CN105575675A - Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor - Google Patents
Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor Download PDFInfo
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- CN105575675A CN105575675A CN201511011426.8A CN201511011426A CN105575675A CN 105575675 A CN105575675 A CN 105575675A CN 201511011426 A CN201511011426 A CN 201511011426A CN 105575675 A CN105575675 A CN 105575675A
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- 238000000034 method Methods 0.000 title claims abstract description 30
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- RJSRQTFBFAJJIL-UHFFFAOYSA-N niobium titanium Chemical compound [Ti].[Nb] RJSRQTFBFAJJIL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 19
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 238000004729 solvothermal method Methods 0.000 title abstract 3
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 19
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 239000010955 niobium Substances 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- OBOYOXRQUWVUFU-UHFFFAOYSA-N [O-2].[Ti+4].[Nb+5] Chemical compound [O-2].[Ti+4].[Nb+5] OBOYOXRQUWVUFU-UHFFFAOYSA-N 0.000 claims abstract description 8
- 230000035484 reaction time Effects 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000001035 drying Methods 0.000 claims abstract description 6
- 239000010936 titanium Substances 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims abstract description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- 238000005406 washing Methods 0.000 claims abstract description 5
- 239000003990 capacitor Substances 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 230000004888 barrier function Effects 0.000 claims description 6
- 239000006258 conductive agent Substances 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000011230 binding agent Substances 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000011889 copper foil Substances 0.000 claims description 4
- 238000011049 filling Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000006230 acetylene black Substances 0.000 claims description 3
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 3
- 150000004702 methyl esters Chemical class 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 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 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 2
- 239000002134 carbon nanofiber Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 239000010439 graphite Substances 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims description 2
- 239000003273 ketjen black Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 3
- 238000001914 filtration Methods 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 5
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 102100031416 Gastric triacylglycerol lipase Human genes 0.000 description 1
- 101000941284 Homo sapiens Gastric triacylglycerol lipase Proteins 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G33/00—Compounds of niobium
-
- 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
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Power Engineering (AREA)
- Materials Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Electric Double-Layer Capacitors Or The Like (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for preparing a titanium-niobium composite oxide by a water/solvothermal method and an application of the method in a lithium-ion supercapacitor. The method comprises the following steps: (1) weighing corresponding titanium source and niobium source to dissolve into a water/organic solvent system at the stoichiometric ratio of a titanium-niobium oxide TiNb<2>O<7>, placing the solution into a reaction kettle employing polytetrafluoroethylene as a lining, adjusting the pH between 0.5 and 2.5 and stirring the solution for 0.5-24 hours; (2) placing the reaction kettle containing the mixture into a homogeneous reactor or an electric drying oven, carrying out water/solvothermal reaction by setting a reaction temperature and reaction time, and filtering, washing and drying the solution after reaction is ended, so as to obtain a precursor of the TiNb<2>O<7>; and (3) putting the precursor material of the TiNb<2>O<7> into a high-temperature furnace for full reaction, and cooling the precursor material along with a room temperature to obtain required titanium-niobium composite oxide TiNb<2>O<7>. The titanium-niobium composite oxide TiNb<2>O<7> prepared by the method has excellent electrochemical properties, and has relatively high energy density and excellent safety performance when used as an anode material for a lithium-ion battery.
Description
Technical field
The invention belongs to energy storage material technical field, relate to a kind of titanium niobium oxide TiNb with good electric chemical property
2o
7the preparation method of material and be the high-performance lithium ion mixed capacitor of negative pole based on this material.
Background technology
Consume gradually along with traditional fossil energy and be tending towards exhausted, finding efficient and clean new green power becomes one of study hotspot of current region of chemistry.Wherein, lithium receives people from hybrid super capacitor because it has numerous advantages and more and more pays close attention to, except the electricity consumption needs meeting portable equipment, lithium-ion mixture super capacitor allows people expect in the development prospect in high-power, high-octane energy storage field especially.And this wherein, the research of electrode material seems especially crucial.Professor Goodenough first proposed a kind of titanium niobium oxide TiNb
2o
7and used as novel lithium ion battery electrode material.The ensuing research display of Goodenough professor, TiNb
2o
7also have good high rate charge-discharge performance simultaneously.Recently, Chinese Academy of Sciences Chen Li spring academician seminar is to TiNb
2o
7doff lithium mechanism conduct in-depth research, think TiNb
2o
7having very little voltage hysteresis and highly stable cycle performance, is be hopeful most to replace the anode material of spinel type lithium titanate as large power, electrically electrical automobile and large-sized battery power station.But it is not yet popularized in the application in high-power lithium ion mixed capacitor field, but can have broad application prospects in lithium-ion mixture super capacitor field according to the known material of quick doff lithium performance of its excellence.
