CN109378464A - A kind of stannic oxide carbon nano-complex and the preparation method and application thereof - Google Patents
A kind of stannic oxide carbon nano-complex and the preparation method and application thereof Download PDFInfo
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- CN109378464A CN109378464A CN201811474688.1A CN201811474688A CN109378464A CN 109378464 A CN109378464 A CN 109378464A CN 201811474688 A CN201811474688 A CN 201811474688A CN 109378464 A CN109378464 A CN 109378464A
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- stannic oxide
- carbon nano
- complex
- oxide carbon
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- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 title claims abstract description 115
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- REDXJYDRNCIFBQ-UHFFFAOYSA-N aluminium(3+) Chemical compound [Al+3] REDXJYDRNCIFBQ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000000463 material Substances 0.000 claims abstract description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000008103 glucose Substances 0.000 claims description 15
- 229910001868 water Inorganic materials 0.000 claims description 14
- 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 claims description 13
- 239000013078 crystal Substances 0.000 claims description 13
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 8
- JXBAVRIYDKLCOE-UHFFFAOYSA-N [C].[P] Chemical compound [C].[P] JXBAVRIYDKLCOE-UHFFFAOYSA-N 0.000 claims description 8
- 239000006229 carbon black Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 6
- 239000011888 foil Substances 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 6
- 239000011733 molybdenum Substances 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 claims description 2
- 239000011324 bead Substances 0.000 claims 1
- 150000002576 ketones Chemical class 0.000 claims 1
- 229920000642 polymer Polymers 0.000 claims 1
- -1 titanium dioxide tin carbon Chemical compound 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 7
- 229910001887 tin oxide Inorganic materials 0.000 abstract description 5
- 238000005054 agglomeration Methods 0.000 abstract description 2
- 230000002776 aggregation Effects 0.000 abstract description 2
- 239000003792 electrolyte Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 6
- 238000001354 calcination Methods 0.000 description 6
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 5
- 239000002033 PVDF binder Substances 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- NJMWOUFKYKNWDW-UHFFFAOYSA-N 1-ethyl-3-methylimidazolium Chemical compound CCN1C=C[N+](C)=C1 NJMWOUFKYKNWDW-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
- 230000009977 dual effect Effects 0.000 description 4
- 239000011152 fibreglass Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000013019 agitation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 2
- 229930006000 Sucrose Natural products 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000010668 complexation reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000005720 sucrose Substances 0.000 description 2
- 241000790917 Dioxys <bee> Species 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- QWJYDTCSUDMGSU-UHFFFAOYSA-N [Sn].[C] Chemical compound [Sn].[C] QWJYDTCSUDMGSU-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011365 complex material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004408 titanium dioxide 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
- H01M4/364—Composites as mixtures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
-
- 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
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- 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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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Composite Materials (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a kind of stannic oxide carbon nano-complexes and the preparation method and application thereof, by carrying out packet carbon to tin oxide nano particles, avoid the agglomeration of tin dioxide nano-particle, reduce the Volumetric expansion in stannic oxide circulation, stannic oxide size obtained is small, large specific surface area, active site are more.Using the stannic oxide carbon nano-complex and aluminum honeycomb match materials at aluminium ion battery possess high discharge capacity, high rate capability and high circulation service life.
Description
Technical field
The invention belongs to electrochmical power source technologies, and in particular to a kind of stannic oxide carbon nano-complex and preparation method thereof with
Using.
