CN106299216A - A kind of Ti3+doping TiO2the preparation method and application of nano-tube array/sulfonated polyphenyl phenol membrane electrode - Google Patents
A kind of Ti3+doping TiO2the preparation method and application of nano-tube array/sulfonated polyphenyl phenol membrane electrode Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 72
- 239000002071 nanotube Substances 0.000 title claims abstract description 58
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229920006389 polyphenyl polymer Polymers 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 135
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 46
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000003792 electrolyte Substances 0.000 claims abstract description 29
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000007743 anodising Methods 0.000 claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 16
- 150000002989 phenols Chemical class 0.000 claims abstract description 14
- 229940061610 sulfonated phenol Drugs 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 239000010936 titanium Substances 0.000 claims description 51
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 30
- 229910052697 platinum Inorganic materials 0.000 claims description 25
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 17
- 239000010409 thin film Substances 0.000 claims description 10
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 8
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical group [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- 235000013024 sodium fluoride Nutrition 0.000 claims description 4
- 239000011775 sodium fluoride Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000006258 conductive agent Substances 0.000 abstract description 9
- 239000011230 binding agent Substances 0.000 abstract description 8
- 239000007772 electrode material Substances 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 238000002848 electrochemical method Methods 0.000 abstract 1
- 230000005518 electrochemistry Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 230000005611 electricity Effects 0.000 description 14
- 239000010408 film Substances 0.000 description 13
- 229910052744 lithium Inorganic materials 0.000 description 11
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 10
- 239000004698 Polyethylene Substances 0.000 description 10
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 9
- 230000004888 barrier function Effects 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 238000001035 drying Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 239000011259 mixed solution Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 238000004088 simulation Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 150000002148 esters Chemical class 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910013872 LiPF Inorganic materials 0.000 description 3
- 101150058243 Lipf gene Proteins 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- QNLVXLJTOLHAMA-UHFFFAOYSA-N N=NC=NN.N=NC=NN.C(O)(O)=O Chemical compound N=NC=NN.N=NC=NN.C(O)(O)=O QNLVXLJTOLHAMA-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010291 electrical method Methods 0.000 description 2
- 230000037427 ion transport Effects 0.000 description 2
- 229920006254 polymer film Polymers 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/02—Electrolytic coating other than with metals with organic materials
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
- H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
- H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
- H01M50/409—Separators, membranes or diaphragms characterised by the material
- H01M50/411—Organic material
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The open a kind of Ti of the present invention3+Doping TiO2The preparation method and application of nano-tube array/sulfonated polyphenyl phenol membrane electrode, first uses anodizing, prepares three-dimensional order TiO2Nano-tube array, then in three-electrode system, prepares Ti by electrochemical method3+The TiO of doping2Nano-tube array, finally with Ti3+The TiO of doping2Nano-tube array, as working electrode, with sulfonated phenol solution as electrolyte, is reacted by electrochemical polymerization, prepares Ti3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode, when being applied to lithium ion battery by the membrane electrode obtained, it is not necessary to add extra conductive agent and binding agent;Present invention process is simple, environmental friendliness, passes through Ti3+Doping improves TiO2The electric conductivity of nano-tube array, and the electrochemistry achieving membrane electrode is integrated, is applied to lithium ion battery, the synergism between film and electrode material improves charge/discharge specific capacity and the stable circulation performance of membrane electrode material.
Description
Technical field
The open a kind of Ti of the present invention3+Doping TiO2The preparation method and application of nano-tube array/sulfonated polyphenyl phenol membrane electrode,
Belong to the research field of new energy materials.
Background technology
TiO2It is a kind of important semiconductor-transition metal-oxide, has that cubical expansivity is little, can avoid lithium metal branch
The plurality of advantages such as partial crystallization goes out, can serve as lithium ion battery negative material, and the pattern of electrode material and dimensional effect are to electric polarity
Can have TiO prepared by material impact, such as anodizing2NT is regular in order, and specific surface area is big, it is not necessary to another adding additives and
Conductive agent, can be directly used as lithium ion battery anode active material.
