CN105552369B - The method for preparing three-dimensional porous niobic acid titanium oxide using template and its application in lithium ion battery - Google Patents

The method for preparing three-dimensional porous niobic acid titanium oxide using template and its application in lithium ion battery Download PDF

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CN105552369B
CN105552369B CN201511011431.9A CN201511011431A CN105552369B CN 105552369 B CN105552369 B CN 105552369B CN 201511011431 A CN201511011431 A CN 201511011431A CN 105552369 B CN105552369 B CN 105552369B
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negative electrode
titanium oxide
template
dimensional porous
lithium ion
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CN105552369A (en
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程新群
娄帅锋
高金龙
马玉林
高云智
尹鸽平
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Harbin Institute of Technology
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Harbin Institute of Technology
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/58Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/5825Oxygenated metallic slats or polyanionic structures, e.g. borates, phosphates, silicates, olivines
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00Compounds of titanium
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01GCOMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G33/00Compounds of niobium
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/05Accumulators with non-aqueous electrolyte
    • H01M10/052Li-accumulators
    • H01M10/0525Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of method for preparing three-dimensional porous niobic acid titanium oxide using template and its applications in lithium ion battery, the method are as follows: one, the titanium source compound of equimolar ratio and niobium source compound be dispersed and dissolved in organic solvent, being sufficiently stirred makes it be uniformly dispersed;Two, a certain amount of mould material is added in above-mentioned solution, then it is filtered under vacuum filtration or baking oven in dry, obtain presoma;Three, presoma is calcined in air atmosphere at 800 ~ 1400 DEG C in high temperature furnace, removes mould material, porous TiNb can be obtained2O7Negative electrode material.Titanium niobium composite oxides TiNb prepared by the present invention2O7Have when being used as lithium ion battery negative material compared with high reversible capacity and first charge discharge efficiency, excellent high rate charge-discharge performance and security performance, and raw material cost is low, it is nontoxic, there is extremely broad application prospect.

