CN110304652A - A kind of synthetic method of magnesium ion electrode material - Google Patents

A kind of synthetic method of magnesium ion electrode material Download PDF

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CN110304652A
CN110304652A CN201910642713.0A CN201910642713A CN110304652A CN 110304652 A CN110304652 A CN 110304652A CN 201910642713 A CN201910642713 A CN 201910642713A CN 110304652 A CN110304652 A CN 110304652A
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magnesium ion
electrode material
synthetic method
magnesium
high annealing
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CN110304652B (en
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洪振生
罗兰
卢熖忠
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Fujian Normal University
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Fujian Normal University
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/003—Titanates
    • C01G23/005—Alkali titanates
    • 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
    • H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
    • 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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
    • C01P2004/16—Nanowires or nanorods, i.e. solid nanofibres with two nearly equal dimensions between 1-100 nanometer
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/40—Electric properties
    • 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

Abstract

The invention belongs to Magnesium ion battery technical fields, and in particular to a kind of magnesium ion electrode material Na2Ti6O13Synthetic method.By TiOSO4It is dissolved in NaOH and H2In the mixed solution of O.After solution is stirred, then 45-48 hour is heated at 150-180 DEG C, by sediment washing 5-7 time, be then dried overnight collection and obtain white titanate nanowire presoma, it is last finally in air 200-280 DEG C obtain final nano wire Na after high annealing 2-5 hours2Ti6O13.Material of the present invention has very high coulombic efficiency for the first time and higher specific capacity, and low manufacture cost has development prospect.