But, due to TiO2Intrinsic characteristic of semiconductor electrical conductivity is low, limits giving full play to of its advantage, the most
There is correlational study that it is carried out Fe3+Or the doping of Ag or modification improve TiO2Electrical conductivity, but can be steady to the heat of material self
Qualitative having undesirable effect, technique is complex simultaneously, and cost is high, realizes TiO by electrochemical process2Ti3+Doping, it is also possible to
Improve TiO2Electric conductivity and technique is simple, environmental protection.
Lithium ion battery is the green energy-storing device of a kind of high efficiency, high-energy-density, has been widely used in moving
Galvanic electricity subset, electrode and barrier film are the critical components of lithium ion battery, of close concern to each other with the performance of lithium ion battery, are current
The focus of research.
Barrier film as one of the critical component of lithium ion battery, its performance determine the interfacial structure between film and electrode,
The internal resistance etc. of battery, and then affect the performance of battery, business-like barrier film is mainly microporous polymer film (such as polyethylene
PE), although this kind of barrier film has good mechanical performance and chemical stability, but breathability and lyophily are poor, are unfavorable for
The moistening of electrolyte and the transmission of lithium ion, cause internal resistance relatively big, therefore, it is necessary to carry out novel lithium ion battery diaphragm aspect
Research.The present invention, with sulfonated phenol as monomer, realizes sulfonated polyphenyl phenol (SPPO) thin film and Ti by electric polymerization reaction3+/
TiO2Electrochemistry between NT electrode is integrated, prepares membrane electrode SPPO/Ti3+/TiO2NT, additionally, Ti3+/TiO2NT combination electrode
Electrical conductivity improve, be also beneficial to the polyreaction of sulfonated phenol, this membrane electrode has merged doping vario-property electrode material and novel
The two-fold advantage of barrier film, can improve electrode material electrical conductivity, reduce the internal resistance of cell, the contact surface increased between film and electrode
Long-pending, improve lithium ion diffusion coefficient, shorten lithium ion transport distance, improve performance of lithium ion battery, to lithium ion battery film electricity
The research of pole is significant.
Summary of the invention
The technical problem to be solved in the present invention: simultaneously improve in terms of the electrode material and two, barrier film of lithium ion battery
The chemical property of lithium ion battery.
It is an object of the invention to provide a kind of Ti3+Doping TiO2The preparation of nano-tube array/sulfonated polyphenyl phenol membrane electrode
Method and application, concrete, prepare Ti3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode, and the film electricity obtained is provided
Pole application in lithium ion battery, is wherein the routine during lithium ion battery is prepared in this area to electrode and reference electrode
Select.
It is an object of the invention to provide described Ti3+Doping TiO2The preparation of nano-tube array/sulfonated polyphenyl phenol membrane electrode
Method, specifically comprises the following steps that
(1) using anodizing, using titanium sheet as working electrode, platinum electrode is to electrode, and fluorine-containing solution is electrolyte, just
Current potential constant voltage reaction 1h ~ 5h, rinses working electrode post-drying well and i.e. can get three-dimensional order TiO2Nano-tube array
TiO2NT;
(2) in three-electrode system, the TiO obtained with step (1)2Nano-tube array is working electrode, and platinum electrode is to electrode,
Saturated calomel electrode is reference electrode, and electrochemicaUy inert solution is electrolyte, reacts 20s ~ 600s in nagative potential constant voltage, obtains
Ti3+Doping TiO2Nano-tube array (Ti3+/TiO2NT);
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT is as working electrode, and platinum electrode is to electrode, full
Being reference electrode with calomel electrode, sulfonated phenol solution is electrolyte, reacts 0.5h ~ 3h by electrochemical polymerization, at Ti3+Doping
TiO2Nanometer pipe array electrode Surface Creation sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol
Membrane electrode (SPPO/Ti3+/TiO2NT).
