CN106082338A - A kind of nano-oxide Ti2nb10o29preparation method - Google Patents

A kind of nano-oxide Ti2nb10o29preparation method Download PDF

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CN106082338A
CN106082338A CN201610411168.0A CN201610411168A CN106082338A CN 106082338 A CN106082338 A CN 106082338A CN 201610411168 A CN201610411168 A CN 201610411168A CN 106082338 A CN106082338 A CN 106082338A
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oxide
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niobium oxalate
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刘国强
刘文彬
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Northeastern University China
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    • C01G33/00—Compounds of niobium
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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Abstract

A kind of nano-oxide Ti2Nb10O29Preparation method: 1) weigh Nb2O5And K2CO3Prepare mixed material；In 950～1150 DEG C of roastings 3～5h；By product of roasting, it is dissolved in distilled water and separates, obtain clear filtrate；Regulation clear filtrate PH=2～4, filters, obtains white precipitate；Wash and be dried, obtain Nb (OH)5；2) Nb (OH) is weighed5And oxalic acid；Oxalic acid, 80～90 DEG C of dissolvings, adds Nb (OH)5Until solution becomes clarification, obtain niobium oxalate solution；3) weigh in butyl titanate and niobium oxalate solution；Adding ethylene glycol to butyl titanate, dropwise dropping niobium oxalate solution obtains mixed solution；Mixed solution is incubated 20～30h at 180～210 DEG C, filters to obtain filter cake, at 950～1150 DEG C, filter cake is incubated 5～10h, obtains nanometer Ti2Nb10O29Powder.Ti of the present invention2Nb10O29The process of discharge and recharge is carried out as lithium ion battery negative material, at 1～3V potential region, under the conditions of 0.1C multiplying power, the capacity of release 350.5mAh/g.