Summary of the invention
The object of this invention is to provide a kind of water/solvent-thermal method that utilizes and prepare the method for titanium niobium composite oxides and the application in lithium ion super capacitor thereof, the method has prepared less, the finely dispersed micro-nano TiNb of particle
2o
7particle.
The object of the invention is to be achieved through the following technical solutions:
Utilize water/solvent-thermal method to prepare a method for titanium niobium composite oxides, comprise the steps:
(1) according to titanium niobium oxide TiNb
2o
7stoichiometric proportion, take corresponding titanium source and niobium source dispersing and dissolving in water/organic solvent system, then be positioned over polytetrafluoroethylene be liner reactor in, add a certain amount of citric acid or careless acid for adjusting pH wherein between 0.5 ~ 2.5, stir 0.5 ~ 24h;
(2) reactor filling said mixture is positioned in homogeneous reactor or Electric heat oven, reaction temperature is set and the reaction time carries out water/solvent thermal reaction, after solution being filtered washing and drying after reaction terminates, can TiNb be obtained
2o
7presoma, wherein reaction temperature is 100 ~ 250 DEG C, and the reaction time is 5 ~ 24h, and baking temperature is 60 ~ 140 DEG C;
(3) by TiNb
2o
7persursor material be placed in high temperature furnace, in air or oxygen atmosphere, be warmed up to 900 ~ 1400 DEG C with the heating rate of 1 ~ 10 DEG C/min, and keep 15 ~ 36h at such a temperature, after abundant reaction, with room temperature cooling, required titanium niobium composite oxides TiNb can be obtained
2o
7.
Titanium niobium composite oxides prepared by said method can as negative material in lithium ion mixed capacitor.Described lithium ion mixed capacitor comprises negative plate, positive plate, barrier film, electrolyte, aluminum shell or aluminum plastic film, wherein: barrier film is placed in the middle of positive plate and negative plate, aluminum plastic film or aluminum shell in the outside of battery core as protection.Described negative plate is formed by copper foil of affluxion body and cathode size manufacture, wherein: cathode size according to mass ratio by 40 ~ 90% titanium niobium composite oxides TiNb
2o
7, 2 ~ 10% conductive agent and 3 ~ 20% binding agent composition, cathode size is at copper foil surface even spread, and surface density is 5 ~ 100g/m
2.
In the present invention, described niobium source is Nb
2o
5or Nb (OH)
5.
In the present invention, described titanium source is TiO
2, butyl titanate, metatitanic acid methyl esters, tetraethyl titanate or isopropyl titanate.
In the present invention, described water/organic solvent system is water or organic solvent, and organic solvent can be absolute ethyl alcohol, ethylene glycol, acetone or acetonitrile.
In the present invention, described cathode conductive agent is a kind of or wherein several mixture in SuperP, acetylene black, Ketjen black, nano-graphite, carbon nano-tube, Graphene or VGCF.
In the present invention, described electrolyte can be the mixed liquor that is a kind of or wherein several solvent in ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC) and the first and second base carbonic esters (EMC).
Tool of the present invention has the following advantages:
1, the invention provides a kind of titanium niobium composite oxides TiNb
2o
7synthetic method, and refinement has been carried out to its synthesis technique, the material particle size making to adopt the present invention to prepare is less, even particle size distribution.
2, the titanium niobium composite oxides TiNb for preparing of this method
2o
7there is outstanding chemical property, have higher energy density, excellent security performance when it is used as lithium ion battery negative material.
3, the cost of raw material is low, nontoxic, has application prospect extremely widely.
