CN102683665A - Lithium-vanadium oxide over-long nano wire and preparation method and application thereof - Google Patents
Lithium-vanadium oxide over-long nano wire and preparation method and application thereof Download PDFInfo
- Publication number
- CN102683665A CN102683665A CN2012101554369A CN201210155436A CN102683665A CN 102683665 A CN102683665 A CN 102683665A CN 2012101554369 A CN2012101554369 A CN 2012101554369A CN 201210155436 A CN201210155436 A CN 201210155436A CN 102683665 A CN102683665 A CN 102683665A
- Authority
- CN
- China
- Prior art keywords
- lithium
- gained
- solution
- barium oxide
- overlong nanowire
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a lithium-vanadium oxide over-long nano wire and a preparation method thereof. The lithium-vanadium oxide over-long nano wire can be taken as an anode active material for a high-power long-service-life lithium ion battery, is 200-300 microns in length, and is 100-200 nanometers in diameter. The lithium-vanadium oxide over-long nano wire is obtained in a simple calcining way. When the lithium-vanadium oxide over-long nano wire is taken as an anode active material for the lithium ion battery, the discharge capacity can still be up to 120mAh/g after circulating at the current density of 2,000mA/g for 600 times, and the capacity attenuation ratio per time is only 0.022 percent. As proved by a result, the lithium-vanadium oxide over-long nano wire has excellent high magnification characteristic, and is a potential application material for the high-power long-service-life lithium ion battery. In a simple hydro-thermal method adopted for preparing a precursor H2V3O8 over-long nano wire, the shape and size of a material can be controlled by changing the reactant concentration, reaction temperature and time, and the prepared material has high purity and high dispersivity.
Description
Technical field
The invention belongs to nano material and technical field of electrochemistry, be specifically related to a kind of lithium-barium oxide overlong nanowire and preparation method thereof, it can be used as high power extended-life lithium ion battery positive electrode active materials.
Background technology
Lithium ion battery has been widely used in portable equipments such as mobile phone, notebook computer as a kind of green energy resource.Though the energy density of lithium ion battery is higher, lower lithium ion and electrons spread speed cause that its multiplying power property is relatively poor, power density is lower.Multiplying power property is relatively poor to be that the required charging interval of battery is longer, and this limits further developing in its portable equipment; Lower power density has then limited the application of lithium ion battery in hybrid vehicle and pure electric automobile.Therefore, research is one of forward position and focus of current low-carbon economy epoch Study on Li-ion batteries using based on big capacity, high power, long-life, the low-cost lithium ion battery of novel nano electrode material.Nano-material has big draw ratio, high specific area and electronics confinement effect radially and axial electron transport property; During as lithium ion battery electrode material and the electrolyte contact area is big, lithium ion takes off embedding apart from weak point; Can effectively improve the electroactive of material, have significant advantage during as the high power lithium ion cell electrode material.
As typical layered metal oxide; Barium oxide nano material system enjoys attention because of the existence of its multiple oxidation state and coordination polyhedrom makes it have the open architecture that can embed metal ion, and is regarded as potential lithium ion battery material and has obtained long-range development.Lithium-barium oxide is when keeping the barium oxide layer structure, and the lithium ion of its interlayer is through ionic bond and V up and down
3O
8Layer interacts and makes it in cyclic process, keep stable structure.In recent years, though lithium-barium oxide as anode material for lithium-ion batteries by broad research, have than the rarely seen report of the lithium-barium oxide nano wire of high length-diameter ratio.
Summary of the invention
The object of the present invention is to provide a kind of lithium-barium oxide overlong nanowire, it has the good electric chemical property.
Another object of the present invention is to provide the preparation method of the simple lithium-barium oxide overlong nanowire of a kind of technology.