Preferably, component and the mass percent of the described fluorine-containing solution of step (1) is: fluoride 0.3% ~ 0.7%, distilled water
14.3% ~ 14.7%, surplus is glycerol, and described fluoride is sodium fluoride, ammonium fluoride or Fluohydric acid..
Preferably, the voltage of step (1) described positive potential constant voltage reaction is 10V ~ 50V.
Preferably, step (2) described electrochemicaUy inert solution is metabisulfite solution, potassium nitrate solution or dilution heat of sulfuric acid.
Preferably, the concentration of step (2) described electrochemicaUy inert solution is 0.1mol/L ~ 5.0mol/L.
Preferably, the voltage of step (2) described nagative potential constant voltage reaction is-1.5V ~-0.5V.
Preferably, the concentration of step (3) described sulfonated phenol solution is 0.02mol/L ~ 0.5mol/L.
Preferably, the voltage range of step (3) described electrochemical polymerization reaction is 1.0V ~ 1.6V.
Another object of the present invention is to provide described Ti3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode
The application of the membrane electrode that preparation method prepares, the membrane electrode prepared is during preparing lithium ion battery, it is not necessary to add
Add extra conductive agent and binding agent, directly with this membrane electrode for as working electrode, with lithium paper tinsel for electrode and reference electrode,
Be full of high-purity argon gas glove box in be assembled into button simulation lithium ion battery, and with the method for constant current charge/discharge test its fill/
Discharge performance and cyclical stability.
Platinum electrode of the present invention, saturated calomel electrode are conventional electrodes, are this area and prepare lithium ion battery mistake
Conventional selection in journey.
The present invention is by scanning electron microscope (SEM), X-ray energy dispersive spectrometer (EDX), x-ray photoelectron energy
Spectrum (XPS) and electrochemical property test technology are to prepared three-dimensional order TiO2The microstructure of nano-tube array, pattern
And chemical property characterizes, SEM photograph clearly shows that Ti3+Doping is to TiO2The microscopic appearance of NT electrode does not has shadow
Ring, still maintain regular orderly nano-tube array structure, after sulfonated phenol electropolymerization, Ti3+/TiO2NT electrode table
One layer of loose thin polymer film is deposited on face;EDX spectrogram also occurs in that carbon, oxygen, sulfur etc. are corresponding with sulfonated polyphenyl phenol
Signal;XPS collection of illustrative plates occurs in that Ti3+The signal peak corresponding with carbon in sulfonated polyphenyl phenol, oxygen, element sulphur;Chemical property is surveyed
Examination SPPO/Ti3+/TiO2The chemical property of NT membrane electrode, and and PE/TiO2NT membrane electrode contrasts.
Advantages of the present invention and beneficial effect:
The present invention improves the chemical property of lithium ion battery in terms of the electrode material and two, barrier film of lithium ion battery, and one
Aspect, passes through Ti3+Doping improve TiO2The electrical conductivity of NT electrode;On the other hand, at Ti3+/TiO2One is deposited on NT electrode
Layer SPPO barrier film, and utilize its proton conductivity, reduce the internal resistance of cell, improve lithium ion diffusion coefficient, simultaneously as
Ti3+/TiO2The electric conductivity of NT increases, beneficially sulfonated polyphenyl phenol and Ti3+/TiO2Electrochemistry between NT electrode is integrated, increases
Contact area between electrode and film, shortens lithium ion transport distance, and membrane electrode of the present invention has merged doping vario-property electricity
Pole material and the two-fold advantage of new types of diaphragm, improve the charge/discharge performance of lithium ion battery.
