CN104269547A - Preparation method of carbon-coating vanadium-doped titanic oxide - Google Patents

Preparation method of carbon-coating vanadium-doped titanic oxide Download PDF

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Publication number
CN104269547A
CN104269547A CN201410531202.9A CN201410531202A CN104269547A CN 104269547 A CN104269547 A CN 104269547A CN 201410531202 A CN201410531202 A CN 201410531202A CN 104269547 A CN104269547 A CN 104269547A
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China
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titanium oxide
vanadium doping
preparation
carbon
atmosphere
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CN201410531202.9A
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Chinese (zh)
Inventor
徐士民
李宏斌
马毅
徐一丹
都云
刘志坚
陈俊桦
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XI'AN ZHONGKE NEW ENERGY SCIENCE & TECHNOLOGY Co Ltd
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XI'AN ZHONGKE NEW ENERGY SCIENCE & TECHNOLOGY Co Ltd
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Priority to CN201410531202.9A priority Critical patent/CN104269547A/en
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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
    • H01M4/48—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
    • 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 discloses a preparation method of carbon-coating vanadium-doped titanic oxide. The method comprises the following steps: firstly, preparing vanadium-doped sodium trititanate Na2TiyVxO7; preparing by utilizing an ion exchange method to obtain vanadium-doped titanic acid H2TiyVxO7; heating the vanadium-doped titanic acid H2TiyVxO7 in the air to prepare vanadium-doped titanic oxide H2TizVxO25; uniformly mixing the vanadium-doped titanic oxide H2TizVxO25 with carbon sources; calcining under the vacuum or protective atmosphere to prepare the carbon-coating vanadium-doped titanic oxide H2TizVxO25. The preparation method is simple in process and has no pollutions during reaction and has a good industrial application prospect.