Description

The method of three-dimensional porous niobic acid titanium oxide is prepared using template and its in lithium ion Application in battery
Technical field
The invention belongs to energy storage material technical fields, are related to a kind of POROUS TITANIUM niobium oxide with excellent chemical property TiNb2O7The preparation method of material and based on the material be cathode high performance lithium ion secondary battery.
Background technique
Tend to be exhausted as traditional fossil energy gradually uses up, find efficient and clean new green energy at For one of the research hotspot of current region of chemistry.Wherein, lithium ion secondary battery is received since it possesses numerous advantages People more and more pay close attention to, and other than the electricity consumption in addition to meeting portable equipment needs, lithium ion battery is high-power, high-energy dynamic Development prospect on power battery is even more that people is allowed to expect.And among these, the research of electrode material seems particularly critical.Nearly ten years, Lithium titanate (Li4Ti5O12) due to its outstanding high rate performance, lower production cost and cause extensive concern, become pole It is possible that commercialized next generation's negative electrode material, however Li4Ti5O12Theoretical capacity it is lower (only 175mAh/g), this limitation The raising of battery energy density, thus find there is higher theoretical capacity, the electrode material of preferable high rate performance becomes new One of research direction.
2011, John.B.Goodenough professor first proposed in " Journal of Power Sources " A kind of titanium niobium oxide TiNb2O7And it is used as novel lithium ion battery electrode material.Theoretical capacity 175 relative to LTO For mAh/g, TiNb2O7Since there are 5 electronics transfer (Nb5+/Nb4+,Nb4+/Nb3+,Ti4+/Ti3+) and there is higher theory Capacity (387.6mAh/g).Goodenough teaches next studies have shown that TiNb2O7Also possess preferable big multiplying power simultaneously Charge-discharge performance.Chen Liquan academician seminar, the Chinese Academy of Sciences is to TiNb2O7Embedding de- lithium mechanism conduct in-depth research, it is believed that TiNb2O7It is most to be hopeful that spinel type lithium titanate is replaced to make with very small voltage hysteresis and highly stable cycle performance For the anode material of high-power electric automobile and large-sized battery power station.Therefore, the TiNb of three-dimensional porous structure is studied2O7Material pair It is significant in power battery of electric vehicle and extensive energy-storage battery.
Summary of the invention
The object of the present invention is to provide it is a kind of using template prepare three-dimensional porous niobic acid titanium oxide method and its Application in lithium ion battery, this method have prepared the TiNb of even porous2O7Material.
The purpose of the present invention is what is be achieved through the following technical solutions:
A method of three-dimensional porous niobic acid titanium oxide being prepared using template, is included the following steps:
One, the titanium source compound of equimolar ratio and niobium source compound are dispersed and dissolved in organic solvent, are sufficiently stirred It is made to be uniformly dispersed;
Two, a certain amount of mould material is added in above-mentioned solution, the mass ratio for controlling solution and template is 1 ~ 80:1, so It is filtered under vacuum filtration afterwards or baking oven in dry, obtain presoma;
Three, presoma is calcined in air atmosphere at 800 ~ 1400 DEG C in high temperature furnace, removes mould material, can obtains To porous TiNb2O7Negative electrode material.
The porous TiNb of above method preparation2O7Negative electrode material can be used in lithium ion battery as negative electrode active material, The lithium ion battery is by negative electrode tab, positive plate, diaphragm, electrolyte, aluminum shell or aluminum plastic film.Its septation is in positive plate Intermediate with negative electrode tab is placed, and aluminum plastic film or aluminum shell are in the external as protection of battery core, and the negative electrode tab is by collector Copper foil and negative electrode slurry are fabricated, in which: negative electrode slurry according to mass ratio by 70 ~ 95% titanium niobium composite oxides TiNb2O7、 2 ~ 10% conductive agent and 3 ~ 20% binder composition, for negative electrode slurry in copper foil surface even spread, surface density is 20 ~ 200g/ m2
In the present invention, the titanium source compound is butyl titanate, isopropyl titanate or titanium tetrachloride.
In the present invention, the niobium source compound is niobium chloride or ethyl alcohol niobium.
In the present invention, the organic solvent is no water glycol, acetone or acetonitrile.
In the present invention, the template can for polystyrene microsphere (PS), poly (methyl methacrylate) micro-sphere (PMMA) or Person's carbosphere etc..
In the present invention, the high temperature furnace can be tube furnace, batch-type furnace or Muffle furnace.
In the present invention, the conductive agent be Super P, acetylene black, Ketjen black, nano-graphite, carbon nanotube, graphene or One of person VGCF or wherein several mixtures.
In the present invention, the electrolyte can be ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), one of diethyl carbonate (DEC) and the first and second base carbonic esters (EMC) or in which several mixed liquors.
The present invention has the advantage that