Accompanying drawing explanation
Fig. 1 is the pure TiO of the embodiment of the present invention 1 preparation2The SEM figure of NT;
Fig. 2 is the Ti of the embodiment of the present invention 1 preparation3+/TiO2The SEM figure of NT;
Fig. 3 is the SPPO/Ti of the embodiment of the present invention 1 preparation3+/TiO2The SEM figure of NT membrane electrode;
Fig. 4 is the SPPO/Ti of the embodiment of the present invention 2 preparation3+/TiO2The EDX collection of illustrative plates of NT membrane electrode;
Fig. 5 is the SPPO/Ti of the embodiment of the present invention 3 preparation3+/TiO2The XPS collection of illustrative plates of NT membrane electrode;
Fig. 6 is the SPPO/Ti of the embodiment of the present invention 4 preparation3+/TiO2NT membrane electrode and contrast PE/TiO2NT membrane electrode is first
Charge/discharge curve;
Fig. 7 is the SPPO/Ti of the embodiment of the present invention 5 preparation3+/TiO2NT membrane electrode and contrast PE/TiO2200 times of NT membrane electrode
Cyclical stability;
Fig. 8 is the SPPO/Ti of the embodiment of the present invention 6 preparation3+/TiO2NT membrane electrode and contrast PE/TiO2The multiplying power of NT membrane electrode
Performance.
Detailed description of the invention
With specific embodiment, the present invention is described in further detail below in conjunction with the accompanying drawings, but protection scope of the present invention is also
It is not limited to described content.
Embodiment 1
Ti described in the present embodiment3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, concrete steps are such as
Under:
(1) using anodizing, using clean titanium sheet as working electrode, platinum electrode is to electrode, and mass percent is
The NaF of 0.5%, the H of 14.5%2The mixed solution of O and glycerol is electrolyte, carries out anodic oxidation 2h, by work by constant voltage (30V)
Make the clean post-drying of electrode washing and i.e. can get three-dimensional order TiO2Nano-tube array TiO2NT;
(2) in three-electrode system, the TiO prepared with step (1) anodizing2NT is working electrode, and platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, and concentration is the Na of 1.0mol/L2SO4Solution is electrolyte, and constant voltage (-1.0V) is reacted
200s, obtains Ti3+The TiO of doping2NT combination electrode Ti3+/TiO2NT;
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT combination electrode as working electrode, platinum electrode is
To electrode, saturated calomel electrode is reference electrode, concentration be the sulfonated phenol solution of 0.02mol/L be electrolyte, constant voltage
(1.0V) electrochemical polymerization reaction 3h, at Ti3+/TiO2NT electrode surface generates sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2
Nano-tube array/sulfonated polyphenyl phenol membrane electrode SPPO/Ti3+/TiO2NT。
It is respectively the pure TiO that step (1) obtains as Figure 1-32The Ti that NT electrode, step (2) obtain3+/TiO2NT is multiple
The SPPO/Ti that composite electrode, step (3) obtain3+/TiO2The SEM figure of NT membrane electrode, as seen from the figure, Ti3+Doping is to TiO2The battle array of NT
Array structure does not affect, and still remains regular orderly nano-tube array structure, after electric polymerization reaction, at Ti3+/
TiO2NT electrode surface one layer of loose thin film of deposition.
Use the Ti that embodiment 1 prepares3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode prepares lithium ion
Battery, it is not necessary to add extra conductive agent and binding agent, directly with SPPO/Ti3+/TiO2NT is working electrode, is right with lithium paper tinsel
Electrode and reference electrode, be assembled into button simulation lithium ion battery in the glove box of full high-purity argon gas, and with constant current discharge charge
The method of electricity tests its charge/discharge performance and cyclical stability, and the first charge-discharge capacity of result display lithium ion battery is high, follows
Ring good stability.
