CN110745863B - Preparation method of zinc titanate/reduced graphene oxide nanocomposite and application of zinc titanate/reduced graphene oxide nanocomposite to lithium ion capacitor - Google Patents
Preparation method of zinc titanate/reduced graphene oxide nanocomposite and application of zinc titanate/reduced graphene oxide nanocomposite to lithium ion capacitor Download PDFInfo
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- CN110745863B CN110745863B CN201910852454.4A CN201910852454A CN110745863B CN 110745863 B CN110745863 B CN 110745863B CN 201910852454 A CN201910852454 A CN 201910852454A CN 110745863 B CN110745863 B CN 110745863B
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- 239000011701 zinc Substances 0.000 title claims abstract description 192
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 132
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 131
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 131
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 68
- 239000003990 capacitor Substances 0.000 title claims abstract description 35
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000725 suspension Substances 0.000 claims abstract description 45
- 238000002156 mixing Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000004108 freeze drying Methods 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000007773 negative electrode material Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract 2
- 239000010936 titanium Substances 0.000 claims description 71
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 34
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 11
- -1 polytetrafluoroethylene Polymers 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 239000007787 solid Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 239000002243 precursor Substances 0.000 claims description 10
- 229910052719 titanium Inorganic materials 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 8
- 239000001099 ammonium carbonate Substances 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 6
- 239000012716 precipitator Substances 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 238000004729 solvothermal method Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 abstract 1
- 239000001257 hydrogen Substances 0.000 abstract 1
- 238000001308 synthesis method Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 241000209094 Oryza Species 0.000 description 10
- 235000007164 Oryza sativa Nutrition 0.000 description 10
- 238000004519 manufacturing process Methods 0.000 description 10
- 235000009566 rice Nutrition 0.000 description 10
- 238000011056 performance test Methods 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 8
- 238000001291 vacuum drying Methods 0.000 description 7
- 229960000314 zinc acetate Drugs 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 5
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 241000482268 Zea mays subsp. mays Species 0.000 description 3
- 239000006256 anode slurry Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical group CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000006138 lithiation reaction Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940057499 anhydrous zinc acetate Drugs 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 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
- 150000004767 nitrides Chemical class 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/50—Electrodes characterised by their material specially adapted for lithium-ion capacitors, e.g. for lithium-doping or for intercalation
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2002/30—Three-dimensional structures
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- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- 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
- Y02E60/13—Energy storage using capacitors
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Abstract
The invention belongs to the technical field of nano composite materials, and relates to a preparation method of a zinc titanate/reduced graphene oxide nano composite material, which comprises the steps of firstly preparing zinc titanate micro-flowers by a solvothermal method, and then preparing a zinc titanate micro-flower suspension A and a graphene solution B; uniformly mixing the suspension A and the solution B to obtain a suspension C; freeze drying to obtain the zinc titanate/graphene oxide nano composite material with the hydrogen content of 5 percent2Calcining for 0.5-2 h at 200-400 ℃ in a mixed atmosphere of/Ar to obtain the catalyst. According to the invention, the pre-lithiated zinc titanate/reduced graphene oxide is used as a negative electrode active material of the lithium ion hybrid supercapacitor, the synthesis method is simple, no pollution is generated before and after reaction, and the cost is low. The good conductivity of the graphene can improve the transmission efficiency of electrons. The lithium ion capacitor has the advantages that the output voltage can reach 4.5V when being applied to the lithium ion capacitor, the energy density of the lithium ion capacitor is greatly improved, and the high energy density characteristic of the lithium ion battery and the high power density characteristic of the electric double layer capacitor are combined.
Description
Technical Field
The invention belongs to the technical field of nano composite materials, relates to preparation of a nano composite material, and particularly relates to a preparation method of a zinc titanate/reduced graphene oxide nano composite material and application of the zinc titanate/reduced graphene oxide nano composite material to a lithium ion capacitor.
Background
The lithium ion capacitor is a novel energy storage device, and has the advantages of high energy density of the lithium ion battery and high power density of the super capacitor. Two poles of the lithium ion capacitor adopt different electrode materials, one pole is a battery type material which mainly provides higher energy density, the common battery type materials mainly comprise transition metal oxides, metal nitrides and the like, and the materials usually have a layered or tunnel structure and are beneficial to ion intercalation; the other pole is a capacitor type material, primarily providing higher power density.
Common capacitor type types mainly include carbon materials such as activated carbon and graphene, and most of the materials have high specific surface area and are beneficial to adsorption and desorption of ions.