Accompanying drawing explanation
Fig. 1 is the TiNb adopting the present invention to prepare
2o
7scanning electron microscope diagram;
Fig. 2 is the TiNb adopting the present invention to prepare
2o
7x ray diffracting spectrum.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but be not limited thereto; everyly technical solution of the present invention modified or equivalent to replace, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: according to titanium niobium oxide TiNb
2o
7stoichiometric proportion, with mol ratio n (TiO
2): n (Nb
2o
5the ratio of)=1:1 gets the nano-sized anatase TiO of corresponding mass
2with Nb
2o
5(particle diameter is about 20nm) is dispersed in the aqueous solution of 30ml respectively, and being then positioned over polytetrafluoroethylene is in the reactor of liner, adds a certain amount of oxalic acid wherein and distilled water is adjusted to pH=1.0, stirs 2h.Then be positioned in homogeneous reactor by the reactor filling above-mentioned mixed solution, regulate reaction temperature to be 180 DEG C, the reaction time is 24h.After solution being filtered washing and drying after hydro-thermal reaction, required TiNb can be obtained
2o
7presoma.
By TiNb
2o
7persursor material is placed in high temperature furnace, in air atmosphere, is warmed up to 1200 DEG C, and keeps 24h at such a temperature with the heating rate of 10 DEG C/min, fully after reaction, with room temperature cooling, can obtain required titanium niobium composite oxides TiNb
2o
7.Fig. 1 and Fig. 2 is the TiNb obtained
2o
7scanning electron microscope (SEM) photograph and XRD collection of illustrative plates, can find out that material possesses nano level pattern and typical monocline crystalline phase.
Embodiment two: present embodiment and embodiment one unlike: by nano-anatase TiO
2replace with butyl titanate, metatitanic acid methyl esters, tetraethyl titanate or isopropyl titanate.
Embodiment three: get the butyl titanate of corresponding mass and each 30ml of ethanolic solution of niobium chloride with the ratio of Ti/Nb mol ratio=1:2, being positioned over polytetrafluoroethylene is in the reactor of liner, adding a certain amount of ethanol wherein regulates cumulative volume to be 70ml, stirs 3h.Then be positioned in homogeneous reactor by the reactor filling above-mentioned mixed solution, regulate reaction temperature to be 200 DEG C, the reaction time is 24h.After solution being filtered washing and drying after hydro-thermal reaction, required presoma can be obtained.
Above-mentioned persursor material is placed in high temperature furnace, in air atmosphere, is warmed up to 900 DEG C with the heating rate of 5 DEG C/min, and keeps 15h at such a temperature, fully after reaction, with room temperature cooling, required titanium niobium composite oxides TiNb can be obtained
2o
7.
Embodiment four: present embodiment execution mode and embodiment three unlike: the reaction temperature in step 3 is 150 DEG C, 160 DEG C, 170 DEG C, 190 DEG C or 200 DEG C.
Embodiment five: with titanium niobium oxide TiNb in present embodiment
2o
7lithium-ion mixture super capacitor for negative material comprises positive plate, negative plate, barrier film and aluminum-plastic composite membrane or aluminum shell, described barrier film is between positive plate and negative plate, aluminum-plastic composite membrane or aluminum shell are wrapped in the periphery of positive plate, negative plate and barrier film, wherein, negative plate is formed by negative current collector and cathode size manufacture, described cathode size by mass percentage by 70 ~ 95% titanium niobium oxide TiNb
2o
7material, the conductive agent of 2 ~ 20% and the binding agent Kynoar composition of 3 ~ 10%, cathode size is in the coating of negative current collector surface uniform, and surface density is 20 ~ 200g/m
2.
When cathode size is coated in the both sides of negative current collector, coating density should be the twice of One-sided coatings.
In present embodiment, negative current collector should be Copper Foil.
The anode pole piece adopted in present embodiment is formed by plus plate current-collecting body and anode sizing agent manufacture, and positive electrode generally uses active carbon.Such as, anode sizing agent can by mass percentage by 85 ~ 95% active carbon, the conductive agent (acetylene black, SuperP etc.) of 2 ~ 10% and 3 ~ 5% binding agent Kynoar composition.
The LIPF of electrolyte used to be concentration be lmol/L in present embodiment
6business electrolyte, the wherein mixed liquor of the ethylene carbonate (EC) of solvent to be volume ratio be 1:1:1, diethyl carbonate (DEC) and dimethyl carbonate (DMC).
