtain.
Embodiment 1：
A kind of Sn of mesoporous carbon nanotube cladding in the present embodiment4P3The preparation of nano particle anode material of lithium-ion battery
Method.
It is as follows：
1, by 1.92g'sF-127 powder is dispersed in the beaker equipped with 30ml deionized water solvents；
2, the sodium hydroxide solution of 1.2g phenol, 4.2ml formaldehyde and a concentration of 0.01mol/L of 30ml is sequentially added into taper
In bottle, 30min is stirred at 70 DEG C；
3, the solution for preparing step 1 is added in the reaction solution of step 2, and temperature is adjusted to 66 DEG C, and 2h is stirred with 340rpm；
4,100ml deionized waters are added in conical flask, original temperature and to stir 18h under original mixing speed, stirring
After, and bottom is observed whether there is or not precipitation, the failure of an experiment if having precipitation is down to room temperature if being cooled down with cold water without precipitation
After obtain mesoporous carbon matrix precursor F127Solution, it is spare；
5,85mg potassium permanganate is added in 40mL deionized waters, is stirring evenly and then adding into 50mg PVP and stirs evenly,
Hydro-thermal reaction 9h at 160 DEG C is cooled to room temperature after hydro-thermal reaction, centrifuges, washs and obtain MnO after dryingxLine presoma；
6, by MnO made from 100mg steps 5x30mL water and alcohol mixed solution (ethanol content is added in line presoma
37.5%) it in, stirs evenly, then sequentially adds 0.9g urea and 0.144g KSnO3·H2O is simultaneously stirred evenly, at 170 DEG C
Hydro-thermal reaction 60min is cooled to room temperature after hydro-thermal reaction, and products therefrom centrifugation is washed simultaneously dry, obtains MnOx@SnO2It receives
Rice noodles；
7, by 40mg MnOx@SnO2Nano wire and 40mg CTAB are added in 30mL deionized waters, and ultrasonic disperse is uniform, so
The mesoporous carbon matrix precursor F that 1.5mL steps 4 obtain is added afterwards127Solution ＆ stir 6h, at 130 DEG C hydro-thermal reaction for 24 hours, hydro-thermal reaction
After be cooled to room temperature, by water and ethyl alcohol centrifuge washing, obtain MnOx@SnO2@CF127Nano wire.
8, the unseasoned MnO for obtaining step 7x@SnO2@CF127Nano wire immerses in the oxalic acid solution of 100mL 0.5M, instead
2h is answered to remove presoma MnOxLine is converted into hollow SnO2@CF127Pipe；
9, by hollow SnO2@CF127Pipe is placed in nitrogen/argon gas atmosphere, is roasted 50min at 500 DEG C, is converted into SnO2@
mC；
10, by SnO2@mC and sodium hypophosphite in molar ratio 1:5 ratio mixing, it is anti-in 280 DEG C of solid phases in nitrogen atmosphere
50min is answered, after reaction with respectively washing four times of 0.05mol/L HCl solutions and ethyl alcohol, is obtained after vacuum drying nanotube-shaped
Sn4P3@mC anode material of lithium-ion batteries.
Fig. 1 and Fig. 2 is respectively the SEM photograph and TEM photos of first step product obtained by the present embodiment, as can be seen from Figure material
Material it is microcosmic it is lower have linear, provide relatively uniform template for next step product.
Fig. 3 and Fig. 4 is respectively the SEM photograph and TEM photos of second step product obtained by the present embodiment, as can be seen from Figure material
One layer of tin oxide nano particles have been expected in microcosmic lower cladding.
Fig. 5 is the SEM photograph that third walks product obtained by the present embodiment, and material is in microcosmic lower previous step as can be seen from Figure
Product coat one layer of F127, providing carbon-coating for tin oxide surface prevents stannic oxide from falling off.
The TEM photos of 4th step product obtained by Fig. 6 the present embodiment, as can be seen from Figure material removed by oxalic acid under microcosmic
Manganese oxide line provides sufficient inner space, alleviates the volume expansion of final product phosphorization tin.
Fig. 7 is the TEM photos of the 5th step product obtained by the present embodiment, and material is in microcosmic lower SnO2@as can be seen from Figure
CF127It is converted to stannic oxide surface and coats one layer of mesoporous carbon.
Fig. 8 and Fig. 9 is respectively the SEM photograph and TEM photos of the 6th step product obtained by the present embodiment, as can be seen from Figure material
Material is coated with granular substance in microcosmic lower carbon-coating, and original pattern is kept substantially.
Figure 10 is the XRD diagram piece of target product obtained by the present embodiment, it can be seen that the characteristic peak of material meets Sn4P3Peak,
Testimonial material is Sn4P3@mC。
Figure 11 is the EDS energy spectrum diagrams of target product obtained by the present embodiment, as can be seen from the figure apparent P elements, tin
The peak of element and carbon.
Figure 12 is the BET pictures of target product obtained by the present embodiment, and as can be seen from the figure target product is mesoporous carbon packet
The phosphorization tin covered, and possess larger specific surface area, provide more ion channels for the transmission of sodium ion.
The battery performance of target product obtained by the present embodiment is tested using blue electric battery test system：
With acetylene black, PVDF it is 7 according to mass ratio by mesoporous carbon-coated phosphorization tin nano material obtained by the present embodiment:2:
1 is uniformly mixed and is dissolved in nmp solution slurries are made；Gained slurry is equably applied in copper foil current collector, work electricity is made
Pole；Using polypropylene screen as diaphragm, electrolyte is that the volume ratio containing EC and DEC is 1:The 1M NaPF of 1 and 5%FEC6, full of
According to the suitable of " anode coat, sodium piece, diaphragm, electrolyte, working electrode, gasket, reed, positive shell " in the glove box of argon gas
Sequence is assembled into 2032 button cells, test voltage ranging from 0.01V-3V vs Na+/Na。
Figure 13 is the cycle performance of target product obtained by the present embodiment, and test multiplying power is 200mA g-1, it can be seen that sample
Product have good coulombic efficiency holding capacity, are still averagely maintained at 98.9% from the 18th circle to the 300th circle, 300 circle of cycle
Still hold 299.9mA h g afterwards-1Reversible specific capacity, show that cycle performance is excellent.