The present invention solves the problems of the technologies described above the technical scheme that is adopted: lithium-barium oxide overlong nanowire, its length reach 200 ~ 300 microns, and diameter is 100 ~ 200 nanometers, adopt following method to make, and include following steps:
1) gets V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, heats and is incubated to molten condition;
2) with step 1) gained fusion V
2O
5Pour quenching in the deionized water at normal temperature rapidly into, gained liquid heat to boiling is not stopped to stir, cooling back suction filtration obtains V with filtrating leaving standstill
2O
5Colloidal sol is demarcated its concentration, and is subsequent use;
3) measure step 2) V of gained 1.1 ~ 1.5 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL V in the deionized water
2O
5Solution is pressed and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.02 ~ 0.06 g and be dissolved in the 15 mL deionized waters, this solution is added in the step 3) gained solution and adds deionized water to overall solution volume is 60 mL;
5) step 4) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, react, from agitated reactor, take out then, naturally cool to room temperature;
6) the product centrifugal filtration that step 5) is obtained with deionized water cyclic washing gained sediment, obtains H after the drying
2V
3O
8Overlong nanowire;
7) take by weighing step 6) gained 0.1 g H
2V
3O
8Nano wire is scattered in the 10 mL absolute ethyl alcohols, and the lithium source that takes by weighing respective amount adds above-mentioned solution, stirred 5 hours, then with mixture in 80 ℃ of air dry ovens, dry hybrid solid;
8) the dried hybrid solid of step 7) gained is transferred to ceramic crucible and places the Muffle furnace sintering, finally obtain product lithium-barium oxide overlong nanowire.
The technical scheme that the preparation method adopted of lithium-barium oxide overlong nanowire is to include following steps:
1) gets V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, heats and is incubated to molten condition;
2) with step 1) gained fusion V
2O
5Pour quenching in the deionized water at normal temperature rapidly into, gained liquid heat to boiling is not stopped to stir, cooling back suction filtration obtains V with filtrating leaving standstill
2O
5Colloidal sol is demarcated its concentration, and is subsequent use;
3) measure step 2) V of gained 1.1 ~ 1.5 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL V in the deionized water
2O
5Solution is pressed and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.02 ~ 0.06 g and be dissolved in the 15 mL deionized waters, this solution is added in the step 3) gained solution and adds deionized water to overall solution volume is 60 mL;
5) step 4) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, react, from agitated reactor, take out then, naturally cool to room temperature;
6) the product centrifugal filtration that step 5) is obtained with deionized water cyclic washing gained sediment, obtains H after the drying
2V
3O
8Overlong nanowire;
7) take by weighing step 6) gained 0.1 g H
2V
3O
8Nano wire is scattered in the 10 mL absolute ethyl alcohols, and the lithium source that takes by weighing respective amount adds above-mentioned solution, stirred 5 hours, then with mixture in 80 ℃ of air dry ovens, dry hybrid solid;
8) the dried hybrid solid of step 7) gained is transferred to ceramic crucible and places the Muffle furnace sintering, finally obtain product lithium-barium oxide overlong nanowire.
Press such scheme, the described reaction temperature of step 5) is 160 ~ 200 ℃; The described reaction time is 36 ~ 60 hours;
Press such scheme, described lithium source is lithium hydroxide, lithium carbonate or lithium acetate, and wherein lithium/vanadium mol ratio is 1.05 ~ 1.25:3.
Press such scheme, the described sintering temperature of step 8) is 400 ~ 500 ℃; Described sintering time is 5 ~ 15 hours.
The lithium-barium oxide overlong nanowire is in the application aspect anode active material of lithium ion battery.
The invention has the beneficial effects as follows: selection of the present invention and lithium-barium oxide have the H of similar layer structure
2V
3O
8Overlong nanowire through simple calcining, obtains the lithium-barium oxide overlong nanowire as presoma.During as anode active material of lithium ion battery, under the current density of 2000 mA/g, circulate that discharge capacity still can reach 120 mAh/g after 600 times, each capacity attenuation rate is merely 0.022 %.This result shows that the lithium-barium oxide overlong nanowire has excellent high magnification characteristic, is the potential Material Used of high power, extended-life lithium ion battery.
In addition, preparation presoma H
2V
3O
8The simple hydro thermal method that overlong nanowire adopted can be passed through to change pattern and the size that reactant concentration, reaction temperature and time get final product control material, and the material purity that makes is high, good dispersion.And the simple calcination method technology that preparation lithium-barium oxide overlong nanowire is adopted is simple, low for equipment requirements, is very beneficial for the marketization and promotes.