Embodiment 2
Ti described in the present embodiment3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, concrete steps are such as
Under:
(1) using anodizing, using clean titanium sheet as working electrode, platinum electrode is to electrode, and mass percent is
The NH of 0.3%4F, the H of 14.7%2The mixed solution of O and glycerol is electrolyte, carries out anodic oxidation 4h by constant potential (40V),
Working electrode is rinsed well post-drying and i.e. can get three-dimensional order TiO2Nano-tube array TiO2NT;
(2) in three-electrode system, the TiO prepared with step (1) anodizing2NT is working electrode, and platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, and concentration is the H of 2.5mol/L2SO4Solution is electrolyte, and constant voltage (-1.5V) is reacted
20s, obtains Ti3+The TiO of doping2NT combination electrode Ti3+/TiO2NT;
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT combination electrode as working electrode, platinum electrode is
To electrode, saturated calomel electrode is reference electrode, concentration be 0.1mol/L sulfonated phenol solution be electrolyte, constant voltage (1.2V) electricity
Chemical polymerization 2.5h, at Ti3+/TiO2NT electrode surface generates sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2Nanotube
Array/sulfonated polyphenyl phenol membrane electrode SPPO/Ti3+/TiO2NT。
Fig. 4 is the SPPO/Ti that the present embodiment prepares3+/TiO2The EDX spectrogram of NT membrane electrode, figure occurs in that carbon,
The signal that oxygen, sulfur etc. are corresponding with sulfonated polyphenyl phenol, illustrates in the material that embodiment prepares containing these materials.
Use the Ti that embodiment 1 prepares3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode prepares lithium ion
Battery, it is not necessary to add extra conductive agent and binding agent, directly with SPPO/Ti3+/TiO2NT is working electrode, is right with lithium paper tinsel
Electrode and reference electrode, be assembled into button simulation lithium ion battery in the glove box of full high-purity argon gas, and with constant current discharge charge
The method of electricity tests its charge/discharge performance and cyclical stability, and result display lithium ion battery first charge-discharge capacity is high, circulation
Good stability.
Embodiment 3
Ti described in the present embodiment3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, concrete steps are such as
Under:
(1) using anodizing, to process clean titanium sheet as working electrode, platinum electrode is to electrode, mass percent
It is HF, 14.3% H of 0.7%2The mixed solution of O and glycerol is electrolyte, carries out anodic oxidation 1h by constant potential (20V), will
Working electrode is rinsed post-drying well and i.e. be can get three-dimensional order TiO2Nano-tube array TiO2NT;
(2) in three-electrode system, the TiO prepared with step (1) anodizing2NT is working electrode, and platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, and concentration is the Na of 2.0mol/L2SO4Solution is electrolyte, and constant voltage (-0.5V) is reacted
600s, obtains Ti3+The TiO of doping2NT combination electrode Ti3+/TiO2NT;
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT combination electrode as working electrode, platinum electrode is
To electrode, saturated calomel electrode is reference electrode, concentration be the sulfonated phenol solution of 0.2mol/L be electrolyte, constant voltage (1.3V)
Electrochemical polymerization reaction 2h, at Ti3+/TiO2NT electrode surface generates sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2Nanotube
Array/sulfonated polyphenyl phenol membrane electrode SPPO/Ti3+/TiO2NT。
Fig. 5 is the SPPO/Ti that the present embodiment prepares3+/TiO2The XPS spectrum figure of NT membrane electrode, as seen from the figure, from
SPPO/Ti3+/TiO2NT membrane electrode detects Ti3+The signal peak corresponding with sulfur in sulfonated polyphenyl phenol, carbon, oxygen element.
Use the Ti that embodiment 3 prepares3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode prepares lithium ion
Battery, it is not necessary to add extra conductive agent and binding agent, directly with SPPO/Ti3+/TiO2NT is working electrode, is right with lithium paper tinsel
Electrode and reference electrode, be assembled into button simulation lithium ion battery in the glove box of full high-purity argon gas, and with constant current discharge charge
The method of electricity tests its charge/discharge performance and cyclical stability, and result display lithium ion battery first charge-discharge capacity is high, circulation
Good stability.