Description

A kind of synthetic method of magnesium ion electrode material
Technical field
The invention belongs to Magnesium ion battery technical fields, and in particular to a kind of magnesium ion electrode material Na2Ti6O13Synthesis Method.
Background technique
Magnesium ion battery is due to high capacity (2205 mAh g-1With 3833 mAh cm-3), low reduction potential (- 2.37 V Vs. SHE), the abundant reserves of magnesium metal and the concern that many scientific research personnel are caused without dendrite formation.Due to Mg2 +Band two There is stronger electrostatic interaction between a charge and anion, lead to Mg2+Ion slow intercalation power in lattice.It is visiting Rigging has the new electrode materials aspect for the ability for being enough to surmount current lithium ion battery technology to still have challenge.In all magnesium Ti sill is due to its low cost, rich reserves and environmental-friendly and receive great attention in ion battery electrode materials.
Summary of the invention
The purpose of the present invention is to provide a kind of magnesium ion electrode material Na2Ti6O13Synthetic method.The present invention for the first time will It finds it with very high coulombic efficiency for the first time and higher specific capacity as Magnesium ion battery electrode material.
To achieve the above object, the present invention adopts the following technical scheme:
The Na2Ti6O13The preparation method of material, comprising the following steps:
(1) titanate nanowire presoma is prepared: by 1-2 g TiOSO4It is dissolved in 30-50 ml 15 M NaOH and 18-30 ml H2In the mixed solution of O.
(2) after stirring solution 7-10 minutes, above-mentioned solution is transferred in the liner that capacity is 60-100 ml, and 45-48 hour is heated at 150-180 DEG C.
(3) finally by sediment be washed with deionized 5-7 times until pH value for neutrality, it is then dried at 60 DEG C Night collects to obtain white titanate nanowire presoma.
(4) finally in air 200-280 DEG C obtain final nano wire Na after high annealing 2-5 hours2Ti6O13。
Magnesium ion battery assembling: it is counted in mass ratio by Na2Ti6O13 : acetylene black: PTFE=70-75:15-20:5-10 stirring Mixing crushes the electrode film being pressed into a thickness of 70-100 mm by roller, and it is small to be cut into quality about 1.3-1.8 mg with scissors Block electrode film, nickel foam is as collector.Just extremely magnesium metal, electrolyte are 0.4 M 2PhMgCl-AlCl3 (APC)/THF Solution.All assemblings carry out (oxygen and moisture content are below 1 ppm) in the glove box full of argon gas.
Remarkable advantage of the invention is:
The present invention provides a kind of novel magnesium ion electrode material Na2Ti6O13Synthetic method preparation method, and find for the first time Its applications well prospect in terms of Magnesium ion battery.Its is easy to operate, at low cost, has excellent performance, and can largely synthesize.
Detailed description of the invention
Fig. 1 Na2Ti6O13XRD diagram；
Fig. 2 Na2Ti6O13SEM figure；
Fig. 3 Na2Ti6O13In 0.01A g-1Charging and discharging curve under current density；
Fig. 4 Na2Ti6O13Multiplying power figure；
Fig. 5 Na2Ti3O7In 0.01 A g-1Charging and discharging curve under current density；
Fig. 6 Na2Ti3O7XRD diagram.
Specific embodiment
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
Embodiment 1
The Na2Ti6O13The preparation method of material, comprising the following steps:
(1) titanate nanowire presoma is prepared: by 1 g TiOSO4It is dissolved in 40 ml 15 M NaOH and 25 ml H2O's In mixed solution.
(2) after stirring solution 7 minutes, above-mentioned solution is transferred in the liner that capacity is 100 ml, and at 160 DEG C 46 hours of lower heating.
(3) finally sediment is washed with deionized 5 times, collection is then dried overnight at 60 DEG C and obtains white titanium Silicate nanometer line presoma.
(4) finally in air 220 DEG C obtain final nano wire Na after high annealing 3 hours2Ti6O13。
Embodiment 2
The Na2Ti6O13The preparation method of material, comprising the following steps:
(1) titanate nanowire presoma is prepared: by 1.5g TiOSO4It is dissolved in 45 ml 15 M NaOH and 26 ml H2O's In mixed solution.
(2) after stirring solution 8 minutes, above-mentioned solution is transferred in the liner that capacity is 100 ml, and at 170 DEG C 47 hours of lower heating.
(3) after sediment being finally washed with deionized 6 times, collection then is dried overnight at 60 DEG C and obtains white Titanate nanowire presoma.
(4) finally in air 230 DEG C obtain final nano wire Na after high annealing 3 hours2Ti6O13。
Embodiment 3
The Na2Ti6O13The preparation method of material, comprising the following steps:
(1) titanate nanowire presoma is prepared: by 2 g TiOSO4It is dissolved in 50 ml 15 M NaOH and 30 ml H2O's In mixed solution.
(2) after ten minutes by solution stirring, above-mentioned solution is transferred in the liner that capacity is 100 ml, and at 180 DEG C 48 hours of lower heating.
(3) finally sediment is washed with deionized for several times after 7 times, is then dried overnight collection at 60 DEG C and obtains White titanate nanowire presoma.
(4) finally in air 240 DEG C obtain final nano wire Na after high annealing 4 hours2Ti6O13。
Comparative example
The Na2Ti3O7The preparation method of material, comprising the following steps:
(1) titanate nanowire presoma is prepared: by 1 g TiOSO4It is dissolved in 40 ml 15 M NaOH and 25 ml H2O's In mixed solution.
(2) after stirring solution 7 minutes, above-mentioned solution is transferred in the liner that capacity is 100 ml, and at 160 DEG C 46 hours of lower heating.
(3) finally sediment is washed with deionized 2 times, then removes remaining alkali with twice of ethanol washing, then existed It is dried overnight collection at 60 DEG C and obtains white titanate nanowire presoma.
(4) finally in air 220 DEG C obtain final nano wire Na after high annealing 3 hours2Ti3O7。
Magnesium ion battery assembling: it is counted in mass ratio by Na2Ti6O13 : acetylene black: PTFE=70-75:15-20:5-10 stirring Mixing crushes the electrode film being pressed into a thickness of 70-100 mm by roller, and it is small to be cut into quality about 1.3-1.8 mg with scissors Block electrode film, nickel foam is as collector.Just extremely magnesium metal, electrolyte are 0.4 M 2PhMgCl-AlCl3 (APC)/THF Solution.All assemblings carry out (oxygen and moisture content are below 1 ppm) in the glove box full of argon gas.Comparative example Na2Ti3O7It is similar to assemble situation.
From Fig. 1 X-ray powder diffraction analysis chart can be seen that the diffraction maximum of prepared sample with JCPDS standard card The diffraction maximum of (14-0277) is consistent, and its diffraction maximum and Fig. 1 diffraction maximum are significantly different as can be seen from Figure 6.Scheme from the SEM of Fig. 2 It can be clearly seen that material is nanowire structure.As shown in figure 3, being in current density under the voltage window of 0.01-2.0V 0.01 A g-1Lower carry out charge and discharge, first discharge specific capacity is up to 165.8 mA h g-1, initial charge capacity is 147.7 mA h g-1, first charge discharge efficiency is up to 89.1%.This is highest efficiency in current titanium-based storage Development of Magnesium Electrode Materials.As shown in figure 4, Na2Ti6O13With excellent high rate performance, it can be seen that in 1 A g-1High current density under, reversible capacity still has 30 mAh g-1.That comparative example obtains is the higher Na of sodium content2Ti3O7Structure, the only change of mode of washing, but for material Store up magnesium performance influence be very big, as shown in figure 5, its coulombic efficiency only has 41.9% for the first time, reversible charging capacity only has 44.7 mAh g-1.This further illustrates advanced and different sodium titanate structure the significantly affecting on storage magnesium performance of material prepared.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with Modification, is all covered by the present invention.