Description of drawings
Fig. 1 is the lithium-barium oxide Li of embodiment 1
(1+x)V
3O
8(x=0) XRD figure of overlong nanowire;
Fig. 2 is the lithium-barium oxide Li of embodiment 1
(1+x)V
3O
8(x=0) the low multiplication factor FESEM figure of overlong nanowire;
Fig. 3 is the lithium-barium oxide Li of embodiment 1
(1+x)V
3O
8(x=0) overlong nanowire and presoma H
2V
3O
8The FESEM figure of nano wire; Wherein, Fig. 3 (a) is presoma H
2V
3O
8The FESEM figure of nano wire, Fig. 3 (b) is Li
(1+x)V
3O
8(x=0) FESEM of overlong nanowire figure;
Fig. 4 is the lithium-barium oxide Li of embodiment 1
(1+x)V
3O
8(x=0) TEM of overlong nanowire figure;
Fig. 5 is the lithium-barium oxide Li of embodiment 1
(1+x)V
3O
8(x=0) the cycle performance of battery curve chart of overlong nanowire.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
Embodiment 1:
Lithium-barium oxide Li
(1+x)V
3O
8(x=0) preparation method of overlong nanowire, it comprises the steps:
1) takes by weighing 20 g V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, is warming up to 800 ℃, is incubated 0.5 hour and makes its abundant fusion;
2) with fusion V
2O
5Pour quenching in the 2 L deionized water at normal temperature rapidly into, the rufous liquid that obtains is heated to boiling did not stop to stir 1 hour on electric furnace, cooling back suction filtration is removed residual solids three times, filtrating is left standstill obtained stable peony V in seven days
2O
5Colloidal sol is got three parts in 10 mL colloidal sol samples, takes by weighing quality after the oven dry respectively and calculates collosol concentration, and averaging is V
2O
5Collosol concentration, subsequent use;
3) measure the V of 1.3 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL solution in the deionized water, by and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.04 g and be dissolved in the 15 mL deionized waters, this solution adding is gone up step 3) gained solution and added deionized water to overall solution volume is 60 mL;
5) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, reaction is 48 hours under 180 ℃ of conditions, takes out agitated reactor, naturally cools to room temperature;
6) with the product centrifugal filtration that obtains, with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, obtain H
2V
3O
8(be also referred to as V
3O
7H
2O) overlong nanowire;
7) take by weighing 0.1 g H
2V
3O
8Nano wire is scattered in 10 mL absolute ethyl alcohols, is that the lithium hydroxide that the ratio of 1.05:3 takes by weighing respective amount adds above-mentioned solution with lithium/vanadium mol ratio, stirs 5 hours, then mixture is dried in 80 ℃ of air dry ovens;
8) dried hybrid solid is transferred to ceramic crucible and places Muffle furnace,, finally obtain lithium-barium oxide overlong nanowire (product) 450 ℃ of following sintering 10 hours.
With the embodiment of the invention 1 products therefrom lithium-barium oxide overlong nanowire is example, and its structure is confirmed by x-ray diffractometer.As shown in Figure 1, the lithium-barium oxide overlong nanowire is LiV basically
3O
8Phase (JCPDS card number be 01-072-1193), the dephasign that contains trace is Li
0.3V
2O
5As shown in Figure 2, the lithium-barium oxide overlong nanowire has kept presoma H basically
2V
3O
8The pattern of nano wire, length can reach 300 microns, and Fig. 3 shows that the diameter of nano wire is 100 ~ 200 nanometers.Fig. 4 is transmission electron microscope (TEM) and SEAD (SAED) test result, shows that this nano wire has tangible mono-crystalline structures, and the direction of growth is < 001>direction.
The lithium-barium oxide overlong nanowire of the present invention's preparation is as anode active material of lithium ion battery, and all the other steps of the preparation method of lithium ion battery are identical with common preparation method.The preparation method of positive plate is following, adopts the lithium-barium oxide overlong nanowire as active material, and acetylene black is as conductive agent, and polytetrafluoroethylene is as binding agent, and the mass ratio of active material, acetylene black, polytetrafluoroethylene is 70:20:10; After their abundant in proportion mixing, add a small amount of isopropyl alcohol, grind evenly, on twin rollers, press the thick electrode slice of about 0.5 mm; The positive plate that presses places 80 ℃ oven drying subsequent use after 24 hours.LiPF with 1 M
6Be dissolved in vinyl carbonate (EC) and the dimethyl carbonate (DMC) as electrolyte, the lithium sheet is a negative pole, and Celgard 2325 is a barrier film, and CR 2025 type stainless steels are that battery case is assembled into the buckle type lithium-ion battery.
As shown in Figure 5, be example with the lithium-barium oxide overlong nanowire, under the current density of 1500 mA/g, this nano wire discharge capacity after circulation 400 times can reach 160 mAh/g, and each capacity attenuation rate is merely 0.025 %.Under the current density of 2000 mA/g, circulate that discharge capacity still reaches 120 mAh/g after 600 times, each capacity attenuation rate is merely 0.022 %.This result shows that the lithium-barium oxide overlong nanowire has excellent high magnification characteristic, is the potential Material Used of high power, extended-life lithium ion battery.
