CN106299344A - A kind of sodium-ion battery nickel titanate negative material and preparation method thereof - Google Patents

A kind of sodium-ion battery nickel titanate negative material and preparation method thereof Download PDF

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CN106299344A
CN106299344A CN201610963046.2A CN201610963046A CN106299344A CN 106299344 A CN106299344 A CN 106299344A CN 201610963046 A CN201610963046 A CN 201610963046A CN 106299344 A CN106299344 A CN 106299344A
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ion battery
nickel
sodium
nickel titanate
titanate
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CN106299344B (en
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张治安
宋俊肖
史晓东
潘迪
李天伟
于航
尹盟
李天凡
解豪
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Central South University
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00Secondary cells; Manufacture thereof
    • H01M10/36Accumulators not provided for in groups H01M10/05-H01M10/34
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/13Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139Processes of manufacture
    • H01M4/1391Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00Electrodes
    • H01M4/02Electrodes composed of or comprising active material
    • H01M4/36Selection of substances as active materials, active masses, active liquids
    • H01M4/48Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries

Abstract

The invention discloses a kind of sodium-ion battery nickel titanate negative material and preparation method thereof.Nickel titanate material of the present invention has loose porous structure, and microscopic appearance is disk like, has electronegative potential as anode material of lithium-ion battery, height ratio capacity and the cycle performance of excellence, and its preparation method is simple, with low cost, there is wide industrial applications prospect.