Claims (4)

1. a kind of magnesium ion Na2Ti6O13The synthetic method of electrode material, it is characterised in that: the following steps are included:
(1) titanate nanowire presoma is prepared: by 1-2 g TiOSO4It is dissolved in 15 M NaOH and 18-30 ml of 30-50 ml H2In the mixed solution of O；
(2) after stirring solution 7-10 minutes, above-mentioned solution is transferred to water in the autoclave liner that capacity is 60-100 ml Thermal response；
(3) finally sediment is washed with deionized 5 ~ 7 times, collection is then dried overnight at 60 DEG C and obtains white metatitanic acid Salt nanowire precursor；
(4) final nano wire Na is obtained after final high annealing in air2Ti6O13。
2. a kind of magnesium ion Na according to claim 12Ti6O13The synthetic method of electrode material, it is characterised in that: step (2) hydro-thermal reaction specifically: 45-48 hour is heated at 150-180 DEG C.
3. a kind of magnesium ion Na according to claim 12Ti6O13The synthetic method of electrode material, it is characterised in that: step (4) high annealing specifically: 200-280 DEG C high annealing 2-5 hours.
4. a kind of a kind of magnesium ion Na as described in claim 12Ti6O13Application of the electrode material on Magnesium ion battery, it is special Sign is: Magnesium ion battery assembling: is counted in mass ratio by Na2Ti6O13 : acetylene black: PTFE=70-75:15-20:5-10 stirring Mixing crushes the electrode film being pressed into a thickness of 70-100 mm by roller, will be cut into quality 1.3-1.8 mg fritter with scissors Electrode film, nickel foam is as collector；Just extremely magnesium metal, electrolyte are 0.4 M 2PhMgCl-AlCl3(APC)/THF is molten Liquid；All assemblings carry out in the glove box full of argon gas, and wherein oxygen and moisture content are below 1 ppm.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1378977A (en) * 2002-05-24 2002-11-13 清华大学 Process for preparing hydrated sodium titanate and nano titanate tube series
CN109326790A (en) * 2018-08-30 2019-02-12 中国石油天然气股份有限公司 A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1378977A (en) * 2002-05-24 2002-11-13 清华大学 Process for preparing hydrated sodium titanate and nano titanate tube series
CN109326790A (en) * 2018-08-30 2019-02-12 中国石油天然气股份有限公司 A kind of 1-dimention nano threadiness sodium titanate and its preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CHENGCHENG CHEN等: "Layered Na2Ti3O7/MgNaTi3O7/Mg0.5NaTi3O7 Nanoribbons as High-Performance Anode of Rechargeable Mg-Ion Batteries", 《ACS ENERGY LETT.》 *
HONGWEI LIU等: "A Raman spectroscopic and TEM study on the structural evolution of Na2Ti3O7 during the transition to Na2Ti6O13", 《J. RAMAN SPECTROSC.》 *

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