CN106410117A - Rod-like NiTiO3 negative electrode material used for sodium ion battery as well as preparation and application - Google Patents
Rod-like NiTiO3 negative electrode material used for sodium ion battery as well as preparation and application Download PDFInfo
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- CN106410117A CN106410117A CN201610981511.5A CN201610981511A CN106410117A CN 106410117 A CN106410117 A CN 106410117A CN 201610981511 A CN201610981511 A CN 201610981511A CN 106410117 A CN106410117 A CN 106410117A
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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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- 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
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Abstract
The invention relates to a rod-like NiTiO3 negative electrode material used for a sodium ion battery as well as preparation and application and discloses a preparation method and application of a high-purity rod-like NiTiO3 material. The preparation method comprises the following steps: dissolving an inorganic nickel source into an organic solvent; sufficiently mixing to obtain a nickel-containing clarified solution; adding a titanium source and stirring for 0.2h to 20h; washing sediment, obtained by reaction, with the organic solvent; then filtering and drying; finally, calcining at 400 DEG C to 1000 DEG C to obtain the NiTiO3 material. The obtained NiTiO3 material is of a rod-like structure with good purity and good dispersion. The material is directly used as the negative electrode material of the sodium ion battery and has good electrochemical performance; the preparation method is simple, has good repeatability and low cost and has a wide industrialized application prospect.
Description
Technical field
The present invention relates to anode material of lithium-ion battery preparation field is and in particular to a kind of NiTiO3Material and its preparation side
Method and application.
Background technology
Lithium ion battery, as a kind of electrochemical energy storing device occupying social leading position, produces in portable electronic
Achieve in product (notebook computer, intelligent mobile is equipped, panel computer etc.), electric automobile and instant-plugging hybrid-power electric vehicle
Good application.Meanwhile, sodium-ion battery due to sodium resource reserves enrich, environmental friendliness also receive extensive concern, sodium from
The research and development of sub- battery can relax to a certain extent because lithium resource shortage cause battery development limitation problem it is considered to be
Electric powered motor power supply of future generation and the ideal chose of extensive energy-accumulating power station outfit power supply.
In tens years in past, researcher the positive electrode of sodium-ion battery has been carried out widely studied, but
Research to anode material of lithium-ion battery is still at an early stage.In existing negative material system, material with carbon element has good
Good cyclical stability, but its specific discharge capacity relatively low (less than 300mAh g-1) it is impossible to meet height ratio capacity sodium-ion battery business
The requirement of industryization application.Transition metal oxide, sulfide and selenides theoretical specific capacity are higher, but it is higher to there is discharge platform
The shortcoming of (generally higher than 1V).Therefore find the negative material that a kind of reversible capacity is high, discharge platform is low very urgent.Recently big
Quantity research result shows, titanate system material has higher theoretical specific capacity in sodium-ion battery, and nickel titanate due to
Synthesis technique is simple, the relatively low extensive concern even more causing scientist of discharge platform.However, due to metatitanic acid nickel material originally
Body electric conductivity is poor, so leading to the circulation volume of this material can gradually decay.Meanwhile, granule is several or tens nm nanoparticles
Son is easily reunited, poor processability, and chemical property decay is serious.Study suitable preparation method, the titanium of synthesis specific morphology
Sour nickel material, plays its good chemical property, becomes the key of its application.
Content of the invention
Present invention aims to the deficiencies in the prior art, there is provided a kind of structural advantage discord using itself is appointed
What Material cladding, just can accelerate the transfer rate of ion-electron, suppress the reunion in charge and discharge process simultaneously, thus improving sodium
The bar-shaped NiTiO of ion battery cycle performance3Negative material.
Another object of the present invention is to providing a kind of process is simple, reproducible, workable, low cost, favourable
NiTiO in industrialization large-scale production3Negative material (also referred to as NiTiO3Material or NiTiO3) method.
Another object of the present invention is to providing one kind to be applied in sodium-ion battery to have high charge-discharge specific capacity, good
High rate performance and stable circulation performance, low-voltage platform containing above-mentioned bar-shaped NiTiO3Negative material sodium-ion battery bear
Pole.