Embodiment 2:
Lithium-barium oxide Li
(1+x)V
3O
8(x=0.1) preparation method of overlong nanowire, it comprises the steps:
1) takes by weighing 20 g V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, is warming up to 800 ℃, is incubated 0.5 hour and makes its abundant fusion;
2) with fusion V
2O
5Pour quenching in the 2 L deionized water at normal temperature rapidly into, the rufous liquid that obtains is heated to boiling did not stop to stir 1 hour on electric furnace, cooling back suction filtration is removed residual solids three times, filtrating is left standstill obtained stable peony V in seven days
2O
5Colloidal sol is got three parts in 10 mL colloidal sol samples, takes by weighing quality after the oven dry respectively and calculates collosol concentration, and averaging is V
2O
5Collosol concentration, subsequent use;
3) measure the V of 1.5 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL solution in the deionized water, by and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.06 g and be dissolved in the 15 mL deionized waters, this solution adding is gone up step 3) gained solution and added deionized water to overall solution volume is 60 mL;
5) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, reaction is 48 hours under 180 ℃ of conditions, takes out agitated reactor, naturally cools to room temperature;
6) with the product centrifugal filtration that obtains, with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, obtain H
2V
3O
8(be also referred to as V
3O
7H
2O) overlong nanowire;
7) take by weighing 0.1 g H
2V
3O
8Nano wire is scattered in 10 mL absolute ethyl alcohols, is that the lithium carbonate that the ratio of 1.15:3 takes by weighing respective amount adds above-mentioned solution with lithium/vanadium mol ratio, stirs 5 hours, then mixture is dried in 80 ℃ of air dry ovens;
8) dried hybrid solid is transferred to ceramic crucible and places Muffle furnace,, finally obtain lithium-barium oxide Li 450 ℃ of following sintering 5 hours
(1+x)V
3O
8(x=0.1) overlong nanowire (product).
This instance gained lithium-barium oxide overlong nanowire length can reach about 250 microns, and diameter is 100 ~ 200 nanometers.Under the current density of 1500 mA/g, this nano wire discharge capacity after circulation 400 times is 147 mAh/g, and each capacity attenuation rate is 0.032 %.Under the current density of 2000 mA/g, circulate that discharge capacity is 112 mAh/g after 600 times, each capacity attenuation rate is 0.027 %.
Embodiment 3:
Lithium-barium oxide Li
(1+x)V
3O
8(x=0.2) preparation method of overlong nanowire, it comprises the steps:
1) takes by weighing 20 g V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, is warming up to 800 ℃, is incubated 0.5 hour and makes its abundant fusion;
2) with fusion V
2O
5Pour quenching in the 2 L deionized water at normal temperature rapidly into, the rufous liquid that obtains is heated to boiling did not stop to stir 1 hour on electric furnace, cooling back suction filtration is removed residual solids three times, filtrating is left standstill obtained stable peony V in seven days
2O
5Colloidal sol is got three parts in 10 mL colloidal sol samples, takes by weighing quality after the oven dry respectively and calculates collosol concentration, and averaging is V
2O
5Collosol concentration, subsequent use;
3) measure the V of 1.1 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL solution in the deionized water, by and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.02 g and be dissolved in the 15 mL deionized waters, this solution adding is gone up step 3) gained solution and added deionized water to overall solution volume is 60 mL;
5) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, reaction is 36 hours under 200 ℃ of conditions, takes out agitated reactor, naturally cools to room temperature;
6) with the product centrifugal filtration that obtains, with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, obtain H
2V
3O
8(be also referred to as V
3O
7H
2O) overlong nanowire;
7) take by weighing 0.1 g H
2V
3O
8Nano wire is scattered in 10 mL absolute ethyl alcohols, is that the lithium acetate that the ratio of 1.25:3 takes by weighing respective amount adds above-mentioned solution with lithium/vanadium mol ratio, stirs 5 hours, then mixture is dried in 80 ℃ of air dry ovens;
8) dried hybrid solid is transferred to ceramic crucible and places Muffle furnace,, finally obtain Li 400 ℃ of following sintering 15 hours
(1+x)V
3O
8(x=0.2) overlong nanowire (product).