Description

A kind of nano-oxide Ti2Nb10O29Preparation method
Technical field
The invention belongs to technical field of nano material, particularly to a kind of nano-oxide Ti2Nb10O29Preparation method.
Background technology
Lithium ion battery has that specific energy is high, has extended cycle life, can fast charging and discharging, efficiency be high and environmental protection etc. is excellent Point, not only has a wide range of applications in small-sized electronic product field, and is the most progressively applied to the field such as power, energy storage.
Negative material is the key factor affecting performance of lithium ion battery, and current commercial Li-ion batteries uses graphite Negative material, exploitation Novel anode material, the performance of raising lithium ion battery have important practical significance.
Niobio compound such as Ti2Nb2O9Have nontoxic, to Li/Li+The oxidation-reduction potential of electrode is the spies such as 1.0-3.0V Point, and each Nb atom can carry out the redox reaction (Nb of 2 electronics5+/Nb3+), each Ti atom can carry out 1 electricity Redox reaction (the Ti of son4+/Ti3+) so that this compounds has the highest lithium storage content.Ti2Nb10O29Theory ratio Capacity is 396mAh g-1, higher than graphite cathode material, and there is constitutionally stable feature, charge-discharge performance is good.
Current commonly used solid phase method prepares oxide Ti2Nb10O29, such as, Toshiki Takashima etc. is with Nb2O5 And TiO2For raw material, by they ball millings, then roasting 24 hours at 1100 DEG C, obtain oxide Ti2Nb10O29, product is rod Strip, length is about 2 μm, at 0.5mA/cm2Under, specific discharge capacity be about 250mAh/g (J.Power Sources, 2015, 276:113-119)；Xiaoyan Wu etc. are with Nb2O5And TiO2For raw material, by them mixing, tabletting, then roast at 1100 DEG C Burn 36 hours, obtain oxide Ti2Nb10O29, product is block, and size is about about 10 μm, and during 0.1C multiplying power discharging, capacity is about For 247mAh/g (Electrochem.Commun.2012,25:39-42)；Wanlin Wang etc. are with Nb2O5And TiO2For raw material, By they ball millings, then roasting 24 hours at 1150 DEG C, obtain oxide Ti2Nb10O29, then be combined with Graphene, product is not Regular shape, for micro-meter scale, under 30mA/g (about 0.12C), specific discharge capacity is about 261mAh/g (J.Power Sources,2015,300:272-278)；Liu Guangyin is with Nb2O5And TiO2For raw material, mix with carbon source, ball milling, at 760-1350 Calcine between DEG C, obtain the Ti for micron grade blocky2Nb10O29/ C composite (patentCN105428619A).Micron order Material is relatively big due to granule, and when carrying out discharge and recharge, lithium ion migration path wherein is long, easily causes capacity and reduces.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of nano-oxide Ti2Nb10O29Preparation method and this oxygen Compound application in lithium ion battery.
The nano-oxide Ti of the present invention2Nb10O29Preparation method, comprise the steps:
Step 1, preparation Nb (OH)5:
(1) in molar ratio, Nb2O5: K2CO3=1:(2.8～3.2) weigh dispensing, ground and mixed is uniform, it is thus achieved that mixture Material；
(2) by mixed material, by room temperature to 950～1150 DEG C, roasting 3～5h；
(3) by the product after roasting, it is dissolved in distilled water, agitated and centrifugation, obtains clear filtrate；To clear filtrate Middle dropping nitric acid, to PH=2～4, filters, it is thus achieved that white precipitate；White precipitate is scrubbed and dry, it is thus achieved that Nb (OH)5；
Step 2, prepares niobium oxalate solution:
(1) in molar ratio, Nb (OH)5: oxalic acid=1:(4.5～5.5) weigh dispensing；
(2) oxalic acid is placed in being completely dissolved in the water-bath of 80～90 DEG C, adds Nb (OH)5, it is stirred continuously, until solution Become clarification, obtain niobium oxalate solution；
Step 3, prepares nano-oxide:
(1) in molar ratio, the titanium elements in butyl titanate: the niobium element=1:(4.5～5.5 in niobium oxalate solution) claim Take dispensing；
(2), after adding ethylene glycol in butyl titanate, niobium oxalate solution is dropwise dripped；Stirring and supersound process mixing are all Even, obtain mixed solution；Wherein, in mass ratio, ethylene glycol: butyl titanate=(10～20): 1；
(3) mixed solution is moved into polytetrafluoroethyllining lining reactor, after 180～210 DEG C of insulations 20～30h, filter Obtain filter cake, by Cake Wash with dry；
(4) by dried filter cake, it is incubated 5～10h at 950～1150 DEG C, obtains nanometer Ti2Nb10O29Powder.
Described step 1 (2), programming rate is 3～5 DEG C/min.
Described step 1 (2), roasting is carried out in Muffle furnace.
Described step 1 (3), the mass concentration of nitric acid is 20～40%.
Described step 1 (3), baking temperature is 50～60 DEG C, and drying time is 4～8h.
In described step 3 (2), add ethylene glycol and prevent tetrabutyl titanate hydrolysis.
In described step 3 (3), the temperature being dried is 80～120 DEG C.
Described step 3 (4), is carried out in Muffle furnace.
Described step 3 (4), programming rate is 3～6 DEG C/min.
The nano-oxide Ti of the present invention2Nb10O29Granule is white rod shape.
The nano-oxide Ti of the present invention2Nb10O29Granular size is 100～400nm.
The nano-oxide Ti of the present invention2Nb10O29Preparation method, the product prepared is nanoscale, as lithium from During sub-cell negative electrode material carries out discharge and recharge, demonstrate good performance.Such as, at 1～3V potential region, 0.1C times Under the conditions of rate (about 35mA/g), it is possible to the capacity of release 350.5mAh/g.
Accompanying drawing explanation
Fig. 1 is nanometer Ti of the embodiment of the present invention 1 preparation2Nb10O29XRD figure spectrum；
Fig. 2 is nanometer Ti of the embodiment of the present invention 1 preparation2Nb10O29SEM image；
Fig. 3 is nanometer Ti of the embodiment of the present invention 1 preparation2Nb10O29Charging and discharging curve under 0.1C multiplying power.
Detailed description of the invention
Embodiment 1
Nano-oxide Ti2Nb10O29Preparation method, comprise the steps:
Step 1, preparation Nb (OH)5:
(1) 5gNb is weighed2O5With 7.8g K2CO3, it is fully ground mix homogeneously, it is thus achieved that mixed material；
(2) mixed material is inserted in Muffle furnace, with the programming rate of 5 DEG C/min by room temperature to 1100 DEG C, roasting 3h；
(3) by the product after roasting, it is dissolved in distilled water, agitated and centrifugation, obtains clear filtrate；To clear filtrate Middle dropping nitric acid, to PH=3, filters, it is thus achieved that white precipitate；White precipitate is scrubbed and dry, it is thus achieved that Nb (OH)5；Wherein, nitre The concentration of acid is 30%；Baking temperature is 55 DEG C, and drying time is 6h.
Step 2, prepares niobium oxalate solution:
(1) Nb (OH) of 5g step 1 preparation is weighed5Standby with 17.7g oxalic acid；
(2) oxalic acid is placed in being completely dissolved in the water-bath of 85 DEG C, adds Nb (OH)5, it is stirred continuously, until solution becomes Clarification, obtains niobium oxalate solution；
Step 3, prepares nano-oxide:
(1) weigh 1.9g butyl titanate, weigh niobium oxalate solution, wherein, the matter of solute niobium oxalate in niobium oxalate solution Amount is 15g；
(2), after adding 30g ethylene glycol in butyl titanate, niobium oxalate solution is dropwise dripped；Stirring and supersound process are mixed Close uniformly, obtain mixed solution；
(3) mixed solution is moved into polytetrafluoroethyllining lining reactor, after 200 DEG C of insulation 25h, filter to obtain filter cake, will Cake Wash is with dry；Wherein, baking temperature is 100 DEG C；
(4) dried filter cake is inserted in Muffle furnace, is warming up to 1050 DEG C of insulation 8h with the programming rate of 5 DEG C/min, Obtain white rod shape nanometer Ti2Nb10O29Powder.
White rod shape nanometer Ti prepared by the present embodiment2Nb10O29Powder, its XRD figure spectrum is as it is shown in figure 1, as can be seen: With the Ti in ICSD data2Nb10O29X-diffraction data basically identical (card number PDF-01-072-0159), shows that product is Ti2Nb10O29.Its SEM image is as in figure 2 it is shown, as can be seen: granular size is 100～400nm.Its filling under 0.1C multiplying power Discharge curve is as it is shown on figure 3, as shown in the figure: Ti2Nb10O29Charging and discharging curve under 0.1C multiplying power, specific discharge capacity is 350.5mAh/g。
Embodiment 2
Nano-oxide Ti2Nb10O29Preparation method, comprise the steps:
Step 1, preparation Nb (OH)5:
(1) 5gNb is weighed2O5With 8.3g K2CO3, it is fully ground mix homogeneously, it is thus achieved that mixed material；
(2) mixed material is inserted in Muffle furnace, with the programming rate of 5 DEG C/min by room temperature to 1150 DEG C, roasting 2.5h；
(3) by the product after roasting, it is dissolved in distilled water, agitated and centrifugation, obtains clear filtrate；To clear filtrate Middle dropping nitric acid, to PH=2.8, filters, it is thus achieved that white precipitate；White precipitate is scrubbed and dry, it is thus achieved that Nb (OH)5；Wherein, The concentration of nitric acid is 40%；Baking temperature is 60 DEG C, and drying time is 4 hours.
Step 2, prepares niobium oxalate solution:
(1) Nb (OH) of 5g step 1 preparation is weighed5Standby with 19.5g oxalic acid；
(2) oxalic acid is placed in being completely dissolved in the water-bath of 85 DEG C, adds Nb (OH)5, it is stirred continuously, until solution becomes Clarification, obtains niobium oxalate solution；
Step 3, prepares nano-oxide:
(1) weigh 1.9g butyl titanate, weigh niobium oxalate solution, wherein, the matter of solute niobium oxalate in niobium oxalate solution Amount is 15g；
(2), after adding 40g ethylene glycol in butyl titanate, niobium oxalate solution is dropwise dripped；Stirring and supersound process are mixed Close uniformly, obtain mixed solution；
(3) mixed solution is moved into polytetrafluoroethyllining lining reactor, after 200 DEG C of insulation 28h, filter to obtain filter cake, will Cake Wash is with dry；Wherein, baking temperature is 120 DEG C；
(4) dried filter cake is inserted in Muffle furnace, is warming up to 1080 DEG C of insulation 7h with the programming rate of 5 DEG C/min, Obtain white rod shape nanometer Ti2Nb10O29Powder.
Embodiment 3
Nano-oxide Ti2Nb10O29Preparation method, comprise the steps:
Step 1, preparation Nb (OH)5:
(1) 5gNb is weighed2O5With 7.3g K2CO3, it is fully ground mix homogeneously, it is thus achieved that mixed material；
(2) mixed material is inserted in Muffle furnace, with the programming rate of 5 DEG C/min by room temperature to 950 DEG C, roasting 5h；
(3) by the product after roasting, it is dissolved in distilled water, agitated and centrifugation, obtains clear filtrate；To clear filtrate Middle dropping nitric acid, to PH=3.5, filters, it is thus achieved that white precipitate；White precipitate is scrubbed and dry, it is thus achieved that Nb (OH)5；Wherein, The concentration of nitric acid is 20%；Baking temperature is 50 DEG C, and drying time is 8 hours.
Step 2, prepares niobium oxalate solution:
(1) Nb (OH) of 5g step 1 preparation is weighed5Standby with 15.9g oxalic acid；
(2) oxalic acid is placed in being completely dissolved in the water-bath of 85 DEG C, adds Nb (OH)5, it is stirred continuously, until solution becomes Clarification, obtains niobium oxalate solution；
Step 3, prepares nano-oxide:
(1) weigh 1.9g butyl titanate, weigh niobium oxalate solution, wherein, the matter of solute niobium oxalate in niobium oxalate solution Amount is 15g；
(2), after adding 20g ethylene glycol in butyl titanate, niobium oxalate solution is dropwise dripped；Stirring and supersound process are mixed Close uniformly, obtain mixed solution；
(3) mixed solution is moved into polytetrafluoroethyllining lining reactor, after 200 DEG C of insulation 30h, filter to obtain filter cake, will Cake Wash is with dry；Wherein, baking temperature is 80 DEG C；
(4) dried filter cake is inserted in Muffle furnace, is warming up to 1000 DEG C of insulation 10h with the programming rate of 5 DEG C/min, Obtain white rod shape nanometer Ti2Nb10O29Powder.