The purpose of the present invention is achieved through the following technical solutions：
A kind of NiTiO for sodium-ion battery3Negative material, described NiTiO3Negative material is rendered as club shaped structure.
Preferably, described NiTiO3A diameter of 100～400nm of negative material, length is 500～3000nm.
Present invention also offers a kind of described NiTiO3The preparation method of negative material, by nickel source dispersion and/or dissolving
In a solvent, obtain nickel solution；Add titanium source stirring reaction again, subsequently again to the product washing of reaction, be dried, calcining be obtained described
NiTiO3Negative material；Described solvent is the alcoholic solution of more than binary.
In the present invention, first nickel source disperseed, be dissolved in described solvent, subsequently add titanium source stirring reaction, reactant
Titanium source in system and nickel source are self-assembled into presoma under described dicyandiamide solution, by stirring reaction solid and liquid separate (for example from
The heart or filtration), wash, be dried to obtain presoma；Subsequently presoma is carried out calcination processing, obtain described there is good electrical
The bar-shaped NiTiO of performance3Negative material.
Preferably, described nickel source is water miscible nickel compound and its hydrate.Well known to those skilled in the art
The inorganic nickel compound of water-soluble and its hydrate can be employed as nickel source.
Preferably, described nickel source is nickel acetate, the nickel acetate with water of crystallization, anhydrous nitric acid nickel, the nitre with water of crystallization
Sour nickel, Nickel dichloride., at least one of the Nickel dichloride. with water of crystallization.
Further preferably, described nickel source is at least one of Glacial acetic acid nickel or the nickel acetate with water of crystallization.
Preferably, described nickel source is four water acetic acid nickel.
In the present invention, in advance described nickel source is dissolved, so that the nickel solution of clarification is obtained, had for being obtained further
The NiTiO of homogeneous Rod-like shape3Negative material, described solvent is preferably the binary containing molecular weight not higher than 1200 and many
The alcoholic solution of unit.
Further preferably, described solvent be glycerol, ethylene glycol, at least one in Polyethylene Glycol.
Preferably, the relative molecular mass of described Polyethylene Glycol is less than or equal to 1200.Further preferably, described
Solvent is preferably the binary of molecular weight not higher than 150 and polynary alcoholic solution.
Most preferably, described solvent is ethylene glycol.
Preferably, in described nickel solution, Ni2+Concentration be 0.10～0.3mol/L；More preferably 0.10～
0.25mol/L；Most preferably 0.10～0.15mol/L.
In the present invention, described titanium source can be had using the titanium that may be dissolved in alcoholic solution well-known to those skilled in the art
Machine compound.Preferably, described titanium source is butyl titanate, tetraethyl titanate, at least one of isopropyl titanate；Enter one
Step is preferably butyl titanate.
In the present invention, the Ti of titanium source4+Ni with nickel source2+Mol ratio be 1: 1.
After adding titanium source, the time of stirring reaction is 0.2～20h, more preferably 1～12h；Most preferably 8～10h.
In the present invention, preferably, the solvent that washing process adopts be ethanol, ethylene glycol, in Polyethylene Glycol at least one
Kind.
Further preferably, the solvent that washing adopts is identical with reaction dissolvent (dissolving the solvent of titanium source)；For example all preferred
For ethylene glycol.
In the present invention, the presoma being obtained is carried out calcination processing, preferably, calcining heat is 400～1000 DEG C；Enter
One step is preferably 500～800 DEG C；Most preferably 600～700 DEG C.
Under described preferred calcining heat, preferred calcination time is 0.5～12h；More preferably 1～4h.
Further preferably, in calcination process, calcining heat is 500～800 DEG C, temperature retention time 1～3h.
Most preferably, in calcination process, calcining heat is 600～700 DEG C, temperature retention time 1～2h.
In the present invention, a kind of preferred NiTiO3The preparation method of material, comprises the following steps：
Step (1)：By nickel acetate or its hydrate dissolution in ethylene glycol, be sufficiently stirred for, obtain clarify concentration (with
Ni2+Meter) be 0.1～0.3mol/L nickel solution, then according to nickel/titanium mol ratio be 1: 1 ratio add butyl titanate, stir
Mix 0.2～20h, the washing of gained sediment spent glycol will be reacted, then filter, dry presoma；
Step (2)：The presoma that step (1) is obtained calcines 0.5～12h at 400～1000 DEG C；Obtain NiTiO3Material
Material.
Preferably, in step (1), in described nickel solution, nickel source concentration is 0.10～0.25mol/L.
In step (2), calcining heat is 500～800 DEG C, temperature retention time 1～3h.
In the present invention, the NiTiO that described preparation method is obtained3Material assumes club shaped structure, rod a diameter of 100～
300nm, length is 500～2000nm.
This also includes described NiTiO3The application of negative material, by described NiTiO3Negative material is used for preparing sodium ion
The negative pole of battery.
For example, in the present invention, by the prepared NiTiO of described preparation method3Negative material prepares the negative of sodium-ion battery
Pole.
Described application, such as by described NiTiO3After negative material is mixed with conductive agent and binding agent, by coating
On Copper Foil, make sodium-ion battery negative pole.The conductive agent that adopted, binding agent can adopt well-known to those skilled in the art
Material.The method that anode material of lithium-ion battery is prepared in assembling also refers to existing method.
For example, the NiTiO that the present invention is obtained3The method that negative pole prepared by material：By NiTiO3Material and conductive black and Sargassum
Sour sodium binding agent is ground according to 7: 1.5: 1.5 mass ratio, adds deionized water to form uniform paste after being sufficiently mixed
Shape thing, is coated on Copper Foil as test electrode, makes button cell using metallic sodium as to electrode, its electrolyte is 1M
NaClO4/ EC: DMC (1: 1)+5wt.%FEC, charging and discharging currents density used by test loop performance is 500mA/g.
Present invention additionally comprises including NiTiO of the present invention3The negative pole of negative material.
Beneficial effects of the present invention：
The present invention prepares NiTiO3The method of negative material is simple and reliable, environmental protection, workable, environmental friendliness,
With low cost, there is wide industrial applications prospect.The present invention selects suitable solvent, only by simple solution stirring,
Using the self assembly between ion, do not use any template, just synthesize the uniformly bar-shaped NiTiO of pattern3Negative material (is received
The excellent structure of rice), this is that those skilled in the art are difficult to expect.
The NiTiO of the present invention3Negative material when as sodium-ion battery, using its unique club shaped structure advantage, phase
Ratio, in grain structure, accelerates the transfer rate of ion-electron, and club shaped structure is difficult to reunite in charge and discharge process simultaneously, thus carrying
The high cycle performance of sodium-ion battery.
Additionally, metatitanic acid nanosized nickel rods (the bar-shaped NiTiO of the present invention that the present invention prepares3Negative material) fill
Discharge platform is extremely low, only 0.2V about, when so this negative material is used for full battery, just can obtain higher electric potential difference, from
And obtain larger energy density.
Brief description
【Fig. 1】The NiTiO being obtained for embodiment 13The X ray diffracting spectrum (XRD) of material；
【Fig. 2】The NiTiO being obtained for embodiment 13The scanning electron microscope (SEM) photograph (SEM) of material；
【Fig. 3】The NiTiO being obtained for embodiment 13The constant current charge-discharge performance map of the sodium-ion battery of material assembling；
【Fig. 4】The NiTiO being obtained for embodiment 13The first circle discharge curve of the sodium-ion battery of material assembling.
Specific embodiment
Following examples are intended to present invention is described in further details；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 8h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace, rise
Temperature, to 600 DEG C, is incubated 2h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.And all diffraction maximums of XRD
All can be mapped to NiTiO3Standard card chip value, does not have any miscellaneous peak, shows the material purity preparing high (see Fig. 1)；Fig. 2
For NiTiO3The scanning electron microscope (SEM) photograph of material；Figure it is seen that NiTiO3Rod a diameter of 100～300nm, length be 500～
2000nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
315mAh/g (see Fig. 3).It can be seen that reaction platform is only 0.2V (see Fig. 4) from first circle discharge curve.
Embodiment 2
Take 0.1mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, Ran Houjia
Enter 0.1mol butyl titanate, stir 8h, product is filtered, spent glycol washs three times, be dried after, be placed in Muffle furnace, rise
Temperature, to 600 DEG C, is incubated 2h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3Excellent is a diameter of
120～350nm, length is 500～2300nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
310mAh/g.
Embodiment 3
Take 0.3mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, Ran Houjia
Enter 0.3mol butyl titanate, stir 10h, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace, heating up
To 600 DEG C, it is incubated 2h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3A diameter of the 150 of rod
～330nm, length is 500～2700nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
303mAh/g.
Embodiment 4
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 8h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace, rise
Temperature, to 600 DEG C, is incubated 12h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3Excellent is a diameter of
100～320nm, length is 500～2100nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
301mAh/g.
Embodiment 5
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15 mol butyl titanate, stir 8h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace,
It is warming up to 600 DEG C, be incubated 0.5h, that is, obtain NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3The diameter of rod
For 150～340nm, length is 500～2300nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
280mAh/g.
Embodiment 6
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 8h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace, rise
Temperature, to 1000 DEG C, is incubated 2h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3Excellent is a diameter of
150～345nm, length is 500～2100nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
291mAh/g.
Embodiment 7
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 0.2h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace,
It is warming up to 600 DEG C, be incubated 2h, that is, obtain NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3Excellent is a diameter of
100～200nm, length is 500～1800nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
273mAh/g.
Embodiment 8
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 20h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace,
It is warming up to 600 DEG C, be incubated 2h, that is, obtain NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3Excellent is a diameter of
150～300nm, length is 500～2000nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
298mAh/g.
Embodiment 9
Take 0.1mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, Ran Houjia
Enter 0.1mol butyl titanate, stir 8h, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace, heating up
To 400 DEG C, it is incubated 1h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3A diameter of the 150 of rod
～380nm, length is 500～2800nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
288mAh/g.
Embodiment 10
Take 0.1mol nickel acetate to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, be subsequently adding
0.1mol butyl titanate, stirs 8h, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace, being warming up to
700 DEG C, it is incubated 2h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3A diameter of the 100 of rod～
320nm, length is 600～3100nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
314mAh/g.
Embodiment 11
In take 0.1mol nickel acetate to be dissolved in first Polyethylene Glycol that 1 molecular weight is 1200, it is sufficiently stirred for, obtains green clarification
Solution, is subsequently adding 0.1mol butyl titanate, stirs 8h, product is filtered, with, after ethanol wash three times, drying, being placed in horse
Not in stove, it is warming up to 600 DEG C, be incubated 2h, that is, obtain NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3Rod
A diameter of 150～360nm, length be 500～3000nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
310mAh/g.
Embodiment 12
Take 0.1mol nickel acetate to be dissolved in 1L glycerol first, be sufficiently stirred for, obtain green settled solution, be subsequently adding
0.1mol butyl titanate, stirs 8h, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace, being warming up to
600 DEG C, it is incubated 2h, that is, obtains NiTiO3Material.XRD result shows that this material is NiTiO3.NiTiO3A diameter of the 120 of rod～
380nm, length is 500～2800nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity may remain in
302mAh/g.
Comparative example 1
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 8h, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace, rise
Temperature, to 600 DEG C, is incubated 5min, obtains product.XRD does not have obvious characteristic peak, shows that this product form is poor.This product rod
A diameter of 150～800nm, length is 500～4000nm.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity is maintained at 200
mAh/g.
Comparative example 2
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, then
Add 0.15mol butyl titanate, stir 2min, product is filtered, with ethanol wash three times, be dried after, be placed in Muffle furnace,
It is warming up to 600 DEG C, be incubated 2h, obtain product.XRD does not detect pure phase material.
Comparative example 3
Take 0.15mol nickel acetate to be dissolved in 1L ethylene glycol first, be sufficiently stirred for, obtain green settled solution, be subsequently adding
0.15mol butyl titanate, stirs 5min, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace, heating up
To 600 DEG C, it is incubated 2h, obtains product.XRD does not detect pure phase material.
Comparative example 4
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L deionized water first, be sufficiently stirred for, obtain green settled solution, so
Add 0.15mol butyl titanate afterwards, stir 20min, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace
In, it is warming up to 600 DEG C, be incubated 2h, obtain product.XRD does not detect pure phase material.
Comparative example 5
Take 0.15mol tetra- water acetic acid nickel to be dissolved in the Polyethylene Glycol that 1L molecular weight is 8000 first, be sufficiently stirred for, obtain green
Color settled solution, is subsequently adding 0.15mol butyl titanate, stirs 20min, product is filtered, uses ethanol wash three times, be dried
Afterwards, it is placed in Muffle furnace, is warming up to 600 DEG C, be incubated 2h, obtain product.XRD shows that this material is NiTiO3.But structure is in
It is now graininess and bar-shaped mixed state.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity is maintained at
190mAh/g.
Comparative example 6
Take 0.15mol tetra- water acetic acid nickel to be dissolved in 1L ethanol first, be sufficiently stirred for, obtain green settled solution, Ran Houjia
Enter 0.15mol butyl titanate, stir 8h, product is filtered, with, after ethanol wash three times, drying, being placed in Muffle furnace, heating up
To 600 DEG C, it is incubated 2h, obtains product.XRD shows that this material is NiTiO3.But structure is mainly graininess.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, fills from constant current
Discharge performance in figure can be seen that under the constant-current discharge density of 500mA/g, and circulation 200 circle specific discharge capacity is maintained at
150mAh/g.
Claims (10)
1. a kind of NiTiO for sodium-ion battery3Negative material is it is characterised in that described NiTiO3Negative material is rendered as
Club shaped structure.
2. it is used for the NiTiO of sodium-ion battery as claimed in claim 13Negative material is it is characterised in that described NiTiO3
A diameter of 100～400nm of negative material, length is 500～3000nm.
3. the NiTiO for sodium-ion battery described in a kind of claim 1 or 23The preparation method of negative material, its feature exists
In, by nickel source dispersion and/or dissolving in a solvent, obtain nickel solution；Add titanium source stirring reaction again, subsequently again to the product reacting
Wash, be dried, calcining obtains described NiTiO3Negative material；Described solvent is the alcoholic solution of more than binary.
4. it is used for the NiTiO of sodium-ion battery as claimed in claim 33The preparation method of negative material is it is characterised in that institute
The solvent stated is the alcoholic solution more than binary of molecular weight not higher than 1200.
5. it is used for the NiTiO of sodium-ion battery as claimed in claim 43The preparation method of negative material is it is characterised in that institute
The solvent stated is glycerol, ethylene glycol, at least one in Polyethylene Glycol.
6. it is used for the NiTiO of sodium-ion battery as claimed in claim 33The preparation method of negative material is it is characterised in that forge
Burn temperature and be 400～1000 DEG C；The calcination reaction time is 0.5～12h.
7. it is used for the NiTiO of sodium-ion battery as claimed in claim 33The preparation method of negative material is it is characterised in that institute
The nickel source stated is water miscible nickel compound and its hydrate；In described nickel solution, Ni2+Concentration be 0.1～0.3mol/L.
8. it is used for the NiTiO of sodium-ion battery as claimed in claim 33The preparation method of negative material is it is characterised in that institute
The titanium source stated is butyl titanate, tetraethyl titanate, at least one of isopropyl titanate.
9. it is used for the NiTiO of sodium-ion battery as claimed in claim 33The preparation method of negative material is it is characterised in that stir
Mix the response time for 0.2～20h.
10. the NiTiO for sodium-ion battery described in a kind of claim 1 or 23The application of negative material it is characterised in that
By described NiTiO3Negative material is used for preparing the negative pole of sodium-ion battery.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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| CN101880067A (en) * | 2010-07-15 | 2010-11-10 | 陕西科技大学 | Preparation method of bar-shaped NiTiO3 nano-crystalline |
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Non-Patent Citations (3)
| Title |
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| RAMCHANDRA S. KALUBARME等: "Nickel-titanium oxide as a novel anode material for rechargeable sodium-ion batteries", 《JOURNAL OF MATERIALS CHEMISTRY A》 * |
| YANG QU等: "Facile preparation of porous NiTiO3 nanorods with enhanced visible-light-driven photocatalytic performance", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
| 冯建 等: "NiTiO3纳米棒的制备及表征", 《精细化工》 * |
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