This instance gained lithium-barium oxide overlong nanowire length can reach about 280 microns, and diameter is 150 ~ 200 nanometers.Under the current density of 1500 mA/g, this nano wire discharge capacity after circulation 400 times is 151 mAh/g, and each capacity attenuation rate is 0.030 %.Under the current density of 2000 mA/g, circulate that discharge capacity is 114 mAh/g after 600 times, each capacity attenuation rate is 0.025 %.
Embodiment 4:
Lithium-barium oxide Li
(1+x)V
3O
8(x=0) preparation method of overlong nanowire, it comprises the steps:
1) takes by weighing 20 g V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, is warming up to 800 ℃, is incubated 0.5 hour and makes its abundant fusion;
2) with fusion V
2O
5Pour quenching in the 2 L deionized water at normal temperature rapidly into, the rufous liquid that obtains is heated to boiling did not stop to stir 1 hour on electric furnace, cooling back suction filtration is removed residual solids three times, filtrating is left standstill obtained stable peony V in seven days
2O
5Colloidal sol is got three parts in 10 mL colloidal sol samples, takes by weighing quality after the oven dry respectively and calculates collosol concentration, and averaging is V
2O
5Collosol concentration, subsequent use;
3) measure the V of 1.3 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL solution in the deionized water, by and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.04 g and be dissolved in the 15 mL deionized waters, this solution adding is gone up step 3) gained solution and added deionized water to overall solution volume is 60 mL;
5) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, reaction is 60 hours under 160 ℃ of conditions, takes out agitated reactor, naturally cools to room temperature;
6) with the product centrifugal filtration that obtains, with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, obtain H
2V
3O
8(be also referred to as V
3O
7H
2O) overlong nanowire;
7) take by weighing 0.1 g H
2V
3O
8Nano wire is scattered in 10 mL absolute ethyl alcohols, is that the lithium hydroxide that the ratio of 1.05:3 takes by weighing respective amount adds above-mentioned solution with lithium/vanadium mol ratio, stirs 5 hours, then mixture is dried in 80 ℃ of air dry ovens;
8) dried hybrid solid is transferred to ceramic crucible and places Muffle furnace,, finally obtain Li 500 ℃ of following sintering 5 hours
(1+x)V
3O
8(x=0) overlong nanowire (product).
This instance gained lithium-barium oxide overlong nanowire length can reach about 300 microns, and diameter is 100 ~ 200 nanometers.Under the current density of 1500 mA/g, this nano wire discharge capacity after circulation 400 times is 155 mAh/g, and each capacity attenuation rate is 0.027 %.Under the current density of 2000 mA/g, circulate that discharge capacity is 116 mAh/g after 600 times, each capacity attenuation rate is 0.023 %.
Embodiment 5:
Lithium-barium oxide Li
(1+x)V
3O
8(x=0.2) preparation method of overlong nanowire, it comprises the steps:
1) takes by weighing 20 g V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, is warming up to 800 ℃, is incubated 0.5 hour and makes its abundant fusion;
2) with fusion V
2O
5Pour quenching in the 2 L deionized water at normal temperature rapidly into, the rufous liquid that obtains is heated to boiling did not stop to stir 1 hour on electric furnace, cooling back suction filtration is removed residual solids three times, filtrating is left standstill obtained stable peony V in seven days
2O
5Colloidal sol is got three parts in 10 mL colloidal sol samples, takes by weighing quality after the oven dry respectively and calculates collosol concentration, and averaging is V
2O
5Collosol concentration, subsequent use;
3) measure the V of 1.3 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL solution in the deionized water, by and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.04 g and be dissolved in the 15 mL deionized waters, this solution adding is gone up step 3) gained solution and added deionized water to overall solution volume is 60 mL;
5) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, reaction is 48 hours under 180 ℃ of conditions, takes out agitated reactor, naturally cools to room temperature;
6) with the product centrifugal filtration that obtains, with deionized water cyclic washing gained sediment, in 80 ℃ of baking ovens, dry, obtain H
2V
3O
8(be also referred to as V
3O
7H
2O) overlong nanowire;
7) take by weighing 0.1 g H
2V
3O
8Nano wire is scattered in 10 mL absolute ethyl alcohols, is that the lithium hydroxide that the ratio of 1.25:3 takes by weighing respective amount adds above-mentioned solution with lithium/vanadium mol ratio, stirs 5 hours, then mixture is dried in 80 ℃ of air dry ovens;
8) dried hybrid solid is transferred to ceramic crucible and places Muffle furnace,, finally obtain Li 400 ℃ of following sintering 15 hours
(1+x)V
3O
8(x=0.2) overlong nanowire (product).