Claims (10)

1. a nano-oxide Ti2Nb10O29Preparation method, it is characterised in that comprise the steps:
Step 1, preparation Nb (OH)5:
(1) in molar ratio, Nb2O5: K2CO3=1:(2.8～3.2) weigh dispensing, ground and mixed is uniform, it is thus achieved that mixed material；(2) By mixed material, by room temperature to 950～1150 DEG C, roasting 3～5h；
(3) by the product after roasting, it is dissolved in distilled water, agitated and centrifugation, obtains clear filtrate；Drip in clear filtrate Add nitric acid to PH=2～4, filtration, it is thus achieved that white precipitate；White precipitate is scrubbed and dry, it is thus achieved that Nb (OH)5；
Step 2, prepares niobium oxalate solution:
(1) in molar ratio, Nb (OH)5: oxalic acid=1:(4.5～5.5) weigh dispensing；
(2) oxalic acid is placed in being completely dissolved in the water-bath of 80～90 DEG C, adds Nb (OH)5, it is stirred continuously, until solution becomes Clarification, obtains niobium oxalate solution；
Step 3, prepares nano-oxide:
(1) in molar ratio, the titanium elements in butyl titanate: the niobium element=1:(4.5～5.5 in niobium oxalate solution) weigh and join Material；
(2), after adding ethylene glycol in butyl titanate, niobium oxalate solution is dropwise dripped；Stirring and supersound process mix homogeneously, Obtain mixed solution；Wherein, in mass ratio, ethylene glycol: butyl titanate=(10～20): 1；
(3) mixed solution is moved into polytetrafluoroethyllining lining reactor, after 180～210 DEG C of insulations 20～30h, filter to obtain filter Cake, by Cake Wash with dry；
(4) by dried filter cake, it is incubated 5～10h at 950～1150 DEG C, obtains nanometer Ti2Nb10O29Powder.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described step 1 (2), programming rate is 3～5 DEG C/min.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described step 1 (2), roasting is carried out in Muffle furnace.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described step 1 (3), the mass concentration of nitric acid is 20～40%；Described step 1 (3), baking temperature is 50～60 DEG C, and drying time is 4～8h.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described step 3 (3), in, the temperature being dried is 80～120 DEG C.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described step 3 (4), carry out in Muffle furnace.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described step 3 (4), programming rate is 3～6 DEG C/min.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described nano oxygen Compound Ti2Nb10O29Granule is white rod shape.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described nano oxygen Compound Ti2Nb10O29Granular size is 100～400nm.
Nano-oxide Ti the most according to claim 12Nb10O29Preparation method, it is characterised in that described method system The Ti obtained2Nb10O29The process of discharge and recharge is carried out, at 1～3V potential region, 0.1C multiplying power bar as lithium ion battery negative material Under part, the capacity of release 350.5mAh/g.
CN201610411168.0A 2016-06-13 2016-06-13 A kind of nano-oxide Ti2Nb10O29Preparation method Expired - Fee Related CN106082338B (en)

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CN105633456A (en) * 2016-04-07 2016-06-01 南阳师范学院 Preparation method of lithium ion battery negative material titanium niobate

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