CN107359333A - A kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof - Google Patents

A kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof Download PDF

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Publication number
CN107359333A
CN107359333A CN201710555473.1A CN201710555473A CN107359333A CN 107359333 A CN107359333 A CN 107359333A CN 201710555473 A CN201710555473 A CN 201710555473A CN 107359333 A CN107359333 A CN 107359333A
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nano
preparation
polypyrrole
nano material
composite material
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王春梅
徐宁
宋英杰
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Tianjin B&M Science and Technology Co Ltd
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Tianjin B&M Science and Technology Co Ltd
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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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/60—Selection of substances as active materials, active masses, active liquids of organic compounds
    • H01M4/602—Polymers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Composite Materials (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)

Abstract

The invention discloses a kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof, and under polyalcohol auxiliary, titanium source and alkaline solution are obtained into Na by back flow reaction2Ti6O13Nanometer sheet presoma；Na is washed with acidic materials2Ti6O13Nanometer sheet presoma obtains H several times2Ti6O13Nanometer sheet；By H2Ti6O13Nanometer sheet is thermally treated resulting in H in air atmosphere2Ti12O25Nanometer sheet；By H2Ti12O25Nanometer sheet is distributed in water and is placed in ice-water bath, is ultrasonically formed suspension；Pyrroles is added in suspension, stirring；By a certain amount of (NH4)2S2O8The aqueous solution, in the suspension being added dropwise to dropwise, filter, washing, dry after reacting under agitation, finally give H2Ti12O25/ polypyrrole nano composite material.Its structure is that polypyrrole is uniformly coated on H2Ti12O25Nano-material surface, form the composite with good electron conduction, the preparation method is simple, and application is strong, be made product specific capacity height, good rate capability, have extended cycle life, security it is good.