This instance gained lithium-barium oxide overlong nanowire length can reach about 300 microns, and diameter is 100 ~ 200 nanometers.Under the current density of 1500 mA/g, this nano wire discharge capacity after circulation 400 times is 135 mAh/g, and each capacity attenuation rate is 0.038 %.Under the current density of 2000 mA/g, circulate that discharge capacity is 108 mAh/g after 600 times, each capacity attenuation rate is 0.033 %.
Claims (9)
1. lithium-barium oxide overlong nanowire, its chemical formula is Li
(1+x)V
3O
8, 0≤x≤0.2 wherein, its length reaches 200 ~ 300 microns, and diameter is 100 ~ 200 nanometers, adopts following method to make, and includes following steps:
1) gets V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, heats and is incubated to molten condition;
2) with step 1) gained fusion V
2O
5Pour quenching in the deionized water at normal temperature rapidly into, gained liquid heat to boiling is not stopped to stir, cooling back suction filtration obtains V with filtrating leaving standstill
2O
5Colloidal sol is demarcated its concentration, and is subsequent use;
3) measure step 2) V of gained 1.1 ~ 1.5 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL V in the deionized water
2O
5Solution is pressed and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.02 ~ 0.06 g and be dissolved in the 15 mL deionized waters, this solution is added in the step 3) gained solution and adds deionized water to overall solution volume is 60 mL;
5) step 4) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, react, from agitated reactor, take out then, naturally cool to room temperature;
6) the product centrifugal filtration that step 5) is obtained with deionized water cyclic washing gained sediment, obtains H after the drying
2V
3O
8Overlong nanowire;
7) take by weighing step 6) gained 0.1 g H
2V
3O
8Nano wire is scattered in the 10 mL absolute ethyl alcohols, and the lithium source that takes by weighing respective amount adds above-mentioned solution, stirred 5 hours, then with mixture in 80 ℃ of air dry ovens, dry hybrid solid;
8) the dried hybrid solid of step 7) gained is transferred to ceramic crucible and places the Muffle furnace sintering, finally obtain product lithium-barium oxide overlong nanowire.
2. lithium-barium oxide overlong nanowire as claimed in claim 1 is characterized in that the described reaction temperature of step 5) is 160 ~ 200 ℃; The described reaction time is 36 ~ 60 hours.
3. lithium-barium oxide overlong nanowire as claimed in claim 1 is characterized in that described lithium source is lithium hydroxide, lithium carbonate or lithium acetate, and wherein lithium/vanadium mol ratio is 1.05 ~ 1.25:3.
4. lithium-barium oxide overlong nanowire as claimed in claim 1 is characterized in that the described sintering temperature of step 8) is 400 ~ 500 ℃; Described sintering time is 5 ~ 15 hours.
5. the preparation method of the described lithium-barium oxide overlong nanowire of claim 1 is characterized in that including following steps:
1) gets V
2O
5Powder is put into ceramic crucible and is placed Muffle furnace, heats and is incubated to molten condition;
2) with step 1) gained fusion V
2O
5Pour quenching in the deionized water at normal temperature rapidly into, gained liquid heat to boiling is not stopped to stir, cooling back suction filtration obtains V with filtrating leaving standstill
2O
5Colloidal sol is demarcated its concentration, and is subsequent use;
3) measure step 2) V of gained 1.1 ~ 1.5 mmol
2O
5Colloidal sol also is diluted in and obtains 40 mL V in the deionized water
2O
5Solution is pressed and V
2O
5Amount of substance splashes into V than the aniline solution of measuring 0.05 mol/L for 0.03:1
2O
5Solution stirred 0.5 hour;
4) take by weighing PEG-4000 0.02 ~ 0.06 g and be dissolved in the 15 mL deionized waters, this solution is added in the step 3) gained solution and adds deionized water to overall solution volume is 60 mL;
5) step 4) gained solution continue was stirred one day and ageing at room temperature a day, change over to then in the 100 mL agitated reactors, react, from agitated reactor, take out then, naturally cool to room temperature;
6) the product centrifugal filtration that step 5) is obtained with deionized water cyclic washing gained sediment, obtains H after the drying
2V
3O
8Overlong nanowire;
7) take by weighing step 6) gained 0.1 g H
2V
3O
8Nano wire is scattered in the 10 mL absolute ethyl alcohols, and the lithium source that takes by weighing respective amount adds above-mentioned solution, stirred 5 hours, then with mixture in 80 ℃ of air dry ovens, dry hybrid solid;
8) the dried hybrid solid of step 7) gained is transferred to ceramic crucible and places the Muffle furnace sintering, finally obtain product lithium-barium oxide overlong nanowire.