Titanium niobium composite oxides TiNb prepared by the present invention2O7Have when being used as lithium ion battery negative material higher reversible Capacity and first charge discharge efficiency, excellent high rate charge-discharge performance and security performance, and raw material cost is low, it is nontoxic, have Extremely broad application prospect.
Detailed description of the invention
Fig. 1 is the three-dimensional porous TiNb for using PS microballoon to prepare for template2O7XRD spectrum in standard diagram;
Fig. 2 is the three-dimensional porous TiNb for using PS microballoon to prepare for template2O7Scanning electron microscope (SEM) photograph;
Fig. 3 is the three-dimensional porous TiNb for using PS microballoon to prepare for template2O7Charging and discharging curve;
Fig. 4 is the three-dimensional porous TiNb for using PS microballoon to prepare for template2O7High rate performance.
Specific embodiment
Further description of the technical solution of the present invention with reference to the accompanying drawing, and however, it is not limited to this, all to this Inventive technique scheme is modified or replaced equivalently, and without departing from the spirit and scope of the technical solution of the present invention, should all be covered Within the protection scope of the present invention.
Specific embodiment 1: the butyl titanate of equimolar ratio and niobium chloride are dispersed and dissolved in dehydrated alcohol, Being sufficiently stirred makes it be uniformly dispersed, and then a certain amount of PS microballoon is added in above-mentioned solution, controls the matter of solution and PS microballoon Amount than be 40:1, it is filtered under vacuum filtration then, obtains presoma, then by presoma in high temperature furnace in 800 DEG C Porous TiNb can be obtained in lower calcining, air atmosphere2O7Negative electrode material.Fig. 1 is to obtain the XRD spectrum of sample, shows material Material belongs to monocline crystal phase.Fig. 2 is the scanning electron microscope (SEM) photograph of material, shows that obtained material has 3-D ordered multiporous pattern
Specific embodiment 2: the isopropyl titanate (isopropyl titanate) and ethyl alcohol niobium of equimolar ratio are dispersed and dissolved in nothing In water-ethanol, being sufficiently stirred makes it be uniformly dispersed, and then a certain amount of PMMA microsphere is added in above-mentioned solution, control solution with The mass ratio of PMMA microsphere is 60:1, then filters it under vacuum filtration, presoma is obtained, then by presoma in high temperature It is calcined at 900 DEG C in furnace, air atmosphere, porous TiNb can be obtained2O7Negative electrode material.
Specific embodiment 3: the isopropyl titanate (isopropyl titanate) and ethyl alcohol niobium of equimolar ratio are dispersed and dissolved in nothing In water-ethanol, being sufficiently stirred makes it be uniformly dispersed, and then a certain amount of PS microballoon is added in above-mentioned solution, controls solution and PS The mass ratio of microballoon is 20:1, then filters it under vacuum filtration, presoma is obtained, then by presoma in high temperature furnace It is calcined at 1000 DEG C, air atmosphere, porous TiNb can be obtained2O7Negative electrode material.
Specific embodiment 4: with POROUS TITANIUM niobium oxide TiNb in present embodiment2O7For the lithium-ion electric of negative electrode material Pond includes positive plate, negative electrode tab, isolation film and aluminum-plastic composite membrane or aluminum shell, and the isolation film is located at positive plate and cathode Between piece, aluminum-plastic composite membrane or aluminum shell are wrapped in the periphery of positive plate, negative electrode tab and isolation film, wherein negative electrode tab by Negative current collector and negative electrode slurry are fabricated, the negative electrode slurry by mass percentage by 70 ~ 95% titanium niobium oxide TiNb2O7Material, 2 ~ 20% conductive agent and 3 ~ 10% binder Kynoar composition, negative electrode slurry is in negative pole currect collecting body surface Face uniformly coats, and surface density is 20 ~ 200g/m2.Fig. 3 and Fig. 4 is performance of the TNO porous material in half-cell, explanation Material has the embedding de- lithium performance of excellent electrochemistry.
When negative electrode slurry is coated in the two sides of negative current collector, coating density should be twice of One-sided coatings.
Negative current collector should be copper foil in present embodiment, and plus plate current-collecting body should be aluminium foil.
Anode pole piece employed in present embodiment is fabricated by plus plate current-collecting body and anode sizing agent, using this field Known positive plate.For example, anode sizing agent can by mass percentage by 85 ~ 95% LiCoO2Or LiFePO4, 2 ~ 10% conductive agent (acetylene black.Super P etc.) and 3 ~ 5% binder Kynoar composition.
Cathode conductive agent is acetylene black, Ketjen black, Super P, nano-graphite, carbon nanotube or stone in present embodiment Black alkene etc..Electrolyte used can be ethylene carbonate (EC), propene carbonate (PC), dimethyl carbonate (DMC), diethyl One of base carbonic ester (DEC) and the first and second base carbonic esters (EMC) or in which several mixed liquors, electrolyte used in the present embodiment It is the LIPF that concentration is lmol/L6Business electrolyte, wherein solvent is ethylene carbonate (EC), the carbonic acid that volume ratio is 1:1:1 The mixed liquor of diethylester (DEC) and dimethyl carbonate (DMC).

Claims (8)

1. a kind of method for preparing three-dimensional porous niobic acid titanium oxide using template, it is characterised in that the method step is such as Under:
One, the titanium source compound of equimolar ratio and niobium source compound are dispersed and dissolved in organic solvent, being sufficiently stirred makes it It is uniformly dispersed to form solution;The organic solvent is no water glycol, acetone or acetonitrile;
Two, a certain amount of mould material is added in above-mentioned solution, the mass ratio for controlling solution and template is 1 ~ 80:1, then will Its filtered under vacuum filtration or baking oven in dry, obtain presoma;
Three, presoma is calcined in air atmosphere at 800 ~ 1400 DEG C in high temperature furnace, it is porous to get arriving to remove mould material TiNb2O7Negative electrode material;The template is polystyrene microsphere, poly (methyl methacrylate) micro-sphere or carbosphere.
2. the method according to claim 1 for preparing three-dimensional porous niobic acid titanium oxide using template, it is characterised in that The titanium source compound is butyl titanate, isopropyl titanate or titanium tetrachloride.
3. the method according to claim 1 for preparing three-dimensional porous niobic acid titanium oxide using template, it is characterised in that The niobium source compound is niobium chloride or ethyl alcohol niobium.
4. the method according to claim 1 for preparing three-dimensional porous niobic acid titanium oxide using template, it is characterised in that The high temperature furnace is tube furnace, batch-type furnace or Muffle furnace.
5. a kind of three-dimensional porous niobic acid titanium oxide of claim 1 ~ 4 any claim the method preparation is living as cathode Application of the property substance in lithium ion battery.
6. three-dimensional porous niobic acid titanium oxide according to claim 5 is as negative electrode active material in lithium ion battery Using, it is characterised in that the lithium ion battery is by negative electrode tab, positive plate, diaphragm, electrolyte, aluminum shell or aluminum plastic film structure At negative electrode tab is fabricated by copper foil of affluxion body and negative electrode slurry, in which: negative electrode slurry is according to mass ratio by 70 ~ 95% TiNb2O7, 2 ~ 10% conductive agent and 3 ~ 20% binder composition.
7. three-dimensional porous niobic acid titanium oxide according to claim 6 is as negative electrode active material in lithium ion battery Be SuperP using, it is characterised in that the conductive agent, acetylene black, Ketjen black, nano-graphite, carbon nanotube, graphene or One of VGCF or wherein several mixtures.
8. three-dimensional porous niobic acid titanium oxide according to claim 6 is as negative electrode active material in lithium ion battery Using, it is characterised in that the electrolyte be ethylene carbonate, propene carbonate, dimethyl carbonate, diethyl carbonate and One of first and second base carbonic esters or in which several mixed liquors.
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CN109167049A (en) * 2018-09-27 2019-01-08 天津普兰能源科技有限公司 A kind of graphene coated titanium niobium oxide combination electrode material, lithium primary battery and 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

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CN104815647A (en) * 2015-05-13 2015-08-05 安徽师范大学 Preparation method of high-activity porous LaMnO3+delta electrocatalyst
CN104968606A (en) * 2013-02-06 2015-10-07 原子能与替代能源委员会 Mixed oxide of titanium and niobium comprising a trivalent metal

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US9806338B2 (en) * 2013-08-23 2017-10-31 Ut-Battele, Llc Nanoporous titanium niobium oxide and titanium tantalum oxide compositions and their use in anodes of lithium ion batteries

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CN104968606A (en) * 2013-02-06 2015-10-07 原子能与替代能源委员会 Mixed oxide of titanium and niobium comprising a trivalent metal
CN104815647A (en) * 2015-05-13 2015-08-05 安徽师范大学 Preparation method of high-activity porous LaMnO3+delta electrocatalyst

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