Embodiment 4
Ti described in the present embodiment3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, concrete steps are such as
Under:
(1) using anodizing, to process clean titanium sheet as working electrode, platinum electrode is to electrode, mass percent
It is the NH of 0.6%4F, the H of 14.4%2The mixed solution of O and glycerol is electrolyte, carries out anodic oxidation 5h by constant potential (10V),
Working electrode is rinsed well post-drying and i.e. can get three-dimensional order TiO2Nano-tube array TiO2NT;
(2) in three-electrode system, the TiO prepared with step (1) anodizing2NT is working electrode, and platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, and concentration is the KNO of 0.1mol/L3Solution is electrolyte, and constant voltage (-1.2V) is reacted
100s, obtains Ti3+The TiO of doping2NT combination electrode Ti3+/TiO2NT;
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT combination electrode as working electrode, platinum electrode is
To electrode, saturated calomel electrode is reference electrode, concentration be the sulfonated phenol solution of 0.25mol/L be electrolyte, constant voltage
(1.4V) electrochemical polymerization reaction 1h, at Ti3+/TiO2NT electrode surface generates sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2
Nano-tube array/sulfonated polyphenyl phenol membrane electrode SPPO/Ti3+/TiO2NT。
Use the Ti that embodiment 4 prepares3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode prepares lithium ion
Battery, it is not necessary to add extra conductive agent and binding agent, directly with SPPO/Ti3+/TiO2NT is working electrode, is right with lithium paper tinsel
Electrode and reference electrode, the LiPF with concentration as 1mol/L6Ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid diformazan
The mixed liquor of ester (DMC) is electrolyte, and wherein the volume ratio of EC, DEC and DMC is 1:1:1, at the glove of full high-purity argon gas
It is assembled into button simulation lithium ion battery in case with lithium paper tinsel, and tests its charge/discharge performance, Fig. 6 with the method for constant current charge/discharge
For SPPO/Ti3+/TiO2NT membrane electrode and contrast PE/TiO2The charge/discharge curve first of NT membrane electrode, as seen from the figure, SPPO/
Ti3+/TiO2The first discharge specific capacity of the lithium ion battery that NT membrane electrode prepares reaches 531mAh/g, much larger than contrast
PE/TiO2The 277mAh/g of NT membrane electrode.
Embodiment 5
Ti described in the present embodiment3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, concrete steps are such as
Under:
(1) using anodizing, to process clean titanium sheet as working electrode, platinum electrode is to electrode, mass percent
It is HF, the H of 14.5% of 0.5%2The mixed solution of O and glycerol is electrolyte, carries out anodic oxidation 2h by constant potential (30V),
Working electrode is rinsed well post-drying and i.e. can get three-dimensional order TiO2Nano-tube array TiO2NT;
(2) in three-electrode system, the TiO prepared with step (1) anodizing2NT is working electrode, and platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, and concentration is the H of 5mol/L2SO4Solution is electrolyte, constant voltage (-0.5V) reaction 500s,
Obtain Ti3+The TiO of doping2NT combination electrode (Ti3+/TiO2NT);
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT combination electrode as working electrode, platinum electrode is
To electrode, saturated calomel electrode is reference electrode, concentration be the sulfonated phenol solution of 0.35mol/L be electrolyte, constant voltage
(1.6V) electrochemical polymerization reaction 0.5h, at Ti3+/TiO2NT electrode surface generates sulfonated polyphenyl phenol thin film, obtains Ti3+Doping
TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode SPPO/Ti3+/TiO2NT。
Use the Ti that embodiment 5 prepares3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode prepares lithium ion
Battery, it is not necessary to add extra conductive agent and binding agent, directly with SPPO/Ti3+/TiO2NT is working electrode, is right with lithium paper tinsel
Electrode and reference electrode, the LiPF with concentration as 1mol/L6Ethylene carbonate (EC) and the mixed liquor of diethyl carbonate (DEC)
For electrolyte, wherein, the volume ratio of EC and DEC is 1:1, is assembled into button mould with lithium paper tinsel in the glove box of full high-purity argon gas
Intend lithium ion battery, and test its stable circulation performance with constant current discharge charge electrical method, if Fig. 7 is SPPO/Ti3+/TiO2NT membrane electrode
And contrast PE/TiO2200 cyclical stabilities of the lithium ion battery that NT membrane electrode prepares.
Embodiment 6
Ti described in the present embodiment3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, concrete steps are such as
Under:
(1) using anodizing, to process clean titanium sheet as working electrode, platinum electrode is to electrode, mass percent
Be the NaF of 0.6 %, the H of 14.4%2The mixed solution of O and glycerol is electrolyte, carries out anodic oxidation by constant potential (50V)
3h, rinses working electrode post-drying well and i.e. can get three-dimensional order TiO2Nano-tube array TiO2NT;
(2) in three-electrode system, the TiO prepared with step (1) anodizing2NT is working electrode, and platinum electrode is to electricity
Pole, saturated calomel electrode is reference electrode, and concentration is the KNO of 4mol/L3Solution is electrolyte, constant voltage (-0.7V) reaction 600s,
Obtain Ti3+The TiO of doping2NT combination electrode Ti3+/TiO2NT;
(3) in three-electrode system, the Ti obtained with step (2)3+/TiO2NT combination electrode as working electrode, platinum electrode is
To electrode, saturated calomel electrode is reference electrode, concentration be the sulfonated phenol solution of 0.5mol/L be electrolyte, constant voltage (1.0V)
Electrochemical polymerization reaction 1.5h, at Ti3+/TiO2NT electrode surface generates sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2Nanometer
Pipe array/sulfonated polyphenyl phenol membrane electrode SPPO/Ti3+/TiO2NT。
Use the Ti that embodiment 6 prepares3+Doping TiO2Nano-tube array/sulfonated polyphenyl phenol membrane electrode prepares lithium ion
Battery, it is not necessary to add extra conductive agent and binding agent, directly with SPPO/Ti3+/TiO2NT is working electrode, is right with lithium paper tinsel
Electrode and reference electrode, the LiPF with concentration as 1mol/L6Ethylene carbonate (EC), diethyl carbonate (DEC), carbonic acid diformazan
The mixed liquor of ester (DMC) is electrolyte, and wherein the volume ratio of EC, DEC and DMC is 1:1:1, at the glove of full high-purity argon gas
It is assembled into button simulation lithium ion battery in case with lithium paper tinsel, and tests its high rate performance with constant current discharge charge electrical method, as Fig. 8 is
SPPO/Ti3+/TiO2Lithium ion battery prepared by NT membrane electrode and contrast PE/TiO2Lithium ion battery prepared by NT membrane electrode
High rate performance.
Claims (10)
1. a Ti3+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is characterised in that specifically walk
Rapid as follows:
(1) using anodizing, using titanium sheet as working electrode, platinum electrode is to electrode, and fluorine-containing solution is electrolyte, just
Current potential constant voltage reaction 1h ~ 5h, obtains TiO2Nano-tube array;
(2) in three-electrode system, the TiO obtained with step (1)2Nano-tube array is working electrode, and platinum electrode is to electrode,
Saturated calomel electrode is reference electrode, and electrochemicaUy inert solution is electrolyte, reacts 20s ~ 600s in nagative potential constant voltage, obtains
Ti3+Doping TiO2Nano-tube array;
(3) in three-electrode system, the Ti obtained with step (2)3+Doping TiO2Nano-tube array is as working electrode, platinum electrode
For to electrode, saturated calomel electrode is reference electrode, and sulfonated phenol solution is electrolyte, by electrochemical polymerization reaction 0.5h ~
3h, at Ti3+Doping TiO2Nanometer pipe array electrode Surface Creation sulfonated polyphenyl phenol thin film, obtains Ti3+Doping TiO2Nanotube battle array
Row/sulfonated polyphenyl phenol membrane electrode.