6. the preparation method of lithium-barium oxide overlong nanowire as claimed in claim 5 is characterized in that the described reaction temperature of step 5) is 160 ~ 200 ℃; The described reaction time is 36 ~ 60 hours.
7. the preparation method of lithium-barium oxide overlong nanowire as claimed in claim 5 is characterized in that, described lithium source is lithium hydroxide, lithium carbonate or lithium acetate, and wherein lithium/vanadium mol ratio is 1.05 ~ 1.25:3.
8. the preparation method of lithium-barium oxide overlong nanowire as claimed in claim 5 is characterized in that the described sintering temperature of step 8) is 400 ~ 500 ℃; Described sintering time is 5 ~ 15 hours.
9. the described lithium-barium oxide overlong nanowire of claim 1 is in the application aspect anode active material of lithium ion battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210155436.9A CN102683665B (en) | 2012-05-18 | 2012-05-18 | Lithium-vanadium oxide over-long nano wire and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210155436.9A CN102683665B (en) | 2012-05-18 | 2012-05-18 | Lithium-vanadium oxide over-long nano wire and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102683665A true CN102683665A (en) | 2012-09-19 |
| CN102683665B CN102683665B (en) | 2014-05-14 |
Family
ID=46815276
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210155436.9A Active CN102683665B (en) | 2012-05-18 | 2012-05-18 | Lithium-vanadium oxide over-long nano wire and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102683665B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103094541A (en) * | 2013-01-16 | 2013-05-08 | 武汉理工大学 | MnO2-loaded V2O5/polymer coaxial structure nanowires as well as preparation method and application thereof |
| CN103208619A (en) * | 2013-03-13 | 2013-07-17 | 武汉理工大学 | Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof |
| CN103700826A (en) * | 2013-12-26 | 2014-04-02 | 武汉理工大学 | Pre-lithiated ultrathin V6O13 nanosheet as well as preparation method and application thereof |
| CN103887480A (en) * | 2012-12-21 | 2014-06-25 | 巴莱诺斯清洁能源控股公司 | Self-assembled Composite Of Graphene Oxide And Tetravalent Vanadium Oxohydroxide |
| CN104466178A (en) * | 2014-12-05 | 2015-03-25 | 武汉理工大学 | Hierarchical mesoporous sodium vanadate bent nanowire as well as preparation method and application thereof |
| CN105680042A (en) * | 2016-01-23 | 2016-06-15 | 武汉理工大学 | Calcium vanadate mesoporous nanowire and preparation method and application thereof |
| CN105731539A (en) * | 2016-02-02 | 2016-07-06 | 山东大学 | Method for synthesizing lithium vanadate Li3VO4 monocrystal micrometer powder with high-temperature and high-pressure mixed solvent thermal system |
| CN114628682A (en) * | 2022-03-22 | 2022-06-14 | 武汉理工大学 | Low-temperature-resistant metal nanowire composite electrode slice and preparation method thereof |
-
2012
- 2012-05-18 CN CN201210155436.9A patent/CN102683665B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| 《J Mater Sci》 20070110 Xiaohong Liu et.al Sol-gel template synthesis of LiV3O8 nanowires 867-871 1-9 第42卷, * |
| XIAOHONG LIU ET.AL: "Sol–gel template synthesis of LiV3O8 nanowires", 《J MATER SCI》 * |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103887480A (en) * | 2012-12-21 | 2014-06-25 | 巴莱诺斯清洁能源控股公司 | Self-assembled Composite Of Graphene Oxide And Tetravalent Vanadium Oxohydroxide |
| CN103887480B (en) * | 2012-12-21 | 2017-01-04 | 巴莱诺斯清洁能源控股公司 | Graphene oxide and the self-assembled compound material of tetravalence vanadium oxyhydroxide |
| CN103094541A (en) * | 2013-01-16 | 2013-05-08 | 武汉理工大学 | MnO2-loaded V2O5/polymer coaxial structure nanowires as well as preparation method and application thereof |
| CN103208619A (en) * | 2013-03-13 | 2013-07-17 | 武汉理工大学 | Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof |
| CN103208619B (en) * | 2013-03-13 | 2015-02-04 | 武汉理工大学 | Potassium ion embedded type vanadium pentoxide nanowire and preparation method thereof and application thereof |
| CN103700826A (en) * | 2013-12-26 | 2014-04-02 | 武汉理工大学 | Pre-lithiated ultrathin V6O13 nanosheet as well as preparation method and application thereof |
| CN103700826B (en) * | 2013-12-26 | 2015-09-30 | 武汉理工大学 | Ultra-thin prelithiation V 6o 13nanometer sheet and its preparation method and application |