Claims (10)
1. utilize water/solvent-thermal method to prepare a method for titanium niobium composite oxides, it is characterized in that described method following steps:
(1) according to titanium niobium oxide TiNb
2o
7stoichiometric proportion, take corresponding titanium source and niobium source dispersing and dissolving in water/organic solvent system, be then positioned over polytetrafluoroethylene be liner reactor in, regulate pH between 0.5 ~ 2.5, stir 0.5 ~ 24h;
(2) reactor filling said mixture is positioned in homogeneous reactor or Electric heat oven, reaction temperature is set and the reaction time carries out water/solvent thermal reaction, after solution being filtered washing and drying after reaction terminates, can TiNb be obtained
2o
7presoma, wherein reaction temperature is 100 ~ 250 DEG C, and the reaction time is 5 ~ 24h, and baking temperature is 60 ~ 140 DEG C;
(3) by TiNb
2o
7persursor material be placed in high temperature furnace, in air or oxygen atmosphere, be warmed up to 900 ~ 1400 DEG C with the heating rate of 1 ~ 10 DEG C/min, and keep 15 ~ 36h at such a temperature, after abundant reaction, with room temperature cooling, required titanium niobium composite oxides TiNb can be obtained
2o
7.
2. the method utilizing water/solvent-thermal method to prepare titanium niobium composite oxides according to claim 1, is characterized in that described niobium source is Nb
2o
5or Nb (OH)
5.
3. the method utilizing water/solvent-thermal method to prepare titanium niobium composite oxides according to claim 1, is characterized in that described titanium source is TiO
2, butyl titanate, metatitanic acid methyl esters, tetraethyl titanate or isopropyl titanate.
4. the method utilizing water/solvent-thermal method to prepare titanium niobium composite oxides according to claim 1, it is characterized in that described reaction temperature is 100 ~ 250 DEG C, the reaction time is 5 ~ 24h.
5. the method utilizing water/solvent-thermal method to prepare titanium niobium composite oxides according to claim 1, is characterized in that described baking temperature is 60 ~ 140 DEG C.
6. the method utilizing water/solvent-thermal method to prepare titanium niobium composite oxides according to claim 1, it is characterized in that described water/organic solvent system is water or organic solvent, organic solvent is absolute ethyl alcohol, ethylene glycol, acetone or acetonitrile.
7. the titanium niobium composite oxides prepared of claim method according to the arbitrary claim of claim 1-6 are as the application of negative material in lithium ion mixed capacitor.
8. titanium niobium composite oxides according to claim 7 are as the application of negative material in lithium ion mixed capacitor, it is characterized in that described lithium ion mixed capacitor comprises negative plate, positive plate, barrier film, electrolyte, aluminum shell or aluminum plastic film, wherein negative plate is formed by copper foil of affluxion body and cathode size manufacture, cathode size according to mass ratio by 40 ~ 90% titanium niobium composite oxides TiNb
2o
7, 2 ~ 10% conductive agent and 3 ~ 20% binding agent composition.
9. titanium niobium composite oxides according to claim 7 are as the application of negative material in lithium ion mixed capacitor, it is characterized in that described cathode conductive agent is a kind of or wherein several mixture in SuperP, acetylene black, Ketjen black, nano-graphite, carbon nano-tube, Graphene or VGCF.
10. titanium niobium composite oxides according to claim 7 are as the application of negative material in lithium ion mixed capacitor, it is characterized in that described electrolyte is the mixed liquor that is a kind of or wherein several solvent in ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate and the first and second base carbonic esters.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511011426.8A CN105575675A (en) | 2015-12-30 | 2015-12-30 | Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201511011426.8A CN105575675A (en) | 2015-12-30 | 2015-12-30 | Method for preparing titanium-niobium composite oxide by water/solvothermal method and application of method in lithium-ion supercapacitor |
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| Publication Number | Publication Date |
|---|---|
| CN105575675A true CN105575675A (en) | 2016-05-11 |
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| CN106025285A (en) * | 2016-06-23 | 2016-10-12 | 南阳师范学院 | Spherical titanium niobate electrode material and preparation method thereof |