Description

The preparation method of the coated vanadium doping titanium oxide of a kind of carbon
Technical field
The invention belongs to technical field of nano material, be specifically related to the preparation method of the coated vanadium doping titanium oxide of a kind of carbon.
Background technology
Lithium ion battery, due to features such as energy density height and good cycle, is subject to increasing attention in New Energy Industry.Ion secondary battery cathode material lithium has graphite, lithium titanate, ashbury metal and silicon alloy etc., wherein lithium titanate (Li 4ti 5o 12) be a kind of ion secondary battery cathode material lithium having applications well prospect, lithium titanate battery has long-life, high magnification, fail safe and outstanding high temperature performance.
Lithium titanate is a kind of composite oxides by lithium metal and electronegative potential transition metals Ti, and spinel structure, space group is Fd3m, non-conductive, in atmosphere can stable existence.As lithium ion secondary battery negative pole, in charge and discharge process, crystal formation change does not occur, and change in volume is less than 1%, is called as " zero strain material ".The structure of this stable densification can provide the passage of turnover for limited lithium ion, make Li 4ti 5o 12there is the cycle performance more excellent than Carbon anode.In charging process, Li 4ti 5o 12crystal embeds 3 lithium ions, generates blue Li 7ti 5o 12crystal structure, under not overcharging condition, can not generate lithium metal, and therefore, lithium titanate anode material is considered to safe lithium cell cathode material.
But the theoretical gram volume of lithium titanate only has 175mAh/g, lower gram volume limits its development in more battery applications fields.
At 25 DEG C, lithium ion is at Li 4ti 5o 12having higher electrochemical diffusion coefficient is 2 × 10 -8cm 2/ s, high diffusion coefficient make lithium titanate can fast, multi cycle discharge and recharge.But Li 4ti 5o 12self-conductive rate about 10 -13s/cm, belongs to insulator, and therefore will make it in high current charge-discharge, obtain application needs to modify or modification it.
In lithium titanate crystal, doped metal ion is a kind of a kind of method improving lithium titanate self-conductive rate.
Japanese industries Technical Integration Studies institute in 2010 (produce to combine and grinds) have developed Li-Ion rechargeable battery new titanium oxide negative material H 2ti 12o 25.
Titanium oxide negative material H 2ti 12o 25except the advantage with lithium titanate, also have high gram volume 225mAh/g, energy density can improve three one-tenth than lithium titanate.
New titanium oxide negative material H 2ti 12o 25have the design feature similar with lithium titanate, self-conductive rate is low.
Therefore, can at titanium oxide H 2ti 12o 25doped metal ion in crystal structure, can increase titanium oxide negative material H 2ti 12o 25conductivity, improves high rate performance.
Prepare carbon coated vanadium doping titanium oxide H at present 2ti 12o 25method have not been reported.
Summary of the invention
In order to improve titanium oxide H 2ti 12o 25the conductivity of material, the present invention proposes the preparation method of the coated vanadium doping titanium oxide of a kind of carbon.
The present invention adopts following technical scheme:
A preparation method for the coated vanadium doping titanium oxide of carbon, its special character is: comprise the following steps:
1) titanium dioxide, sodium carbonate and vanadic oxide are mixed, be placed in air and calcine, naturally cool, prepare vanadium doping sodium trititanate Na 2ti yv xo 7powder, wherein x+y=3,0≤x≤0.5;
2) by vanadium doping sodium trititanate Na 2ti yv xo 7be immersed in hydrochloric acid solution, after sodium ion and hydrogen exchange, heat drying in atmosphere, prepares vanadium doping metatitanic acid H 2ti yv xo 7, wherein x+y=3,0≤x≤0.5;
3) by vanadium doping metatitanic acid H 2ti yv xo 7heating prepares vanadium doping titanium oxide H in atmosphere 2ti zv xo 25, wherein x+z=12,0≤x≤0.5;
4) by vanadium doping titanium oxide H 2ti zv xo 25calcine under vacuum or protective atmosphere with carbon source, naturally cool to room temperature, Formed coated titanium oxide H 2ti zv xo 25.
The crystal formation of above-mentioned titanium dioxide is rutile-type, Detitanium-ore-type, brookite type or unformed;
Described carbon source comprises one or more in pitch, starch, glucose, maltose, citric acid, cyclodextrin, acetate fiber, epoxy resin, phenolic resins, Lauxite, furfural resin, polyvinyl alcohol and polyvinylidene.
Above-mentioned carbon source and vanadium doping titanium oxide H 2ti zv xo 25the mass percent of powder is 1 ~ 20:100;
Above-mentioned protective gas is one or more of nitrogen, helium and argon gas.
Above-mentioned steps 1) calcination condition is: in air atmosphere, is warmed up to 500 ~ 900 DEG C with the speed of 2 ~ 5 DEG C/min, and keeps 5 ~ 30 hours at this temperature, after reaction terminates, in air atmosphere, naturally cool to room temperature.
Above-mentioned steps 2) heating condition is: in air atmosphere, adds hot temperature 50 ~ 100 DEG C, and keeps 0.5 ~ 36 hour at this temperature, then in air atmosphere, naturally cool to room temperature.
Above-mentioned steps 3) calcination condition is: in air atmosphere, is warmed up to 200 ~ 500 DEG C with the speed of 2 ~ 5 DEG C/min, and keeps 0.5 ~ 20 hour at this temperature, after reaction terminates, in air atmosphere, naturally cool to room temperature.
Above-mentioned steps 4) calcination condition is: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature; and then continue to be warmed up to 500 ~ 950 DEG C with the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
The invention has the beneficial effects as follows:
1, the present invention is the preparation method that ion secondary battery cathode material lithium adds that a kind of new material provides this material simultaneously.
2, preparation process of the present invention is simple, and equipment requirement is low, and course of reaction is pollution-free, and product uniformity is good, has good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is embodiment step 2) the vanadium doping metatitanic acid H that generates 2ti 2. 8v 0. 2o 7xRD spectra;
Fig. 2 is embodiment step 3) the vanadium doping titanium oxide H that generates 2ti 11. 8v 0. 2o 25xRD spectra.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but the present invention is not limited thereto.
Embodiment raw materials, is analysis pure, content >=99.9%.
Embodiment
A preparation method for the coated vanadium doping titanium oxide of carbon, comprises the following steps:
Step 1) vanadium doping sodium trititanate Na 2ti yv xo 7preparation
After Na:Ti:V=2:2.8:0.2 weighing sodium carbonate 4.74g in molar ratio, titanium dioxide 10.00g, vanadic oxide 0.813g mixed grinding is even, 800 DEG C of calcining 20h in air, take out grinding again evenly, then in air 800 DEG C of calcining 20h, obtain yellow solid vanadium doping sodium trititanate Na 2ti 2.8v 0.2o 7.
Step 2) vanadium doping metatitanic acid H 2ti yv xo 7preparation
By ion-exchange, according to molecular formula mol ratio, get and soak Na little over amount 10%HCl solution at 60 DEG C 2ti 2.8v 0.2o 75 days.The vanadium doping metatitanic acid H that ion-exchange is obtained 2ti 2.8v 0.2o 7respectively clean 5 times with ultra-pure water and absolute ethyl alcohol, then 60 DEG C of heat dryings 1 day in atmosphere, mill, obtain vanadium doping metatitanic acid H 2ti 2.8v 0.2o 7yellow fine-powder.
Step 3) vanadium doping titanium oxide H 2ti zv xo 25preparation
By step 2) the vanadium doping metatitanic acid H for preparing 2ti 2.8v 0.2o 7250 DEG C are heated 5 hours in atmosphere, then cool room temperature, prepare vanadium doping titanium oxide H 2ti 11.8v 0.2o 25, mill and obtain yellow powder product.
Step 4) carbon coated vanadium doping titanium oxide H 2ti zv xo 25preparation
By step 3) the vanadium doping titanium oxide H for preparing 2ti 11.8v 0.2o 25powder and glucose is 100:10 Homogeneous phase mixing in mass ratio, is then placed in Nanjing Univ. Instrument Factory QM-2SP12 type ball mill argon gas atmosphere ball milling 6 hours.Uniform for ball milling blend sample is placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd JQF1400-30 high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then be warmed up to 450 DEG C with the speed of 5 DEG C/min, and keep 1 hour at this temperature, and then continue to be warmed up to 900 DEG C with the speed of 2 DEG C/min; and keep 2 hours at this temperature; naturally, after cooling, stop passing into nitrogen, obtain grey carbon coated vanadium doping titanium oxide H 2ti 11.8v 0.2o 25powder.
In claim 2, other carbon source reaction environments and condition all can reach the present embodiment equifinality.
Material property characterizes
Crystal structure test is carried out on Japanese Shimadzu X-ray diffractometer XRD-7000, adopts copper target, sweep speed 2 °/minute, measuring accuracy ± 0.04 °, sweep limits 5 ~ 90 °.
Fig. 1 is embodiment step 2) the vanadium doping metatitanic acid H that generates 2ti 2.8v 0.2o 7xRD spectra;
Fig. 2 is embodiment step 3) the vanadium doping titanium oxide H that generates 2ti 11.8v 0.2o 25xRD spectra.

Claims (8)

1. a preparation method for the coated vanadium doping titanium oxide of carbon, is characterized in that: comprise the following steps:
1) titanium dioxide, sodium carbonate and vanadic oxide are mixed, be placed in air and calcine, naturally cool, prepare vanadium doping sodium trititanate Na 2ti yv xo 7powder, wherein x+y=3,0≤x≤0.5;
2) by vanadium doping sodium trititanate Na 2ti yv xo 7be immersed in hydrochloric acid solution, after sodium ion and hydrogen exchange, heat drying in atmosphere, prepares vanadium doping metatitanic acid H 2ti yv xo 7, wherein x+y=3,0≤x≤0.5;
3) by vanadium doping metatitanic acid H 2ti yv xo 7heating prepares vanadium doping titanium oxide H in atmosphere 2ti zv xo 25, wherein x+z=12,0≤x≤0.5;
4) by vanadium doping titanium oxide H 2ti zv xo 25calcine under vacuum or protective atmosphere with carbon source, naturally cool to room temperature, Formed coated titanium oxide H 2ti zv xo 25.
2. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that:
The crystal formation of described titanium dioxide is rutile-type, Detitanium-ore-type, brookite type or unformed;
Described carbon source comprises one or more in pitch, starch, glucose, maltose, citric acid, cyclodextrin, acetate fiber, epoxy resin, phenolic resins, Lauxite, furfural resin, polyvinyl alcohol and polyvinylidene.
3. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that:
Described carbon source and titanium oxide H 2ti zv xo 25mass percent be 1 ~ 20:100.
4. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that: described protective gas is one or more in nitrogen, helium and argon gas.
5. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that:
Step 1) calcination condition is: in air atmosphere, is warmed up to 500 ~ 900 DEG C with the speed of 2 ~ 5 DEG C/min, and keeps 5 ~ 30 hours at this temperature, after reaction terminates, in air atmosphere, naturally cool to room temperature.
6. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that:
Step 2) heating condition is: in air atmosphere, adds hot temperature 50 ~ 100 DEG C, and keeps 0.5 ~ 36 hour at this temperature, then in air atmosphere, naturally cool to room temperature.
7. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that:
Step 3) calcination condition is: in air atmosphere, is warmed up to 200 ~ 500 DEG C with the speed of 2 ~ 5 DEG C/min, and keeps 0.5 ~ 20 hour at this temperature, after reaction terminates, in air atmosphere, naturally cool to room temperature.
8. the preparation method of the coated vanadium doping titanium oxide of a kind of carbon according to claim 1, is characterized in that:
Step 4) calcination condition is: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature; and then continue to be warmed up to 500 ~ 950 DEG C with the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
CN201410531202.9A 2014-10-10 2014-10-10 Preparation method of carbon-coating vanadium-doped titanic oxide Pending CN104269547A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112103495A (en) * 2020-08-25 2020-12-18 江苏理工学院 Na2Ti3-xMxO7Preparation method and application of material
CN112820876A (en) * 2021-01-21 2021-05-18 江苏理工学院 Na2Ti3O7@Fe2O3Composite material, preparation method thereof and application thereof in sodium-ion battery

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101567442A (en) * 2008-07-28 2009-10-28 新乡市中科科技有限公司 Method for preparing spinel lithium titanate
CN101679066A (en) * 2007-03-13 2010-03-24 独立行政法人产业技术总合研究所 New titanium oxide and manufacture method thereof and the lithium secondary battery that this titanium oxide is used as active substance
JP2010254482A (en) * 2009-04-21 2010-11-11 Ishihara Sangyo Kaisha Ltd Method for manufacturing alkali metal titanate compound, titanate compound or titanium oxide, and electrode active material and power storage device using them
CN102910671A (en) * 2011-08-05 2013-02-06 微宏新材料(湖州)有限公司 Preparation method for cathode active material of lithium ion battery

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101679066A (en) * 2007-03-13 2010-03-24 独立行政法人产业技术总合研究所 New titanium oxide and manufacture method thereof and the lithium secondary battery that this titanium oxide is used as active substance
CN101567442A (en) * 2008-07-28 2009-10-28 新乡市中科科技有限公司 Method for preparing spinel lithium titanate
JP2010254482A (en) * 2009-04-21 2010-11-11 Ishihara Sangyo Kaisha Ltd Method for manufacturing alkali metal titanate compound, titanate compound or titanium oxide, and electrode active material and power storage device using them
CN102910671A (en) * 2011-08-05 2013-02-06 微宏新材料(湖州)有限公司 Preparation method for cathode active material of lithium ion battery

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112103495A (en) * 2020-08-25 2020-12-18 江苏理工学院 Na2Ti3-xMxO7Preparation method and application of material
CN112820876A (en) * 2021-01-21 2021-05-18 江苏理工学院 Na2Ti3O7@Fe2O3Composite material, preparation method thereof and application thereof in sodium-ion battery
CN112820876B (en) * 2021-01-21 2022-02-11 江苏理工学院 Na2Ti3O7@Fe2O3Composite material, preparation method thereof and application thereof in sodium-ion battery

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