The above is merely preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
All any modification, equivalent and improvement made by within principle etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of Sn of mesoporous carbon nanotube cladding4P3The preparation method of nano particle anode material of lithium-ion battery, feature exist
In：It is the SnO coated with mesoporous carbon nanotube2Nano particle and sodium hypophosphite are that raw material is obtained by heating phosphating reaction preparation
.
2. preparation method according to claim 1, it is characterised in that include the following steps：
Step 1：By 1.8-2.5g'sF-127 powder is dispersed in the beaker equipped with 30ml deionized water solvents
In；
Step 2：By 1.0-1.8g phenol, the sodium hydroxide solution of 3.8-4.8ml formaldehyde and a concentration of 0.01mol/L of 20-40ml
It sequentially adds in conical flask, 20-50min is stirred at 60-80 DEG C；
Step 3：The solution that step 1 is prepared is added in the reaction solution of step 2, and 4 DEG C are reduced on the basis of original temperature, with
280-400rpm stirs 1.5-3h；
Step 4：80-120ml deionized waters are added in conical flask, original temperature and mixing speed is kept to stir 15-24h,
After stirring, and bottom is observed whether there is or not precipitation, the failure of an experiment if having precipitation is down to if being cooled down with cold water without precipitation
Mesoporous carbon matrix precursor F is obtained after room temperature127Solution, it is spare；
Step 5：Potassium permanganate is added in deionized water, PVP is stirring evenly and then adding into and stirs evenly, after hydro-thermal reaction
It is cooled to room temperature, centrifuges, wash and obtains MnO after dryingxLine presoma；
Step 6：By MnO made from step 5xLine presoma is added in water and alcohol mixed solution, stirs evenly, and then adds successively
Enter urea and KSnO3·H2O is simultaneously stirred evenly, and is cooled to room temperature after hydro-thermal reaction, products therefrom centrifugation, washing and drying,
It obtains tin oxide nanoparticles and coats MnOx, i.e. MnOx@SnO2Nano wire；
Step 7：By MnOx@SnO2Nano wire and CTAB are added in deionized water, and ultrasonic disperse is uniform, and step 4 is then added and obtains
Mesoporous carbon matrix precursor F127Solution ＆ stir is uniform, is cooled to room temperature after hydro-thermal reaction, is washed by water and ethyl alcohol centrifugation
It washs, obtains the MnO of mesoporous carbon matrix precursor claddingx@SnO2Nano wire, i.e. MnOx@SnO2@CF127Nano wire；
Step 8：The unseasoned MnO that step 7 is obtainedx@SnO2@CF127Nano wire, which immerses, removes presoma MnO in oxalic acid solutionx
Line is converted into hollow SnO2@CF127Pipe；
Step 9：By hollow SnO2@CF127Pipe is placed in inert atmosphere and roasts, and is converted into SnO2@mC；
Step 10：By SnO2@mC are mixed with sodium hypophosphite, carry out phosphating reaction in an inert atmosphere, after reaction with
0.05mol/L HCl solutions and ethyl alcohol washing obtain the Sn of mesoporous carbon nanotube cladding after vacuum drying4P3Nano particle sodium from
Sub- cell negative electrode material.
3. preparation method according to claim 2, it is characterised in that：
In step 5, the adding proportion of potassium permanganate, PVP and solvent is 85-90mg：40-60mg：35-45ml；Hydro-thermal reaction temperature
Degree is 160 DEG C, reaction time 8-10h.
4. preparation method according to claim 2, it is characterised in that：
In step 6, MnOx、urea、KSnO3·H2O, the adding proportion of water and alcohol mixed solution is 90-110mg：700-
1000mg：100-164mg：25-35ml；The volume content of ethyl alcohol is 37.5% in water and alcohol mixed solution；Hydro-thermal reaction temperature
Degree is 170 DEG C, reaction time 1-3h.
5. preparation method according to claim 2, it is characterised in that：
In step 7, MnOx@SnO2Nano wire, CTAB and mesoporous carbon matrix precursor F127The mass volume ratio of solution is 100mg:70-
120mg：1.0-3.5ml；Hydrothermal temperature is 120-130 DEG C.
6. preparation method according to claim 2, it is characterised in that：
In step 8, a concentration of 0.4-0.6M of oxalic acid solution.
7. preparation method according to claim 2, it is characterised in that：
In step 9, step 10, the inert atmosphere is nitrogen or argon gas.
8. preparation method according to claim 2, it is characterised in that：
In step 9, calcination temperature is 500-700 DEG C, roasting time 40-80min.
9. preparation method according to claim 2, it is characterised in that：
In step 10, SnO2The molar ratio of@mC and sodium hypophosphite is 1：4-6；Phosphating reaction temperature is 260-300 DEG C, the reaction time
For 15-60min.
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| CN110993913A (en) * | 2019-12-06 | 2020-04-10 | 湘潭大学 | Tin phosphide/expanded graphite cathode composite material of sodium ion battery and preparation method thereof |
| CN112201782A (en) * | 2020-10-16 | 2021-01-08 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
| CN112201782B (en) * | 2020-10-16 | 2022-09-30 | 西南大学 | Nickel phosphide/carbon/nickel phosphide composite material and preparation method and application thereof |
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