| CN106082338A (en) * | 2016-06-13 | 2016-11-09 | 东北大学 | A kind of nano-oxide Ti2nb10o29preparation method |
| CN107808956A (en) * | 2017-10-27 | 2018-03-16 | 哈尔滨理工大学 | A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode |
| CN109950489A (en) * | 2019-03-21 | 2019-06-28 | 浙江大学 | Carbon cloth/carbon fiber array supported titanium niobium O compoiste material and its preparation method and application |
| CN110156081A (en) * | 2019-05-22 | 2019-08-23 | 合肥学院 | A kind of porous flake TiNb of negative electrode of lithium ion battery2O7Nanocrystalline preparation method |
| WO2019164561A1 (en) * | 2018-02-13 | 2019-08-29 | Nanotek Instruments, Inc. | Hybrid supercapacitor containing a niobium composite metal oxide as an anode active material |
| CN111646510A (en) * | 2020-05-27 | 2020-09-11 | 武汉工程大学 | High-rate titanium niobium oxide microsphere and preparation method and application thereof |
| CN112103493A (en) * | 2020-08-13 | 2020-12-18 | 华北电力大学 | Preparation method of lithium battery negative electrode material titanium-niobium composite oxide |
| CN113683120A (en) * | 2021-08-31 | 2021-11-23 | 合肥工业大学 | Mixed-phase niobium-based oxide and preparation method and energy storage application thereof |
| CN113772728A (en) * | 2021-10-14 | 2021-12-10 | 合肥工业大学 | Mixed-phase niobium-titanium oxide, and preparation method and energy storage application thereof |
| CN114789050A (en) * | 2022-04-29 | 2022-07-26 | 浙江大学 | Bimetal titanium niobium oxide, preparation method thereof and application of bimetal titanium niobium oxide as catalyst of hydrogen storage material |
| CN115966775A (en) * | 2022-12-14 | 2023-04-14 | 惠州市数威科技有限公司 | Rechargeable lithium battery with ultralow self-discharge rate and preparation method thereof |
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| CN106082338A (en) * | 2016-06-13 | 2016-11-09 | 东北大学 | A kind of nano-oxide Ti2nb10o29preparation method |
| CN106025285A (en) * | 2016-06-23 | 2016-10-12 | 南阳师范学院 | Spherical titanium niobate electrode material and preparation method thereof |
| CN107808956A (en) * | 2017-10-27 | 2018-03-16 | 哈尔滨理工大学 | A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode |
| CN107808956B (en) * | 2017-10-27 | 2019-09-24 | 哈尔滨理工大学 | A kind of preparation method of titanium niobium oxygen nanometer rods/carbon nanofiber arrays electrode |
| US11037738B2 (en) | 2018-02-13 | 2021-06-15 | Nanotek Instruments Group, Llc | Hybrid supercapacitor containing a niobium composite metal oxide as an anode active material |
| WO2019164561A1 (en) * | 2018-02-13 | 2019-08-29 | Nanotek Instruments, Inc. | Hybrid supercapacitor containing a niobium composite metal oxide as an anode active material |
| CN109950489A (en) * | 2019-03-21 | 2019-06-28 | 浙江大学 | Carbon cloth/carbon fiber array supported titanium niobium O compoiste material and its preparation method and application |
| CN110156081A (en) * | 2019-05-22 | 2019-08-23 | 合肥学院 | A kind of porous flake TiNb of negative electrode of lithium ion battery2O7Nanocrystalline preparation method |
| CN110156081B (en) * | 2019-05-22 | 2021-05-14 | 合肥学院 | Porous flaky TiNb for lithium ion battery cathode2O7Method for preparing nanocrystalline |
| CN111646510A (en) * | 2020-05-27 | 2020-09-11 | 武汉工程大学 | High-rate titanium niobium oxide microsphere and preparation method and application thereof |
| CN112103493A (en) * | 2020-08-13 | 2020-12-18 | 华北电力大学 | Preparation method of lithium battery negative electrode material titanium-niobium composite oxide |
| CN113683120A (en) * | 2021-08-31 | 2021-11-23 | 合肥工业大学 | Mixed-phase niobium-based oxide and preparation method and energy storage application thereof |
| CN113772728A (en) * | 2021-10-14 | 2021-12-10 | 合肥工业大学 | Mixed-phase niobium-titanium oxide, and preparation method and energy storage application thereof |
| CN114789050A (en) * | 2022-04-29 | 2022-07-26 | 浙江大学 | Bimetal titanium niobium oxide, preparation method thereof and application of bimetal titanium niobium oxide as catalyst of hydrogen storage material |
| CN115966775A (en) * | 2022-12-14 | 2023-04-14 | 惠州市数威科技有限公司 | Rechargeable lithium battery with ultralow self-discharge rate and preparation method thereof |
| CN115966775B (en) * | 2022-12-14 | 2023-08-29 | 东莞市晟驰动力技术有限公司 | Rechargeable lithium battery with ultralow self-discharge rate and preparation method thereof |
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