The zinc titanate is a transition metal titanium-based oxide, has the advantages of large specific surface area, good electrochemical stability, high theoretical capacity and the like, and can be used as a negative electrode material of a lithium ion capacitor. However, zinc titanate has low intrinsic conductivity and ion transmission rate, so that its electrochemical performance is limited. The reduced graphene oxide has a large specific surface area and high conductivity, and can well make up for the defect of poor conductivity of titanic acid.
According to the invention, the reduced graphene oxide is coated on the surface of the zinc titanate in a controllable and uniform manner, so that the conductivity of the nano composite material is effectively improved, the self-aggregation problem of the zinc titanate and the reduced graphene oxide is reduced, the reaction active sites of the nano composite material are fully exposed, and the capacity and the electrochemical stability of the nano composite material are obviously improved. The zinc titanate/reduced graphene oxide nano composite material is pre-lithiated and then matched with a carbon material with double electric layer capacitive performance to assemble a lithium ion capacitor, the working output voltage of the lithium ion capacitor can reach 4.5V, the power density and the energy density are obviously improved, and the lithium ion capacitor has a certain practical application prospect.
Disclosure of Invention
In view of the above-mentioned shortcomings of the prior art, the present invention provides a zinc titanate/reduced graphene oxide (Zn)2Ti3O8A preparation method of/rGO) nano composite material.
Technical scheme
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving a zinc source, a titanium source and a precipitator in ethylene glycol, transferring a zinc titanate precursor solution into a polytetrafluoroethylene lined reaction kettle, and reacting at 120-220 ℃ for 8-24 h, preferably at 200 ℃ for 12 h; cooling to room temperature; centrifugally separating precipitates, washing solids for several times by using deionized water and absolute ethyl alcohol respectively, and drying the solids for 2-5 hours in vacuum at the temperature of 60-80 ℃ to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 1 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 1: 4-2: 1, preferably 2:1, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain fluffy zinc titanate/graphene oxide nano composite material, and then carrying out freeze-drying on the fluffy zinc titanate/graphene oxide nano composite material at 5% H2Calcining at 200-400 ℃ for 0.5-2 h, preferably 400 ℃ for 0.5h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
In a preferred embodiment of the invention, in the step A, a zinc source, a titanium source and a precipitating agent are dissolved in ethylene glycol, wherein the dosage ratio of the zinc source, the titanium source, the precipitating agent and the ethylene glycol is 1-3 mmol: 1-4 mmol: 1-6 mmol: 10-30 ml, preferably 2mmol: 3mmol: 4mmol: 30 ml; the zinc source comprises zinc acetate, zinc nitrate, zinc chloride and the like, and preferably zinc acetate; the titanium source comprises tetrabutyl titanate, tetraisopropyl titanate, titanium tetrachloride and the like, and tetrabutyl titanate is preferred; the precipitant includes sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, etc., preferably ammonium carbonate.
In the preferred embodiment of the invention, the freeze-drying conditions in the step D are-45 ℃ and 48 hours.
It is a further object of the present invention to disclose the zinc titanate/reduced graphene oxide (Zn) produced2Ti3O8the/rGO) nano composite material is used as a negative electrode active material of a lithium ion capacitor to obtain an energy storage device with higher energy and power density.
A lithium ion super capacitor with high energy and high power density comprises a positive plate, a negative plate, a diaphragm, a gasket and electrolyte. The positive plate is Keqin conductive carbon black, and the negative plate is made of a negative materialPre-lithiation, the electrolyte is 1M LiPF6。
Furthermore, the negative plate is formed by coating negative slurry consisting of a negative active material, a conductive agent, a dispersing agent and a binder on the surface of a copper sheet. Wherein the negative active material is zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO); the conductive agent is Ketjenblack EC-600 JD; the dispersant is N-methyl pyrrolidone (NMP); the binder is an oily binder polyvinylidene fluoride (PVDF); the mass percentages are 80%, 10% and 10% in sequence.
Further, the pre-lithiation is to assemble the cathode material into a 2032 coin cell, pre-lithiate the cathode material for ten circles under the current density of 100 mA/g under the potential window of 0.01-3V to obtain LixZn2Ti3-xO8And a negative plate.
In order to match the negative plate so as to obtain the optimal performance, the positive electrode material is prepared by mixing ketjen conductive carbon black Ketjenblack EC-600JD with a binder (PTFE) according to the weight ratio of 9: 1, using ethanol as a dispersing agent to form anode slurry, coating the anode slurry on an aluminum sheet, and drying the anode slurry in a bellows at the temperature of 80 ℃ for 6 hours. Preferably, the ratio of the active mass (0.3-0.5 mg) on the negative plate to the active mass on the positive plate is 1: 5. 1: 6. 1: 7.
and (2) assembling the negative plate and the positive plate with different mass ratios into a full-cell device by taking lithium hexafluorophosphate as electrolyte, measuring cyclic voltammetry curves at different scanning rates under a potential window of 0.01-4.5V, and testing the multiplying power performance and the cyclic performance under current density, wherein the result shows that the mass ratio of the negative plate (0.5 mg) to the positive plate active material (3 mg) is 1: the performance is best when 6, the maximum power density is 67500W/kg, and the maximum energy density is 204 Wh/kg.
Advantageous effects
The present invention prelithiates zinc titanate/reduced graphene oxide (Li)xZn2Ti3-xO8/rGO) is used as a negative active material of a lithium ion hybrid super capacitor, and is a novel negative material with high energy density. The preparation method is simpleAnd the method has no pollution before and after reaction and relatively low cost. Meanwhile, the graphene is uniformly compounded with graphene, so that respective self-aggregation effect can be reduced; in addition, the good conductivity of the graphene can improve the transmission efficiency of electrons, so that the power density of the full-battery device is improved. Pre-lithiated zinc titanate/reduced graphene oxide (Li) as compared to other negative electrode materialsxZn2Ti3-xO8the/rGO) nano composite material has higher specific capacity, the output voltage of the lithium ion capacitor can reach 4.5V, and the energy density of the lithium ion capacitor is greatly improved, so that the lithium ion capacitor has the characteristics of high energy density of the lithium ion battery and high power density of an electric double layer capacitor.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of the zinc titanate nanomaterial obtained in example 1;
FIG. 2 Scanning Electron Micrographs (SEM) of zinc titanate popcorn (A) and zinc titanate/reduced graphene oxide (B) obtained in example 1;
FIG. 3 Transmission Electron Microscopy (TEM) images of zinc titanate popcorn (C) and zinc titanate/reduced graphene oxide (D) obtained in example 1;
FIG. 4 is a graph of rate capability and cycle stability of zinc titanate popcorn and zinc titanate/reduced graphene oxide obtained in example 1;
fig. 5 is a picture of the cycling stability of a lithium ion capacitor assembled from the zinc titanate/reduced graphene oxide obtained in example 1 and ketjen conductive carbon black.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8A method of making/rGO) nanocomposites comprising:
solvothermal method for preparing zinc titanate (Zn)2Ti3O8) Micro-flower rice: respectively adding 2mmol of anhydrous zinc acetate and 7.5 mmol of carbonic acidAdding solid sodium powder and 3mmol tetrabutyl titanate into a 100 mL beaker, adding 30mL ethylene glycol, and placing into an ultrasonic instrument for ultrasonic treatment for 15 min to uniformly mix; then, transferring the mixed solution into a 50 mL reaction kettle with a polytetrafluoroethylene substrate, sealing and placing the reaction kettle into an oven, controlling the temperature of the oven to be 200 ℃, and reacting for 12 hours; after the reaction is finished, cooling to room temperature, centrifugally separating a precipitate, and washing with deionized water and absolute ethyl alcohol for several times respectively; finally, the obtained solid product is dried for 3 hours in vacuum at the temperature of 80 ℃ to obtain the zinc titanate (Zn)2Ti3O8) Micro-flower of rice.
In FIG. 1, the diffraction peak positions and relative intensities match those of JPCDS cards (# 38-0500), indicating that the product is zinc titanate.
Weighing 200 mg of the obtained zinc titanate nanoparticles, dispersing the zinc titanate nanoparticles into 200 mL of deionized water to prepare 1g/L solution, and performing ultrasonic treatment for 30 min to uniformly disperse the solution to obtain a suspension A for later use; weighing 100 mg of graphene oxide, dispersing into 200 mL of deionized water to prepare a 0.5g/L solution, and performing ultrasonic treatment for 30 min to uniformly disperse the graphene oxide to obtain a solution B for later use; mixing the suspension A and the solution B according to a volume ratio of 2:1, and obtaining a suspension C after uniform mixing, namely the zinc titanate/graphene oxide nano composite material.
The suspension C is subjected to freeze drying treatment for 48 hours at the temperature of minus 45 ℃ to obtain a fluffy zinc titanate/graphene oxide nano composite material, and then the fluffy zinc titanate/graphene oxide nano composite material is subjected to freeze drying treatment at the temperature of 5% H2Calcining at 200-400 ℃ in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ per minute−1Keeping the temperature for 0.5-2 h to obtain the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8/rGO) nanocomposite with a conductive agent and a binder in a weight ratio of 8: 1: 1, manufacturing an electrode, assembling the electrode and a lithium sheet into a half cell, and carrying out performance test. The cycle is performed 500 times under the current density of 1.0A/g, and the performance stability in the cycle process is better, as shown in figure 4.
The zinc titanate/reduced graphene oxide (Zn) prepared in this example was used2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black, and the lithium ion capacitor is subjected to performance test to obtain the lithium ion capacitor with the maximum power density of 67500W/Kg and the maximum energy density of 204 Wh/Kg. The capacity retention was 76% after 1000 cycles at a current density of 1.0A/g, as shown in FIG. 5.
Example 2
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving 2mmol of zinc nitrate, 3mmol of tetrabutyl titanate and 4mmol of sodium bicarbonate in 30ml of ethylene glycol, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at 200 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 60 deg.C for 3 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 1 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 2:1, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 400 ℃ for 1 h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 55000W/Kg, and the maximum energy density is 180 Wh/Kg; the capacity retention rate was 70% after 1000 cycles at a current density of 1.0A/g.
Example 3
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving 2mmol of zinc acetate, 3mmol of tetraisopropyl titanate and 4mmol of ammonium carbonate in 30ml of ethylene glycol, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 24 hours at 200 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 60 deg.C for 3 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 2 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 1: 1, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 200 ℃ for 2h in a/Ar mixed atmosphere at the temperature rise rate of 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 49500W/Kg, and the maximum energy density is 190 Wh/Kg; the capacity retention rate was 65% after 1000 cycles at a current density of 1.0A/g.
Example 4
Zinc titanate/reduction oxidationGraphene (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving 3mmol of zinc acetate, 3mmol of tetrabutyl titanate and 2mmol of sodium carbonate in 30ml of ethylene glycol, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 12 hours at 200 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 60 deg.C for 6 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 2 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 1: 2, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 400 ℃ for 2h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 50000W/Kg, and the maximum energy density is 160 Wh/Kg; the capacity retention rate was 62% after 1000 cycles at a current density of 1.0A/g.
Example 5
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving 2mmol of zinc nitrate, 2mmol of tetrabutyl titanate and 2mmol of sodium carbonate in 30ml of ethylene glycol, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 16 hours at 200 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 80 deg.C for 6 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 2 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 1: 3, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 250 ℃ for 1.5 h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 52000W/Kg, and the maximum energy density is 140 Wh/Kg; the capacity retention rate was 65% after 1000 cycles at a current density of 1.0A/g.
Example 6
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Micro-flower, dissolving 3mmol of zinc acetate, 3mmol of tetrabutyl titanate and 2mmol of sodium carbonate in 30ml of ethylene glycol, and transferring the zinc titanate precursor solution into polytetrafluoroethyleneReacting for 12 hours at 200 ℃ in a lined reaction kettle; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 80 deg.C for 8 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 2 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 2:1, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 300 ℃ for 1.5 h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 57500W/Kg, and the maximum energy density is 170 Wh/Kg; the capacity retention rate was 65% after 1000 cycles at a current density of 1.0A/g.
Example 7
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving 3mmol of zinc acetate, 3mmol of tetrabutyl titanate and 2mmol of ammonium carbonate in 20 ml of ethylene glycol, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 12 hours at 200 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 80 deg.C for 6 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flowers in deionized water, and performing ultrasonic dispersion uniformly to obtain a suspension A with the mass concentration of 2 g/L; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 2: 3, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 400 ℃ for 2h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 45000W/Kg, and the maximum energy density is 125 Wh/Kg; the capacity retention rate was 55% after 1000 cycles at a current density of 1.0A/g.
Example 8
Zinc titanate/reduced graphene oxide (Zn)2Ti3O8The preparation method of the/rGO) nano composite material comprises the following steps:
A. solvothermal production of zinc titanate (Zn)2Ti3O8) Dissolving 3mmol of zinc acetate, 4mmol of tetrabutyl titanate and 6mmol of sodium carbonate in 30ml of ethylene glycol, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 6 hours at 200 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and anhydrous ethanol for several times, and vacuum drying at 60 deg.C for 6 hr to obtain zinc titanate (Zn)2Ti3O8) Micro-flower rice;
B. mixing zinc titanate (Zn)2Ti3O8) Dispersing the micro-flower in deionized water, and ultrasonically dispersing uniformly to obtain the productThe suspension A with the mass concentration of 2 g/L is obtained; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. mixing the suspension A and the solution B according to a volume ratio of 1: 2, uniformly mixing to obtain a suspension C;
D. freeze-drying the suspension C to obtain a fluffy zinc titanate/graphene oxide nano composite material; then at 5% H2Calcining at 400 ℃ for 1 h in a mixed atmosphere of/Ar, wherein the heating rate is 2 ℃ min−1Obtaining the zinc titanate/reduced graphene oxide (Zn)2Ti3O8/rGO) nanocomposites.
The zinc titanate/reduced graphene oxide (Zn) prepared in the example2Ti3O8the/rGO) nano composite material is pre-lithiated and then is made into a lithium ion capacitor with Keqin conductive carbon black for performance test. The maximum power density is 42000W/Kg, and the maximum energy density is 120 Wh/Kg; the capacity retention rate was 68% after 1000 cycles at a current density of 1.0A/g.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (9)
1. Preparation method of zinc titanate/reduced graphene oxide nano composite material, wherein molecular formula of zinc titanate is Zn2Ti3O8The method is characterized by comprising the following steps:
A. dissolving a zinc source, a titanium source and a precipitator in ethylene glycol, transferring a zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining, and reacting for 8-24 hours at 120-220 ℃; cooling to room temperature; centrifuging the precipitate, washing the solid with deionized water and absolute ethyl alcohol for several times respectively, and drying in vacuum at the temperature of 60-80 ℃ for 2-5 h to obtain the zinc titanate micro-flowers, wherein the molecular formula of the zinc titanate is Zn2Ti3O8Wherein the dosage ratio of the zinc source, the titanium source, the precipitator and the glycol is 1-3 mmol: 1E4mmol, 1-6 mmol, 10-30 ml; the zinc source comprises zinc acetate, zinc nitrate and zinc chloride; the titanium source comprises tetrabutyl titanate, tetraisopropyl titanate and titanium tetrachloride; the precipitant comprises sodium carbonate, sodium bicarbonate, ammonium carbonate and ammonium bicarbonate;
B. dispersing zinc titanate micro flowers in deionized water, and obtaining suspension A with the mass concentration of 1g/L after uniform ultrasonic dispersion; performing ultrasonic dispersion, and preparing 0.5g/L graphene oxide aqueous solution to obtain solution B;
C. uniformly mixing the suspension A and the solution B according to the volume ratio of 1: 4-2: 1 to obtain a suspension C;
D. freeze-drying the suspension C to obtain fluffy zinc titanate/graphene oxide nano composite material, and then carrying out freeze-drying on the fluffy zinc titanate/graphene oxide nano composite material at 5% H2Calcining for 0.5-2 h at 200-400 ℃ in a/Ar mixed atmosphere, wherein the heating rate is 2 ℃ per minute−1And (5) obtaining the product.
2. The method of preparing a zinc titanate/reduced graphene oxide nanocomposite according to claim 1, wherein: the dosage ratio of the zinc source, the titanium source, the precipitating agent and the ethylene glycol in the step A is 2mmol: 3mmol: 4mmol: 30 ml.
3. The method of preparing a zinc titanate/reduced graphene oxide nanocomposite according to claim 1, wherein: in the step A, the zinc source is zinc acetate, the titanium source is tetrabutyl titanate, and the precipitator is ammonium carbonate.
4. The method of preparing a zinc titanate/reduced graphene oxide nanocomposite according to claim 1, wherein: and C, transferring the zinc titanate precursor solution into a reaction kettle with a polytetrafluoroethylene lining in the step A, and reacting for 12 hours at 200 ℃.
5. The method of preparing a zinc titanate/reduced graphene oxide nanocomposite according to claim 1, wherein: and C, uniformly mixing the suspension A and the solution B according to the volume ratio of 2:1 to obtain a suspension C.
6. The method of preparing a zinc titanate/reduced graphene oxide nanocomposite according to claim 1, wherein: and D, performing freeze drying for 48 hours at the temperature of-45 ℃.
7. The method of preparing a zinc titanate/reduced graphene oxide nanocomposite according to claim 1, wherein: said at 5% H in step D2Calcining for 0.5h at 400 ℃ in an/Ar mixed atmosphere.
8. The zinc titanate/reduced graphene oxide nanocomposite prepared according to the method of any one of claims 1 to 7.
9. Use of the zinc titanate/reduced graphene oxide nanocomposite material of claim 8, wherein: the obtained product is used as a negative electrode active material of a lithium ion capacitor.
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| "Synthesis of the graphene-ZnTiO3 nanocomposite for solar light assisted photodegradation of ethylene blue";Shunmugiah Gayathri1 et al;《Journal of Physics D:Applied Physics》;20150924;第48卷;第2页右栏第4段，第3页左栏第1段） * |
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