Background technique
Lithium ion battery (LIBs) achieves in portable electronic device, the energy fields such as electric car and power grid
Huge success, however, since lithium is at high cost, safety is bad, the especially limited reason of resource, lithium ion battery at present
Using still having many urgent problems to be solved.It is developing low-cost, Gao An about the research emphasis of secondary cell at present
The battery of Quan Xing, high-energy density, such as Zinc ion battery, sodium-ion battery, Magnesium ion battery and aluminium ion battery.Wherein, aluminium
Ion battery (AIB) is resourceful due to cheap, and safety is good and is concerned.Al3+Due to its trivalent property, in electricity
It displaced three electronics in chemical reaction, which results in the height ratio capacity of aluminium ion battery (2980Ah kg-1).However, there are also one
A little critical issues urgently to be resolved, most important one is exactly to find suitable positive electrode.Most of AIB positive electrodes exist
Low (the about 100mAh g of discharge capacity-1), long-term cycle stability is poor (stablizing circulation less than 200 circles), and capacity attenuation etc. is asked
Topic, therefore the positive electrode for studying high capacity high stability is still challenging.
Summary of the invention
It is a kind of suitable for aluminium ion battery the technical problem to be solved by the present invention is in view of the deficiencies of the prior art, provide
The stannic oxide carbon nano-complex and preparation method thereof of anode.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows:
A kind of preparation method of stannic oxide carbon nano-complex, includes the following steps:
(1) SnCl is taken4·5H2O crystal is dissolved in deionized water water, and obtained aqueous solution is heated to 190~230 DEG C, is protected
It holds 18~72 hours, obtains the first mixed liquor, be cooled to room temperature；
(2) it is added glucose into step (1) the first mixed liquor after cooling, after stirring and dissolving, is heated to 190~230
DEG C keep 18~24 hours, obtain the second mixed liquor, be cooled to room temperature；
(3) step (2) the second mixed liquor after cooling being centrifuged, taking precipitate is cooled to room temperature, it is subsequently placed in 500~
800 DEG C, 3~10h is calcined in argon atmosphere, obtains stannic oxide carbon nano-complex.
Wherein, in step (1), the obtained aqueous solution refers to 1~5g SnCl4·5H2O crystal is dissolved in 100~
In 150mL deionized water water.
What the cooling centrifugation of the first mixed liquor that step (1) obtains obtained is the stannic oxide nanometer crystalline deposit of white.
In step (2), the additional amount and SnCl of the glucose4·5H2The mass ratio of O crystal is (10~20): (1~
5), preferably 10:1.
In step (2), on the one hand stirring makes the glucose being added dissolution, and step (1) is on the other hand enabled to obtain
Stannic oxide nanometer crystallization be uniformly scattered in solution.Second mixed liquor is that the nano-scale carbon of brown to black coats
Stannic oxide particle dispersion liquid.
In step (3), the condition of the centrifugation is 500~10000 revs/min.
For obtained stannic oxide carbon nano-complex particle partial size between 50~80nm, partial size is more uniform.
The stannic oxide carbon nano-complex that above-mentioned preparation method obtains is also within protection scope of the present invention.
Although stannic oxide early has application in lithium ion battery negative material, do not ground also in aluminium ion battery
Study carefully.Reason is that electrolyte used in two kinds of battery systems is very different.Lithium-ion battery electrolytes are mostly the six of alkalinity
Lithium fluophosphate-carbonic ester system, and the electrolyte that aluminium ion battery uses is acid alchlor-[EMIm] Cl system, with
Traditional oxide, there are serious corrosion side reactions for sulfide electrode material, this results in most of lithium-ion battery system
Applicable electrode material can not use in aluminium ion battery.In addition to this, the two is in electrochemical energy storage mechanism, battery assembly skill
Art etc. has bigger difference, and the application is that the one one or two stannic oxide is applied in aluminium ion cell positive material, tool
There is great novelty.
Meanwhile the application also utilizes porous carbon-coated method, greatly improves stannic oxide in circulating battery process
In chemical property.By being advanced optimized to preparation technology parameter, so that the product uniformity and partial size that are prepared
It has a distinct increment in terms of size.
The present invention is also claimed the above-mentioned stannic oxide carbon nano-complex being prepared and makees just in aluminium ion battery
The application of pole.
Further, the present invention also provides a kind of aluminium ion cell positive materials, it is by the above-mentioned titanium dioxide being prepared
Tin carbon nanometer compound, Kynoar and super phosphorus carbon black are according to mass ratio (70-90): (5-20): dividing after (5-20) mixing
It dissipates in solvent, is then coated on 20~50 microns thick of light molybdenum foil and obtains.
The solvent is N-Methyl pyrrolidone；Wherein, the mass volume ratio of Kynoar and N-Methyl pyrrolidone
For 0.5~100mg/ml.
Specifically the preparation method comprises the following steps: weighing stannic oxide carbon nano-complex, Kynoar (PVDF) and super phosphorus carbon black
(Super P) is scattered in N-Methyl pyrrolidone (NMP) after mixing, and stirring dissolves Kynoar (PVDF), and makes it
He is uniformly mixed material, is coated on 20~50 microns thick of dual light molybdenum foil, obtains positive paillon, directly negative with aluminium after cutting
Pole match materials form aluminium ion battery.
Unaccounted content can be realized all in accordance with industry routine operation in technical solution of the present invention.
The utility model has the advantages that
The present invention provide it is a kind of can be with the matched positive stannic oxide carbon nano-complex material of Al cathode and its preparation side
Method avoids the agglomeration of tin dioxide nano-particle, reduces dioxy by carrying out packet carbon to tin oxide nano particles
Change the Volumetric expansion in tin circulation, stannic oxide size obtained is small, and large specific surface area, active site is more, using described
Stannic oxide carbon nano-complex and aluminum honeycomb match materials at aluminium ion battery possess high discharge capacity, high rate capability
And the high circulation service life.
Detailed description of the invention
The present invention is done with reference to the accompanying drawings and detailed description and is further illustrated, of the invention is above-mentioned
And/or otherwise advantage will become apparent.
Fig. 1 is the SEM figure of stannic oxide carbon nano-complex prepared by embodiment 1；
Fig. 2 is the BET specific surface area measurement chart of stannic oxide carbon nano-complex prepared by embodiment 1.
Specific embodiment
According to following embodiments, the present invention may be better understood.
Reagent source: super phosphorus carbon black (Super P) is purchased from Switzerland Te Migao graphite Co., Ltd.What other were not explained
Reagent is the commercially available gained in market.
The preparation of 1 stannic oxide carbon nano-complex of embodiment
The following steps are included:
(1) 1g SnCl is accurately weighed4·5H2O crystal is dissolved in 120mL deionized water, is transferred in reaction kettle, 190
It is heated 18 hours at DEG C, obtains the first mixed liquor, taking-up is cooled to room temperature；
(2) it accurately weighs 10g glucose to be added in the first mixed liquor, is dissolved in wherein, and stir and make wherein to have obtained
Tin oxide nano particles are good to be scattered in solution, after glucose is completely dissolved, then is placed it in reaction kettle, in
It is heated 18 hours at 190 DEG C, obtains the second mixed liquor, taking-up is cooled to room temperature；
(3) step (2) the second mixed liquor after cooling is centrifuged with 1000 revs/min, taking precipitate is placed in 500 DEG C of temperature
Under, it is calcined in argon atmosphere 3 hours and obtains stannic oxide carbon nano-complex.
SEM characterization is carried out to above-mentioned stannic oxide carbon nano-complex, it is found that the partial size of stannic oxide is about 50nm,
Particle size is small, and the uniformity is high, sees Fig. 1.BET specific surface area test, discovery are carried out to above-mentioned stannic oxide carbon nano-complex
Grain specific surface area is about 204.8m2g-1, see Fig. 2.
Application of the 2 stannic oxide carbon nano-complex of embodiment in aluminium ion battery
Using 1: accurately weighing the stannic oxide carbon nano-complex that 160mg embodiment 1 prepares, 20mg PVDF, 20mg
Super P is scattered in 1.5mL NMP, and magnetic agitation is coated on afterwards for 24 hours on 20 microns thick dual light molybdenum foil, needed for obtaining
The positive paillon wanted, obtains anode pole piece after cutting.Cathode, ionic liquid are used as using high-purity Al disk (with a thickness of 0.02mm)
(molar ratio AlCl3: [EMIm] Cl=1.3:1) it is that electrolyte is being full of using Whatmann company GF/D fibreglass diaphragm
The glove box ([O of argon gas2]<0.1ppm,[H2O] < 0.1ppm) in be assembled into CR2032 button cell, each battery contains electrolyte
50 microlitres.(in the application, the mass ratio of stannic oxide carbon nano-complex, Kynoar and super phosphorus carbon black is 80:10:
10)
Using 2: accurately weighing the stannic oxide carbon nano-complex that 140mg embodiment 1 prepares, 10mg PVDF, 20mg
Super P is scattered in 1.5mL NMP, and magnetic agitation is coated on afterwards for 24 hours on 20 microns thick dual light molybdenum foil, needed for obtaining
The positive paillon wanted, obtains anode pole piece after cutting.Cathode, ionic liquid are used as using high-purity Al disk (with a thickness of 0.02mm)
(molar ratio AlCl3: [EMIm] Cl=1.3:1) it is that electrolyte is being full of using Whatmann company GF/D fibreglass diaphragm
The glove box ([O of argon gas2]<0.1ppm,[H2O] < 0.1ppm) in be assembled into CR2032 button cell, each battery contains electrolyte
50 microlitres.(in the application, the mass ratio of stannic oxide carbon nano-complex, Kynoar and super phosphorus carbon black is 70:10:
20)
Using 3: accurately weighing the stannic oxide carbon nano-complex that 180mg embodiment 1 prepares, 5mg PVDF, 5mg
Super P is scattered in 1.5mL NMP, and magnetic agitation is coated on afterwards for 24 hours on 20 microns thick dual light molybdenum foil, needed for obtaining
The positive paillon wanted, obtains anode pole piece after cutting.Cathode, ionic liquid are used as using high-purity Al disk (with a thickness of 0.02mm)
(molar ratio AlCl3: [EMIm] Cl=1.3:1) it is that electrolyte is being full of using Whatmann company GF/D fibreglass diaphragm
The glove box ([O of argon gas2]<0.1ppm,[H2O] < 0.1ppm) in be assembled into CR2032 button cell, each battery contains electrolyte
50 microlitres.(in the application, the mass ratio of stannic oxide carbon nano-complex, Kynoar and super phosphorus carbon black is 90:5:5)
To aluminium ion battery made above using battery test system carry out performance detection, test voltage window be 0~
2V the results are shown in Table 1.(coulombic efficiency refers to the ratio between discharge capacity and charging capacity；Stablize circulating ring number and refers to the stable charge and discharge of battery
And the number of the discharge capacity of 100mAh/g or more is kept, it completes primary charging and discharging process and is counted as a circle；Discharge capacity 1 refers to
Discharge capacity of the battery under the current density of 100mA/g；Discharge capacity 2 refers to battery putting under the current density of 200mA/g
Capacitance；Stannic oxide carbon nano-complex: Kynoar is shown in mass ratio: super phosphorus carbon black)
Table 1
As can be seen from the table: the discharge capacity highest of battery when mass ratio is 80:10:10, therefore should be preferred
The formula of size technique (being best applications using 1) that mass ratio is 80:10:10.
Embodiment 3
The preparation of stannic oxide carbon nano-complex, comprising the following steps:
(1) 1g SnCl is accurately weighed4·5H2O crystal is dissolved in 120mL pure water, is transferred in reaction kettle, at 210 DEG C
Heating 36 hours, obtains the first mixed liquor, taking-up is cooled to room temperature；
(2) it accurately weighs 10g glucose to be added in the first mixed liquor, is dissolved in wherein, and stir and make wherein to have obtained
Tin oxide nano particles are good to be scattered in solution, after glucose is completely dissolved, then is placed it in reaction kettle, in
It is heated 36 hours at 210 DEG C, obtains the second mixed liquor, taking-up is cooled to room temperature；
(3) step (2) the second mixed liquor after cooling is centrifuged with 1000 revs/min, taking precipitate is placed in 500 DEG C of temperature
Under, it is calcined in argon atmosphere 3 hours and obtains stannic oxide carbon nano-complex.
Embodiment 4
The preparation of stannic oxide carbon nano-complex, comprising the following steps:
(1) 1g SnCl is accurately weighed4·5H2O crystal is dissolved in 120mL pure water, is transferred in reaction kettle, at 230 DEG C
Heating 72 hours, obtains the first mixed liquor, taking-up is cooled to room temperature；
(2) it accurately weighs 10g glucose to be added in the first mixed liquor, is dissolved in wherein, and stir and make wherein to have obtained
Tin oxide nano particles are good to be scattered in solution, after glucose is completely dissolved, then is placed it in reaction kettle, in
It is heated 72 hours at 230 DEG C, obtains the second mixed liquor, taking-up is cooled to room temperature；
(3) step (2) the second mixed liquor after cooling is centrifuged with 1000 revs/min, taking precipitate is placed in 500 DEG C of temperature
Under, it is calcined in argon atmosphere 3 hours and obtains stannic oxide carbon nano-complex.
Embodiment 5
Preparation manipulation with embodiment 1, the difference is that:
In step (1), 3g SnCl is weighed4·5H2O crystal is dissolved in 150mL pure water；
In step (2), accurately weighs 15g glucose or sucrose is added in the first mixed liquor.
Embodiment 6
Preparation manipulation with embodiment 1, the difference is that:
In step (1), 5g SnCl is weighed4·5H2O crystal is dissolved in 150mL pure water；
In step (2), accurately weighs 15g glucose or sucrose is added in the first mixed liquor.
Embodiment 7
Preparation manipulation with embodiment 1, the difference is that:
In step (3), calcination temperature is 650 DEG C, and calcination time is 5 hours.
Embodiment 8
Preparation manipulation with embodiment 1, the difference is that:
In step (3), calcination temperature is 800 DEG C, and calcination time is 10 hours.
The stannic oxide carbon nano-complex that embodiment 1,3~8 is prepared is located respectively according to the application 1 of embodiment 2
Reason is used as cathode, ionic liquid (molar ratio AlCl as anode, high-purity Al piece (with a thickness of 0.02mm)3: [EMIm] Cl=1.3:
It 1) is electrolyte, using Whatman company GF/D fibreglass diaphragm, in the glove box ([O for being full of argon gas2]<0.1ppm,
[H2O] < 0.1ppm) in be assembled into CR2032 button cell, each battery contains 50 microlitres of electrolyte.
To aluminium ion battery made above using battery test system carry out performance detection, test voltage window be 0~
2V the results are shown in Table 2.(coulombic efficiency refers to the ratio between discharge capacity and charging capacity；Stablize circulating ring number and refers to the stable charge and discharge of battery
And the number of the discharge capacity of 100mAh/g or more is kept, it completes primary charging and discharging process and is counted as a circle；Discharge capacity 1 refers to
Discharge capacity of the battery under the current density of 100mA/g；Discharge capacity 2 refers to battery putting under the current density of 200mA/g
Capacitance)
Table 2
As can be seen from the table: 1g SnCl4·5H2It is preferred that O crystal, which is dissolved in 120mL pure water,；10g glucose is
It is preferred that；190,210,230 DEG C of hydrothermal temperature of comparison, 190 DEG C are preferred；Compare the hydro-thermal reaction time 18,36,72h, 18h
It is preferred；500,650,800 DEG C of calcination temperature of comparison, 500 DEG C are preferred；Calcination time 3,5,10h are compared, 3h is preferred.It is comprehensive
It is upper described: 1g SnCl4·5H2O crystal is dissolved in 120mL pure water, 10g glucose, and 190 DEG C of hydro-thermal 18h, 500 DEG C are calcined 3h's
Preparation process, i.e. embodiment 1 are most preferred embodiment.
The present invention provides the thinking and method of a kind of stannic oxide carbon nano-complex and the preparation method and application thereof, tools
Body realizes that there are many method of the technical solution and approach, the above is only a preferred embodiment of the present invention, it is noted that right
For those skilled in the art, without departing from the principle of the present invention, several improvement can also be made
And retouching, these modifications and embellishments should also be considered as the scope of protection of the present invention.Each component part being not known in the present embodiment is equal
It can be realized with the prior art.
Claims (9)
1. a kind of preparation method of stannic oxide carbon nano-complex, which comprises the steps of:
(1) SnCl is taken4·5H2O crystal is dissolved in deionized water water, and obtained aqueous solution is heated to 190~230 DEG C, keeps 18
~72 hours, the first mixed liquor is obtained, is cooled to room temperature；
(2) it is added glucose into step (1) the first mixed liquor after cooling, after stirring and dissolving, is heated to 190~230 DEG C of guarantors
It holds 18~24 hours, obtains the second mixed liquor, be cooled to room temperature；
(3) step (2) the second mixed liquor after cooling being centrifuged, taking precipitate is cooled to room temperature, 500~800 DEG C are subsequently placed in,
3~10h is calcined in argon atmosphere, obtains stannic oxide carbon nano-complex.
2. the preparation method of stannic oxide carbon nano-complex according to claim 1, which is characterized in that in step (1),
The obtained aqueous solution refers to 1~5g SnCl4·5H2O crystal is dissolved in 100~150mL deionized water water.
3. the preparation method of stannic oxide carbon nano-complex according to claim 1, which is characterized in that in step (2),
The additional amount and SnCl of the glucose4·5H2The mass ratio of O crystal is (10~20): (1~5).
4. the preparation method of stannic oxide carbon nano-complex according to claim 1, which is characterized in that in step (3),
The condition of the centrifugation is 500~10000 revs/min.
5. the stannic oxide carbon nano-complex that any one preparation method is prepared in Claims 1 to 4.
6. stannic oxide carbon nano-complex according to claim 5, which is characterized in that the titanium dioxide tin carbon nanometer is multiple
Polymer beads partial size is 50~80nm.
7. the application that stannic oxide carbon nano-complex described in claim 5 makees anode in aluminium ion battery.
8. a kind of aluminium ion cell positive material, which is characterized in that its stannic oxide carbon as described in claim 5 is nano combined
Object, Kynoar and super phosphorus carbon black are according to mass ratio (70-90): (5-20): being scattered in solvent after (5-20) mixing, so
It is coated on 20~50 microns thick of light molybdenum foil and obtains afterwards.
9. aluminium ion cell positive material according to claim 8, which is characterized in that the solvent is N- crassitude
Ketone；Wherein, the mass volume ratio of Kynoar and N-Methyl pyrrolidone is 0.5~100mg/ml.
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| CN111682184A (en) * | 2020-06-23 | 2020-09-18 | 欣旺达电动汽车电池有限公司 | Tin-based composite material and preparation method thereof, negative plate and lithium ion battery |
| CN113437287A (en) * | 2021-05-10 | 2021-09-24 | 南昌航空大学 | Preparation method and application of tin oxide carbon-coated carbon and carbon composite material |
| CN113439908A (en) * | 2021-06-10 | 2021-09-28 | 深圳市顺成欣电子材料有限公司 | Heating shoe-pad that generate heat performance is good |
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| CN111453765A (en) * | 2020-04-09 | 2020-07-28 | 吉林大学 | Porous carbon-loaded ultra-small SnO2Nano particle composite material and preparation method and application thereof |
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| CN113437287A (en) * | 2021-05-10 | 2021-09-24 | 南昌航空大学 | Preparation method and application of tin oxide carbon-coated carbon and carbon composite material |
| CN113439908A (en) * | 2021-06-10 | 2021-09-28 | 深圳市顺成欣电子材料有限公司 | Heating shoe-pad that generate heat performance is good |
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