| CN104466178A (en) * | 2014-12-05 | 2015-03-25 | 武汉理工大学 | Hierarchical mesoporous sodium vanadate bent nanowire as well as preparation method and application thereof |
| CN105680042A (en) * | 2016-01-23 | 2016-06-15 | 武汉理工大学 | Calcium vanadate mesoporous nanowire and preparation method and application thereof |
| CN105680042B (en) * | 2016-01-23 | 2017-12-05 | 武汉理工大学 | Calcium vanadate meso-porous nano line and its preparation method and application |
| CN105731539A (en) * | 2016-02-02 | 2016-07-06 | 山东大学 | Method for synthesizing lithium vanadate Li3VO4 monocrystal micrometer powder with high-temperature and high-pressure mixed solvent thermal system |
| CN114628682A (en) * | 2022-03-22 | 2022-06-14 | 武汉理工大学 | Low-temperature-resistant metal nanowire composite electrode slice and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102683665B (en) | 2014-05-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102683665B (en) | Lithium-vanadium oxide over-long nano wire and preparation method and application thereof | |
| Zhang et al. | An overview of modification strategies to improve LiNi0· 8Co0· 1Mn0· 1O2 (NCM811) cathode performance for automotive lithium-ion batteries | |
| CN107403913B (en) | Surface-modified nickel-cobalt lithium aluminate cathode material and preparation method thereof | |
| CN105006561B (en) | A kind of barium oxide ultrathin nanometer band of ion insertion and its preparation method and application | |
| CN105938899B (en) | A kind of preparation method and application of fast-ionic conductor coating modification anode material for lithium-ion batteries | |
| CN105932250B (en) | A kind of metal-doped spinel structure fast-ionic conductor coats the preparation method and application of nickeliferous positive electrode | |
| CN105070888A (en) | Coupled carbon nano tube-graphene composite three-dimensional network structure-coated ternary material and preparation method thereof | |
| CN101420034A (en) | Carbon coated granularity controllable spherical lithium ferric phosphate composite positive pole material and preparation method thereof | |
| CN101826617B (en) | Preparation method of lithium iron phosphate | |
| CN109873140B (en) | Graphene composite ternary cathode material of lithium ion battery and preparation method of graphene composite ternary cathode material | |
| CN106356509A (en) | Cobaltosic oxide coated and modified nickel-doped lithium manganate and preparation method thereof | |
| CN103151528A (en) | Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material | |
| CN106025208A (en) | Preparation method for carbon-coated ternary positive electrode material | |
| CN105789606A (en) | Preparation method of lithium titanate coated lithium ion battery nickel cobalt manganese cathode material | |
| CN103151506A (en) | Preparation method of nanoscale zirconium-doped lithium titanate material | |
| CN102208647A (en) | Lithium ferrous silicate anode material coated with crystalline carbon and preparation method thereof | |
| Wen et al. | Design and preparation of spherical high voltage LiNi0. 5Mn1. 5O4 with a novel concentration-gradient shell for lithium ion batteries | |
| CN110444740A (en) | A method of the small scale nanometer composite material of synthesizing graphite alkene/carbon-coated LiFePO 4 for lithium ion batteries is acted on by aniline polymerization confinement | |
| CN102412400A (en) | Silver vanadium oxide / polymer three coaxial nanowire and preparation method and application thereof | |
| CN102479945A (en) | Preparation method of spherical lithium iron phosphate cathode material | |
| CN102832381A (en) | Preparation method of high-voltage cathode material Lil+xMn3/2-yNil/2-zMy+zO4 of lithium ion battery with long service life | |
| CN104466139A (en) | Preparation method of polyaniline-clad germanium-doped lithium manganate composite cathode material | |
| CN103117379B (en) | B-phase vanadium dioxide self-buffering hybrid nano-material as well as preparation method and application thereof | |
| CN105895890A (en) | Application of Sn3O4 solar catalyst in negative electrode material of lithium ion battery | |
| CN107180965B (en) | A kind of nano-scale lithium iron phosphate/graphene composite material and its preparation method and application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |