CN104091917A - Titanic oxide negative electrode material used as sodium-ion battery and preparation method of thereof - Google Patents
Titanic oxide negative electrode material used as sodium-ion battery and preparation method of thereof Download PDFInfo
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- CN104091917A CN104091917A CN201410328415.1A CN201410328415A CN104091917A CN 104091917 A CN104091917 A CN 104091917A CN 201410328415 A CN201410328415 A CN 201410328415A CN 104091917 A CN104091917 A CN 104091917A
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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
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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
- 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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- 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
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Abstract
The invention relates to a titanic oxide negative electrode material used as a sodium-ion battery and a preparation method of the material. According to the titanic oxide negative electrode material, part of titanium is replaced by using doped ions, so that an ion transmission channel is expanded. The negative electrode material contains MxTi<1-x>Oy, wherein x is greater than 0 and less than 0.25, y is greater than 1.5 and less than 2.25, and M is selected from one or several out of Mn, Fe, Co, Ni, Cu, Zn, Mo, Nb, In, Sn, Bi, B or Zr. Compared with the prior art, the doped titanic oxide negative electrode material prepared by the method provided by the invention is good in electro-chemical properties such as relatively good circulation property, relatively high reversible specific capacity and good capability of removing sodium and embedding sodium; the titanic oxide negative electrode material is abundant in raw materials, low in cost and simple in preparation process; the titanic oxide negative electrode material is expected to become a sodium-ion battery negative electrode material.
Description
Technical field
The invention belongs to energy storage material and technical field of chemical power, especially relate to a kind of titanium oxide negative material that can be used as sodium-ion battery and preparation method thereof.
Background technology
Since commercialization in 1991 starts, lithium ion battery is in research or application aspect has all experienced leap progress, has developed into a kind of more ripe accumulation power supply.Although the advantages such as lithium ion battery is high with its energy density, the life-span is long are widely applied on portable equipment,, along with lithium ion battery large-scale application, lithium resource shortage problem becomes increasingly conspicuous.In this case, people start to turn one's attention to the more sodium of horn of plenty of resource, recently more and more to the research of sodium-ion battery.
Sodium element and lithium belong to alkali metal together, have a lot of similarities in chemical property, and reserves are abundant, and cheap, if can successfully develop the sodium-ion battery of chemical property excellence, its market prospects will be far above lithium ion battery.But sodium atom radius is large compared with lithium atom, in electrode material, sodium ion is difficult to reversible embedding/deviate from, and then causes the problems such as its reversible specific capacity is low, and cycle performance is poor.Because the characteristic performance of sodium-ion battery depends on the chemical property of electrode material, the electrode material of therefore finding suitable sodium-ion battery is most important.In sodium-ion battery, the research of positive electrode is more, makes some progress.But the research for anode material of lithium-ion battery is less, mainly concentrate on carbon negative pole, alloy anode and a few compounds negative pole etc.
In carbon negative pole material, the storage sodium effect of disordered carbon is best, the carbon-coating degree of disorder of hard carbon is maximum, thereby its storage sodium effect is best, specific capacity can reach 200-300mAh/g (Stevens DA, Dahn JR.The mechanisms of lithium and sodium insertion in carbon materials.J Electrochem Soc2001; 148:A803.).Application number is that 201210038789.0 Chinese invention patent discloses " a kind of anode material of lithium-ion battery ", this patent adopts the sodium alloy that can form alloy with sodium as negative material, although the initial capacity of alloy material is high, but the carrying out along with circulation, alloy volume zone of swelling has come cyclical stability to fall sharply, such as forming, Sn/ acetylene black composite material and sodium circulates after alloy 20 times time, de-sodium capacity has dropped to 221mAh/g by secondary 440mAh/g, and capacity attenuation rate reaches 50%.Compound negative material is typically oxide and sodium ascorbyl phosphate negative material.As Na
2ti
3o
7(P.Senguttuvan.G.Rousse, V.Seznec, J.M.Taraascon, M.R.Palacin, Chem.Mater.23 (2011) 4109.) and NaTi
2(PO
4)
3(P.Senguttuvan.G.Rousse, M.E.Arroyo y de Dompablo, H.Vezin, J.M.Taraascon, M.R.Palacin, J.Am.Chem.Soc.135 (2013) 3897.) compound, its specific capacity and cyclical stability all have much room for improvement.Therefore, in order to adapt to the requirement of high-energy-density sodium-ion battery, in the urgent need to exploitation long-life, the anode material of lithium-ion battery of high power capacity.
Summary of the invention
Object of the present invention is exactly to provide a kind of titanium oxide negative material that can be used as sodium-ion battery in order to overcome the defect of above-mentioned prior art existence, this negative material is because the effect of doping ion makes the ion transfer passage of material become more spacious, the embedding of sodium ion with deviate to be more prone to carry out, thereby the chemical property of material is improved.
Object of the present invention can be achieved through the following technical solutions:
Can be used as a titanium oxide negative material for sodium-ion battery, utilize doping ion to replace partial-titanium, widened ion transfer passage, negative material consist of M
xti
(1-x)o
y, 0 < x < 0.25,1.5 < y < 2.25 wherein, M is one or more in Mn, Fe, Co, Ni, Cu, Zn, Mo, Nb, In, Sn, Bi, B or Zr.
Doping ion is preferably Nb, In, Sn, Bi.
Can be used as the preparation method of the titanium oxide negative material of sodium-ion battery, adopt following steps:
(1) by titanium source and doped source, be 1 in molar ratio: dry after the ratio of 0.002-0.33 mixes in liquid phase, obtain presoma;
(2) presoma step (1) being obtained is warming up to 400-800 ℃ and be incubated 3-10h with 2-10 ℃/min speed under air, oxygen, nitrogen, argon gas or ammonia condition, naturally cooling, obtains titanium oxide negative material.
Described titanium source is butyl titanate, tetraethyl titanate, titanium dioxide, one or more in isopropyl titanate, titanium tetrachloride or titanyl sulfate.
Described doped source is one or more of oxide, hydroxide, halide or salt compounds of Mn, Fe, Co, Ni, Cu, Zn, Mo, Nb, In, Sn, Bi, B or Zr.
Described liquid phase is one or more and the mixture of water or concentrated hydrochloric acid in ethanol, ethylene glycol, cyclohexane.
Atmosphere when presoma heats up is preferably nitrogen or air.
Compared with prior art, the adulterated TiOx negative material that the present invention prepares, this negative material is because the effect of doping ion makes the ion transfer passage of material become more spacious, the embedding of sodium ion with deviate to be more prone to carry out, thereby there is good chemical property, as good cycle performance and higher reversible specific capacity and good de-sodium embedding sodium ability, its abundant raw material, cheap preparation technology is simple, is expected to become a kind of anode material of lithium-ion battery.
Accompanying drawing explanation
Fig. 1 is that embodiment 1 contrasts collection of illustrative plates with the XRD of comparative example 1;
Fig. 2 is embodiment 1 and the Capacitance reserve performance map of comparative example 1 under different discharging currents.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1
The ethanol of 20ml is mixed with the concentrated hydrochloric acid of 5ml, then add wherein the NbCl of 0.002mol
5, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under air atmosphere, is warming up to 500 ℃ with the heating rate of 3 ℃/min, and is incubated 5h and obtains product niobium adulterated TiOx.
Embodiment 2
The ethylene glycol of 30ml is mixed with the concentrated hydrochloric acid of 1ml, then add wherein the NbCl of 0.004mol
5, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under oxygen atmosphere, is warming up to 700 ℃ with the heating rate of 10 ℃/min, and is incubated 3h and obtains product niobium adulterated TiOx.
Embodiment 3
The cyclohexane of 15ml is mixed with the concentrated hydrochloric acid of 2ml, then add wherein the InCl of 0.0001mol
3, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under argon atmosphere, is warming up to 400 ℃ with the heating rate of 2 ℃/min, and is incubated 10h and obtains product indium adulterated TiOx.
Embodiment 4
The ethanol of 20ml, 10ml ethylene glycol are mixed with the concentrated hydrochloric acid of 1.5mL, then add wherein the SnCl of 0.006mol
2, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under ammonia atmosphere, is warming up to 600 ℃ with the heating rate of 5 ℃/min, and is incubated 4h and obtains product tin dope titanium oxide.
Embodiment 5
The cyclohexane of the ethanol of 20ml, 5ml is mixed with the deionized water of 0.8mL, add wherein the dense HCl of 3ml, then add wherein the InCl of 0.002mol
3, SnCl
2, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under nitrogen atmosphere, is warming up to 600 ℃ with the heating rate of 5 ℃/min, and is incubated 4h and obtains product indium, tin dope titanium oxide.
Embodiment 6
The alcohol of 20ml is mixed with the deionized water of 0.8mL, then add wherein the boric acid of 0.002mol, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under nitrogen atmosphere, is warming up to 400 ℃ with the heating rate of 8 ℃/min, and is incubated 8h and obtains product boron adulterated TiOx.
Embodiment 7
The alcohol of 20ml is mixed with the deionized water of 0.8mL, then add wherein the zirconium nitrate of 0.002mol, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under nitrogen atmosphere, is warming up to 800 ℃ with the heating rate of 10 ℃/min, and is incubated 1h and obtains product zirconium adulterated TiOx.
Comparative example 1
The ethanol of 20ml is mixed with the deionized water of 0.5ml, under stirring, add the butyl titanate of 0.02mol, subsequently by solution heating, drying under agitation.The product that oven dry is obtained, under air atmosphere, is warming up to 500 ℃ with the heating rate of 3 ℃/min, and is incubated 5h and obtains product pure phase titanium oxide.
Electrochemical property test:
The adulterated TiOx negative material that the inventive method is synthetic mixes in mass ratio with conductive carbon black and binding agent polyvinylidene fluoride (PVDF) respectively at 70: 15: 15, is coated on Copper Foil, is cut into electrode slice, in 100 ℃ of vacuumize 24h after being dried.
Take sodium metal as to electrode;
By electrolyte NaClO
4it is to form NaClO in the mixed solution of ethylene carbonate (EC)/Merlon (PC) of 1: 1 that salt is dissolved in mass ratio
4the concentration of salt is the electrolyte of 1mol/L;
In argon gas glove box, be assembled into button cell.
Adopt the blue electric CT2001A type cell tester in Wuhan to carry out electrochemical property test, charging/discharging voltage scope is 0.03V-2.5V (vs.Na
+/ Na).
Fig. 1 is that embodiment 1 contrasts collection of illustrative plates with the XRD of comparative example 1.As can be seen from the figure, the diffraction maximum before and after doping is basically identical, illustrates that the titanium oxide crystal structure before and after doping does not change; Relative pure phase, the diffraction maximum of adulterated TiOx is offset toward low angle, illustrates that the rear material lattice parameter of doping becomes large, and the embedding that is conducive to sodium ion takes off.
Fig. 2 is the embodiment of the present invention 1 and the Capacitance reserve performance map of comparative example 1 under different discharging currents.As can be seen from the figure, within the scope of the charging/discharging voltage of 0.03-2.5V, under 15mA/g discharging current, after 15 circulations, the Capacitance reserve of adulterated TiOx is up to 118.8mAh/g, and the capacity of pure phase titania meterial is only 20.1mAh/g; When discharging current is elevated to 30mA/g, 60mA/g, 150mA/g, the capacity of adulterated TiOx remains respectively 98.4mAh/g, 85.6mAh/g, 65mAh/g, and the capacity of pure phase titanium oxide is only 17.4mAh/g, 14.1mAh/g, 10.5mAh/g.The relative pure phase titanium oxide of cyclical stability that adulterated TiOx material prepared by the present invention is described has increased significantly, and especially stability is being had under the high power charging-discharging condition of considerable influence, and the improvement of stability is obvious.
Claims (7)
1. a titanium oxide negative material that can be used as sodium-ion battery, is characterized in that, utilizes doping ion to replace partial-titanium, has widened ion transfer passage, negative material consist of M
xti
(1-x)o
y, 0 < x < 0.25,1.5 < y < 2.25 wherein, M is one or more in Mn, Fe, Co, Ni, Cu, Zn, Mo, Nb, In, Sn, Bi, B or Zr.
2. a kind of titanium oxide negative material that can be used as sodium-ion battery according to claim 1, is characterized in that, doping ion is preferably Nb, In, Sn, Bi.
3. according to the preparation method of the titanium oxide negative material that can be used as sodium-ion battery described in any one in claim 1-2, it is characterized in that, the method adopts following steps:
(1) by titanium source and doped source, be 1 in molar ratio: dry after the ratio of 0.002-0.33 mixes in liquid phase, obtain presoma;
(2) presoma step (1) being obtained is warming up to 400-800 ℃ and be incubated 3-10h with 2-10 ℃/min speed under air, oxygen, nitrogen, argon gas or ammonia condition, naturally cooling, obtains titanium oxide negative material.
4. the preparation method who can be used as the titanium oxide negative material of sodium-ion battery according to claim 3, it is characterized in that, described titanium source is butyl titanate, tetraethyl titanate, titanium dioxide, one or more in isopropyl titanate, titanium tetrachloride or titanyl sulfate.
5. the preparation method who can be used as the titanium oxide negative material of sodium-ion battery according to claim 3, it is characterized in that, described doped source is one or more of oxide, hydroxide, halide or salt compounds of Mn, Fe, Co, Ni, Cu, Zn, Mo, Nb, In, Sn, Bi, B or Zr.
6. the preparation method who can be used as the titanium oxide negative material of sodium-ion battery according to claim 3, is characterized in that, described liquid phase is one or more and the mixture of water or concentrated hydrochloric acid in ethanol, ethylene glycol, cyclohexane.
7. the preparation method who can be used as the titanium oxide negative material of sodium-ion battery according to claim 3, is characterized in that, atmosphere when presoma heats up is preferably nitrogen or air.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328928A (en) * | 2016-11-07 | 2017-01-11 | 中国科学院化学研究所 | Anode material for sodium-ion battery, preparation method thereof and method for increasing air stability |
| CN107565114A (en) * | 2017-08-30 | 2018-01-09 | 北京理工大学 | A kind of binder free anode material of lithium-ion battery and preparation method thereof |
| CN108511727A (en) * | 2018-04-20 | 2018-09-07 | 南京林业大学 | A kind of sodium titanate negative material and preparation method thereof of high-valence cationic doping |
| CN109065870A (en) * | 2018-08-10 | 2018-12-21 | 陕西科技大学 | It is a kind of to prepare Mo6+Adulterate δ-MnO2The method of bouquet particle |
| CN110931264A (en) * | 2019-10-31 | 2020-03-27 | 武汉理工大学 | Iron in-situ doped sodium titanate electrode material and preparation method thereof |
| CN113976162A (en) * | 2021-11-16 | 2022-01-28 | 盐城工学院 | Co-doped TiO2Photocatalyst, supported preparation method and preparation device |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328928A (en) * | 2016-11-07 | 2017-01-11 | 中国科学院化学研究所 | Anode material for sodium-ion battery, preparation method thereof and method for increasing air stability |
| CN106328928B (en) * | 2016-11-07 | 2019-04-16 | 中国科学院化学研究所 | A kind of sodium-ion battery positive material, preparation method and the method for improving air stability |
| CN107565114A (en) * | 2017-08-30 | 2018-01-09 | 北京理工大学 | A kind of binder free anode material of lithium-ion battery and preparation method thereof |
| CN108511727A (en) * | 2018-04-20 | 2018-09-07 | 南京林业大学 | A kind of sodium titanate negative material and preparation method thereof of high-valence cationic doping |
| CN109065870A (en) * | 2018-08-10 | 2018-12-21 | 陕西科技大学 | It is a kind of to prepare Mo6+Adulterate δ-MnO2The method of bouquet particle |
| CN110931264A (en) * | 2019-10-31 | 2020-03-27 | 武汉理工大学 | Iron in-situ doped sodium titanate electrode material and preparation method thereof |
| CN110931264B (en) * | 2019-10-31 | 2021-07-06 | 武汉理工大学 | Iron in-situ doped sodium titanate electrode material and preparation method thereof |
| CN113976162A (en) * | 2021-11-16 | 2022-01-28 | 盐城工学院 | Co-doped TiO2Photocatalyst, supported preparation method and preparation device |
| CN113976162B (en) * | 2021-11-16 | 2023-04-21 | 盐城工学院 | Co-doped TiO 2 Photocatalyst, supported preparation method and preparation device |
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Application publication date: 20141008 |