Description

A kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof
Technical field
The present invention relates to ion secondary battery cathode material lithium field, more particularly to a kind of hydrogen titanium oxide/polypyrrole to receive Nano composite material and preparation method thereof.
Background technology
Titanium base material has higher intercalation potential (1.55V (vs.Li+/ Li)), the embedding lithium reaction potential of the height can avoid gold Belong to Li dendrite appearance, and under high voltages discharge and recharge when will not be reacted with electrolyte, be favorably improved large current density The security of battery when electric.In addition, in de- lithium and process of intercalation, hardly recurring structure and volume change titanium base material Become, so titanium base material has extraordinary cyclical stability.In titanium base material, the layer structure of Idemoto et al. reports H2Ti12O25With higher capacity (significantly larger than Li4Ti5O12Theoretical capacity), so the material is expected to turn into a kind of new Type high-energy, long circulation life and the titanium-based negative material with high security.But the material there is also it is certain the defects of, such as Poor electron conduction can limit its high rate capability, make it difficult to realize the application in terms of electrokinetic cell.
The content of the invention
The technical problem to be solved by the invention is to provide a kind of hydrogen titanium oxide/polypyrrole nano composite material and its Preparation method, H prepared by this method2Ti12O25/ polypyrrole nano composite material has specific capacity height, high rate capability is good and follows The advantages such as ring long lifespan.
In order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is：A kind of hydrogen titanium oxide/polypyrrole nanometer The preparation method of composite, in turn includes the following steps：
(1)H2Ti12O25The preparation of nano material
1) using titanium dioxide and alkaline solution as raw material, Na is obtained through polyalcohol auxiliary reflux legal system2Ti6O13Before nano material Drive body；
2) Na is washed with acidic materials2Ti6O13Nano material presoma obtains H2Ti6O13Nano material；
3) by H2Ti6O13Nano material is in air atmosphere, is thermally treated resulting in H at 250~270 DEG C2Ti12O25Nanometer material Material；
(2)H2Ti12O25The preparation of/polypyrrole nano composite material
1) by H made from step (1)2Ti12O25Nano material is distributed in water and is placed in ice-water bath, and wherein liquid-solid ratio is 200~300ml/g；
2) pyrroles, wherein pyrroles under agitation, are added：H2Ti12O25For 1~10ml:1g；
3) by (NH4)2S2O8Soluble in water, liquid-solid ratio is 25~100ml/g, and its aqueous solution is added dropwise into step dropwise (2) in solution 2), wherein pyrroles：(NH4)2S2O8For 1ml:2g, filter, wash after 6~12h of reaction under agitation, Dry, finally give H2Ti12O25/ polypyrrole nano composite material.
Specifically, step (1) H2Ti12O25The step of preparation of nano material：
1) under polyalcohol auxiliary, by alkaline solution that titanium source and concentration are 1~6M at 150~200 DEG C back flow reaction 6 ~10h obtains Na2Ti6O13Nano material presoma；
2) Na is washed with the acidic materials that concentration is 0.01~0.1M2Ti6O13Nano material presoma obtains several times H2Ti6O13Nano material；
3) by H2Ti6O13Nano material is in air atmosphere, is thermally treated resulting in H at 250-270 DEG C2Ti12O25Nano material.
Hydrogen titanium oxide/polypyrrole nano composite material made from above-mentioned preparation method.
Beneficial effects of the present invention：Product specific capacity height, good rate capability, have extended cycle life, security it is good, it is high to prepare The electrokinetic cell of power density provides favourable support.
Brief description of the drawings
Fig. 1 is H2Ti12O25The X-ray diffractogram of/polypyrrole nano composite material.
Fig. 2 is H2Ti12O25Charge-discharge cycle of/polypyrrole the nano composite material under 0.2A/g and 4A/g current densities Can curve map.
Embodiment
Technical scheme is described in detail with reference to embodiments.
The preparation method of hydrogen titanium oxide/polypyrrole nano composite material of the present invention, in turn includes the following steps：
(1)H2Ti12O25The preparation of nano material
1) using titanium dioxide and alkaline solution as raw material, Na is obtained through polyalcohol auxiliary reflux legal system2Ti6O13Before nano material Drive body；
2) Na is washed with acidic materials2Ti6O13Nano material presoma obtains H2Ti6O13Nano material；
3) by H2Ti6O13Nano material is in air atmosphere, is thermally treated resulting in H at 250~270 DEG C2Ti12O25Nanometer material Material；
(2)H2Ti12O25The preparation of/polypyrrole nano composite material
1) by H made from step (1)2Ti12O25Nano material is distributed in water and is placed in ice-water bath, and wherein liquid-solid ratio is 200~300ml/g；
2) pyrroles, wherein pyrroles under agitation, are added：H2Ti12O25For 1~10ml:1g；
3) by (NH4)2S2O8Soluble in water, liquid-solid ratio is 25~100ml/g, and its aqueous solution is added dropwise into step dropwise (2) in solution 2), wherein pyrroles：(NH4)2S2O8For 1ml:2g, filter, wash after 6~12h of reaction under agitation, Dry, finally give H2Ti12O25/ polypyrrole nano composite material.
Specifically, step (1) H2Ti12O25The step of preparation of nano material：
1) under polyalcohol auxiliary, by alkaline solution that titanium source and concentration are 1~6M at 150~200 DEG C back flow reaction 6 ~10h obtains Na2Ti6O13Nano material presoma；
2) Na is washed with the acidic materials that concentration is 0.01~0.1M2Ti6O13Nano material presoma obtains several times H2Ti6O13Nano material；
3) by H2Ti6O13Nano material is in air atmosphere, is thermally treated resulting in H at 250-270 DEG C2Ti12O25Nano material.
Hydrogen titanium oxide/polypyrrole nano composite material made from above-mentioned preparation method.
Embodiment 1
A kind of preparation method of hydrogen titanium oxide/polypyrrole nano composite material, comprises the following steps：
1) by the alkyl titanium oxide of 2g PEG-8 00 and 0.68g be dissolved in 48ml ethanol solution formed mixing it is molten Liquid, and the solution and 24ml, 2mol/L potassium hydroxide solution are formed into Na at 200 DEG C after back flow reaction 6h2Ti6O13Nanometer Piece presoma；
2) Na is cleaned with 0.01M acetic acid2Ti6O13Nanometer sheet presoma obtains H 3 times2Ti6O13Nanometer sheet；
3) with distillation water washing H2Ti6O13Nanometer sheet dries 24h to remove unnecessary acetic acid at 80 DEG C, then 260 Final product H is thermally treated resulting at DEG C2Ti12O25Nanometer sheet；
4) by 1g H2Ti12O25Nano material is distributed in water and is placed in ice-water bath, and ultrasonic 0.5h forms suspension, its Middle liquid-solid ratio is 200ml/g；
5) by a certain amount of pyrroles (pyrroles：H2Ti12O25For 2ml:1g) it is added in the suspension of step 4), stirs 30min；
6) by a certain amount of (NH4)2S2O8The formation aqueous solution (wherein liquid-solid ratio is 25ml/g) soluble in water, then should The aqueous solution is added dropwise in the suspension of step 5) (wherein, pyrroles dropwise：(NH4)2S2O8For 1ml:2g), under agitation instead Answer and filter after 8h, washing, dry, finally give H2Ti12O25/ polypyrrole nano composite material.
As shown in figure 1, it is H manufactured in the present embodiment2Ti12O25The X-ray diffractogram of/polypyrrole nano composite material. H2Ti12O25The chemical property result of/polypyrrole nano composite material is as shown in Figure 2.From the figure, it can be seen that in 0.2A/g electricity Under current density during discharge and recharge, initial charge capacity is 330.4mAh/g, during discharge and recharge under 2A/g current densities, initial charge Capacity is 232.4mAh/g, and after 100 circulations, capacity still can reach 230mAh/g, show H2Ti12O25/ polypyrrole is received Nano composite material has good high rate capability.
Embodiment 2
A kind of preparation method of hydrogen titanium oxide/polypyrrole nano composite material, comprises the following steps：
1) rutile titanium dioxide of 8g ethylene glycol and 0.34g is dispersed in be formed in 48ml ethanol solution and mixed Solution, and the solution and 24ml, 6M lithium hydroxide solution are formed into Na at 180 DEG C after back flow reaction 8h2Ti6O13Nanometer sheet Presoma；
2) Na is cleaned with 0.05M oxalic acid2Ti6O13Nanometer sheet presoma obtains H 3 times2Ti6O13Nanometer sheet；
3) with distillation water washing H2Ti6O13Nanometer sheet dries 24h to remove unnecessary oxalic acid at 80 DEG C, then 260 Final product H is thermally treated resulting at DEG C2Ti12O25Nanometer sheet；
4) by 1 H2Ti12O25Nano material is distributed in water and is placed in ice-water bath, and ultrasonic 0.5h forms suspension, its Middle liquid-solid ratio is 200ml/g；
5) by a certain amount of pyrroles (pyrroles：H2Ti12O25For 5ml:1g) it is added in the suspension of step 4), stirs 30min；
6) by a certain amount of (NH4)2S2O8The formation aqueous solution (wherein liquid-solid ratio is 25ml/g) soluble in water, then should The aqueous solution is added dropwise in the suspension of step 5) (wherein, pyrroles dropwise：(NH4)2S2O8For 1ml:2g), under agitation instead Answer and filter after 8h, washing, dry, finally give H2Ti12O25/ polypyrrole nano composite material.
Embodiment 3
A kind of hydrogen titanium oxide/polypyrrole nano composite material preparation method, comprises the following steps：
1) molten be dispersed in 0.34g rutile titanium dioxide in 48ml ethanol solution of 4g diethylene glycol is formed Mixed solution, and the solution and 24ml, 4M sodium hydroxide solution are formed into Na at 160 DEG C after back flow reaction 10h2Ti6O13 Nanometer sheet presoma；
2) Na is cleaned with 0.1M acetic acid2Ti6O13Nanometer sheet presoma obtains H 3 times2Ti6O13Nanometer sheet；
3) with distillation water washing H2Ti6O13Nanometer sheet dries 24h to remove unnecessary acetic acid at 80 DEG C, then 260 Final product H is thermally treated resulting at DEG C2Ti12O25Nanometer sheet；
4) by 1 H2Ti12O25Nano material is distributed in water and is placed in ice-water bath, and ultrasonic 0.5h forms suspension, its Middle liquid-solid ratio is 200ml/g；
5) by a certain amount of pyrroles (pyrroles：H2Ti12O25For 8ml:1g) it is added in the suspension of step 4), stirs 30min；
6) by a certain amount of (NH4)2S2O8The formation aqueous solution (wherein liquid-solid ratio is 25ml/g) soluble in water, then should The aqueous solution is added dropwise in the suspension of step 5) (wherein, pyrroles dropwise：(NH4)2S2O8For 1ml:2g), under agitation instead Answer and filter after 8h, washing, dry, finally give H2Ti12O25/ polypyrrole nano composite material.
The invention provides a kind of in-situ polymerization oxidizing process, the polypyrrole with good electron conduction is coated on H2Ti12O25Nano-material surface, form H2Ti12O25/ polypyrrole nano composite material, the H prepared using this method2Ti12O25/ Polypyrrole nano composite material has the high rate performance being obviously improved.
Hydrogen titanium oxide/polypyrrole nano composite material prepared by the present invention, polypyrrole are uniformly coated on H2Ti12O25Receive Rice material surface, forms nano composite material, wherein H2Ti12O25Pattern be nano wire, nanometer rods, nanotube or nanometer sheet.
The battery of composite assembling prepared by the present invention has very high capacity (discharge and recharge under 0.2A/g, discharge capacity Can reach 330.4mAh/g), good high rate performance (charge/discharge capacity can reach 232.4mAh/g under 2A/g) and cycle performance (charge and discharge cycles are after 100 weeks under 2A/g, capability retention 99%).The composite is expected to turn into new electrokinetic cell material Material.
In summary, present disclosure is not limited in the above embodiments, and the knowledgeable people in same area can Can propose other embodiments easily within the technological guidance's thought of the present invention, but this embodiment is included in this hair Within the scope of bright.

Claims (3)

1. a kind of preparation method of hydrogen titanium oxide/polypyrrole nano composite material, it is characterised in that include following step successively Suddenly：
(1)H2Ti12O25The preparation of nano material
1) using titanium dioxide and alkaline solution as raw material, Na is obtained through polyalcohol auxiliary reflux legal system2Ti6O13Nano material presoma；
2) Na is washed with acidic materials2Ti6O13Nano material presoma obtains H2Ti6O13Nano material；
3) by H2Ti6O13Nano material is in air atmosphere, is thermally treated resulting in H at 250~270 DEG C2Ti12O25Nano material；
(2)H2Ti12O25The preparation of/polypyrrole nano composite material
1) by H made from step (1)2Ti12O25Nano material is distributed in water and is placed in ice-water bath, and wherein liquid-solid ratio is 200 ~300ml/g；
2) pyrroles, wherein pyrroles under agitation, are added：H2Ti12O25For 1~10ml:1g；
3) by (NH4)2S2O8Soluble in water, liquid-solid ratio is 25~100ml/g, and its aqueous solution is added dropwise into step (2) dropwise 2) in solution, wherein pyrroles：(NH4)2S2O8For 1ml:2g, filtered under agitation after 6~12h of reaction, wash, dry, Finally give H2Ti12O25/ polypyrrole nano composite material.
2. the preparation method of hydrogen titanium oxide/polypyrrole nano composite material according to claim 1, it is characterised in that institute State step (1) H2Ti12O25The step of preparation of nano material：
1) under polyalcohol auxiliary, by alkaline solution that titanium source and concentration are 1~6M at 150~200 DEG C back flow reaction 6~ 10h obtains Na2Ti6O13Nano material presoma；
2) Na is washed with the acidic materials that concentration is 0.01~0.1M2Ti6O13Nano material presoma obtains H several times2Ti6O13 Nano material；
3) by H2Ti6O13Nano material is in air atmosphere, is thermally treated resulting in H at 250-270 DEG C2Ti12O25Nano material.
3. hydrogen titanium oxide/polypyrrole nano composite material made from preparation method as claimed in claim 1 or 2.
CN201710555473.1A 2017-07-07 2017-07-07 A kind of hydrogen titanium oxide/polypyrrole nano composite material and preparation method thereof Pending CN107359333A (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101400608A (en) * 2006-03-07 2009-04-01 石原产业株式会社 Titanium oxide, conductive titanium oxide, and processes for producing these
CN102082259A (en) * 2010-12-30 2011-06-01 常州华科新能源科技有限公司 Lithium secondary battery electrodes and production method thereof
CN102104170A (en) * 2010-12-30 2011-06-22 常州华科新能源科技有限公司 Great-capacity high-power lithium secondary battery and preparation method thereof
CN106058194A (en) * 2016-07-21 2016-10-26 天津巴莫科技股份有限公司 Inlaid polyaniline/H2Ti12O25 nanosheet composite material and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101400608A (en) * 2006-03-07 2009-04-01 石原产业株式会社 Titanium oxide, conductive titanium oxide, and processes for producing these
CN102082259A (en) * 2010-12-30 2011-06-01 常州华科新能源科技有限公司 Lithium secondary battery electrodes and production method thereof
CN102104170A (en) * 2010-12-30 2011-06-22 常州华科新能源科技有限公司 Great-capacity high-power lithium secondary battery and preparation method thereof
CN106058194A (en) * 2016-07-21 2016-10-26 天津巴莫科技股份有限公司 Inlaid polyaniline/H2Ti12O25 nanosheet composite material and preparation method thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘承美，等: "《现代高分子化学实验与技术 第1版》", 31 May 2008 *
蒋阳等: "《粉体工程 第1版》", 31 December 2008 *

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