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, component and the mass percent of the described fluorine-containing solution of step (1) be: fluoride 0.3% ~ 0.7%, distilled water 14.3% ~
14.7%, surplus is glycerol.
Ti the most according to claim 23+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, described fluoride is sodium fluoride, ammonium fluoride or Fluohydric acid..
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, the voltage of step (1) described positive potential constant voltage reaction is 10V ~ 50V.
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, step (2) described electrochemicaUy inert solution is metabisulfite solution, potassium nitrate solution or dilution heat of sulfuric acid.
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, the concentration of step (2) described electrochemicaUy inert solution is 0.1mol/L ~ 5.0mol/L.
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, the voltage of step (2) described nagative potential constant voltage reaction is-1.5V ~-0.5V.
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, the concentration of step (3) described sulfonated phenol solution is 0.02mol/L ~ 0.5mol/L.
Ti the most according to claim 13+Doping TiO2The preparation method of nano-tube array/sulfonated polyphenyl phenol membrane electrode, it is special
Levying and be, the voltage of step (3) described electrochemical polymerization reaction is 1.0V ~ 1.6V.
10. Ti described in claim 1-9 any one3+Doping TiO2The preparation side of nano-tube array/sulfonated polyphenyl phenol membrane electrode
The membrane electrode that method prepares application in lithium ion battery.
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Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109301192A (en) * | 2018-09-13 | 2019-02-01 | 欣旺达电子股份有限公司 | Lithium ion battery anode slurry preparation method, lithium ion battery negative material and lithium ion battery |
CN110158108A (en) * | 2019-06-11 | 2019-08-23 | 铜仁学院 | Material containing trivalent titanium ion auto-dope titanium dioxide and preparation method thereof and energy storage device |
CN111792706A (en) * | 2020-08-27 | 2020-10-20 | 南京师范大学 | Electrochemical oxidation treatment reactor with cation exchange membrane and method for treating pyridine wastewater |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102644099A (en) * | 2012-04-27 | 2012-08-22 | 昆明理工大学 | Preparing method for sulfonate polyphenol thin films |
CN104593849A (en) * | 2014-12-23 | 2015-05-06 | 昆明理工大学 | Preparation method and applications of carburized titanium dioxide nanotube array |
-
2016
- 2016-08-10 CN CN201610650081.9A patent/CN106299216A/en active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN102644099A (en) * | 2012-04-27 | 2012-08-22 | 昆明理工大学 | Preparing method for sulfonate polyphenol thin films |
CN104593849A (en) * | 2014-12-23 | 2015-05-06 | 昆明理工大学 | Preparation method and applications of carburized titanium dioxide nanotube array |
Non-Patent Citations (4)
Title |
---|
JIXIANG DUAN ET AL.,: ""High performance PPO/ Ti3+/ TiO2NT membrane/electrode for lithium ion battery"", 《CERAMICS INTERNATIONAL》 * |
JIXIANG DUAN, ET AL.,: ""In situ Ti3+ doped TiO2 nanotubes anode for lithium ion battery"", 《JOURNAL OF POROUS MATERIALS》 * |
RUIJIN MENG ET AL.,: ""Reassessment of the roles of Ag in TiO2 nanotubes anode material for lithium ion battery"", 《CERAMICS INTERNATIONAL》 * |
段继祥等: ""苯酚及其衍生物的电聚合研究进展"", 《工程塑料应用》 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109301192A (en) * | 2018-09-13 | 2019-02-01 | 欣旺达电子股份有限公司 | Lithium ion battery anode slurry preparation method, lithium ion battery negative material and lithium ion battery |
CN110158108A (en) * | 2019-06-11 | 2019-08-23 | 铜仁学院 | Material containing trivalent titanium ion auto-dope titanium dioxide and preparation method thereof and energy storage device |
CN111792706A (en) * | 2020-08-27 | 2020-10-20 | 南京师范大学 | Electrochemical oxidation treatment reactor with cation exchange membrane and method for treating pyridine wastewater |
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