Description

A kind of sodium-ion battery nickel titanate negative material and preparation method thereof
Technical field
The present invention relates to a kind of novel anode material of lithium-ion battery and preparation method thereof, particularly to a kind of sodium ion electricity Pond nickel titanate negative material and preparation method, belong to sodium-ion battery field.
Background technology
Since the eighties in last century, lithium ion battery came out, as third generation rechargeable battery have specific energy high, The advantages such as memory-less effect, length in service life and environmental pollution are little and receive much concern, and be widely used in electric automobile and Notebook computer, the mobile electronic device such as smart mobile phone.But, owing to elemental lithium content in the earth's crust is relatively fewer, therefore It is necessary to develop a kind of novel secondary cell system.
Sodium-ion battery is considered as the ideal chose of energy storage of future generation and converting system.Sodium element is in nature Reserves the abundantest, account for the 2.74% of the earth's crust, and widely distributed, significantly reduce development of resources extraction cost.With Time, sodium and elemental lithium be all periodic table of elements I major element, and both have similar physicochemical characteristics.Therefore, sodium ion Battery has the response mechanism similar with lithium ion battery and energy storage advantage.
At present, study more sodium ion negative material and be mainly various carbon-based material, as graphite, carbonaceous mesophase spherules, Hard carbons etc., the chemical property of carbon-based material is relevant with each self-structure.Such as, although graphite has higher lithium storage content, but The ability being its storage sodium is the most weak, is widely considered to be sodium ion radius caused away from not mating with graphite layers.And the stone of amorphous carbon Inkization degree is low, and its structure is mainly formed by the accumulation that interlocks of the most unordered carbon crystallite, and graphite layers, away from greatly, contain again in a large number Nanometer micropore, provides preferable avtive spot for the storage of sodium ion, and therefore amorphous carbon material is (carbonaceous mesophase spherules, hard Carbon etc.) there is higher reversible storage sodium capacity, but this type of material circulation poor stability, capacity attenuation is fast, strongly limit it Sodium-ion battery is applied.Showing according to up-to-date result of study, transition metals Ti silicate system is born as sodium-ion battery Pole material not only has the low take-off potential similar to carbon negative pole material and long circulating performance, and has and be better than material with carbon element Height ratio capacity.Additionally, due to transition metal mineral resources rich reserves, so this material system also has potential production cost Advantage.
Nickel titanate material is potential sodium-ion battery/lithium ion battery negative material, but existing nickel titanate material Without fixing pattern, crystal is the purest, does not have great advantage as its cycle performance of electrode material and high rate performance.
Summary of the invention
The defect existed for existing sodium ion battery electrode material, the invention provides one and has loose porous disk like The nickel titanate material of structure, this material not only has the embedding-abjection storage sodium mechanism similar to material with carbon element, and has excellence Charging and discharging capacity, high rate performance and stable circulation performance.
Another object of the present invention is to be to provide a kind of technique above-mentioned material simple, with low cost, eco-friendly Preparation method.
In order to realize above-mentioned technical purpose, the invention provides a kind of sodium-ion battery nickel titanate negative material, this material Present loose porous saucer-like configuration.
Preferably scheme, described nickel titanate is nano-particle, and they are a size of 200~800nm years old.
Present invention also offers a kind of method preparing described sodium-ion battery nickel titanate negative material, will contain nickel salt and Transition metal salt containing titanium salt composition is with organic ligand in organic solvent, in 150-200 DEG C, double golden by solvent structure Belong to MOFs presoma;Then, in bimetallic MOFs presoma, it is passed through oxygen, is first heated to 100~200 DEG C and carries out at preheating Reason, is again heated to 500~800 DEG C and carries out heat treatment;Finally, gained heat-treated products is sequentially passed through washing, is dried, to obtain final product.
Preferably scheme, in described solvent-thermal method, the response time is 12~24h.
Preferably scheme, described transition metal salt is 1:3~1:9 with the mol ratio of organic ligand.
Preferably scheme, described transition metal salt is 1:200~1:700 with the mol ratio of organic solvent.
Preferably scheme, described is 2:1~1:2 containing nickel salt and the mol ratio containing titanium salt.
Preferably scheme, described is at least one in nickel nitrate, nickel sulfate, nickel acetate or Nickel dichloride. containing nickel salt;Described It is at least one in butyl titanate, tetraisopropyl titanate or tetraethyl titanate containing titanium salt.
Preferably scheme, described organic ligand is Isosorbide-5-Nitrae-p-phthalic acid or 1, at least in 3,5-trimesic acids Kind.
Preferably scheme, described organic solvent is at least one in methanol, N ' dinethylformamide or ethanol.
Preferably scheme, the described the pre-heat treatment time is 1~2h;Described heat treatment time is 3~9h.
Preferably scheme, after described heat treatment product uses dilute acid soln and water cyclic washing, is placed in 50~80 DEG C Under temperature conditions, it is vacuum dried 8~12h.
The dilute acid soln that dilute acid soln is known in the art, uses diluted acid and water alternately and repeatedly to wash, can be by the gold of residual Belong to the Impurity removal produced in oxide and carbonisation.
More preferably scheme, described dilute acid soln is at least one in dilute hydrochloric acid, dilute sulfuric acid or dust technology.
In the preparation method of the present invention, contain transiting metal nickel by high-temperature process, the bimetallic MOFs forerunner of titanium ion Body, bimetallic MOFs (Metal Organic Frameworks-metal-organic framework material) presoma is keeping it original Carry out carbonization on the premise of basic pore passage structure and microscopic appearance, obtain the loose porous titanium with disk like nanostructured Acid nickel material.
In concrete preparation process, by the pre-heat treatment, promote organic solvent volatilization in pore passage structure, fully open double Pore passage structure within metal MOFs presoma, heat treatment continuous after bonding, carry out high temperature cabonization, make Titanium ion and nickel Ion occurs fully oxidized, on the premise of keeping its stable appearance, retains the pore passage structure that bimetallic MOFs presoma has, Finally give the disk like nickel titanate material with loose and porous structure.Loose porous nickel titanate negative material is possible not only to increase Add the wetting contact area of electrode material and electrolyte, and can effectively alleviate electrode material in sodium ion intercalation/deintercalation During the change in volume that causes, thus be conducive to improving the cyclical stability of sodium-ion battery and high rate performance.
The bimetallic MOFs presoma of the present invention by transition metal salt, organic ligand and organic solvent according to certain ratio After example mixing, prepared by solvent-thermal method.
The disk like nano barium titanate nickel material of the present invention by bimetallic MOFs presoma through low-temperature prewarming and high temperature cabonization two Individual step generates.
Further preferably prepare the method for nickel titanate negative material and include step in detail below:
1) transition metal salt containing nickel salt with containing titanium salt composition is completely dissolved in organic solvent, there was added while stirring Machine part;
2), after stirring, move to politef inner liner of reaction kettle is carried out solvent thermal reaction, by centrifugation, washing, dry After dry, i.e. can get Ti-Ni bimetallic MOFs presoma;
3) gained bimetallic MOFs presoma is placed in vacuum tube furnace, under oxygen atmosphere, first carries out low-temperature prewarming Process, then carry out high temperature cabonization;
4) by step 3) products therefrom dilute sulfuric acid and deionized water cyclic washing, it is dried, obtains nickel titanate negative material.
The sodium-ion battery performance test methods of nickel titanate negative material prepared by the present invention: weigh above-mentioned material, adds 10wt.%Super P as conductive agent, 10wt.% sodium carboxymethyl cellulose (CMC) as binding agent, ground fully after Add a small amount of deionized water and be mixed to form uniform black paste slurry, slurry is coated in copper foil current collector as test electricity Pole, becomes 2025 button cells with metallic sodium sheet electrode assembling as a comparison, and it uses electrolyte system to be 1M NaClO4/EC: DEC (1:1)+5%FEC, the barrier film of employing is Celgard 2400, and charging and discharging currents density used by test loop performance is 50mA/g。
Hinge structure, the beneficial effect that technical scheme is brought:
1) the nickel titanate negative material of the present invention has loose porous saucer-like configuration, this architecture provides abundant storage sodium and lives Property site and sodium ion transmission channel.Meanwhile, the loose structure of nano material is possible not only to the moistening increasing material with electrolyte Contact area, and can effectively alleviate electrode material and the volumetric expansion of generation in sodium ion course of reaction, and then be conducive to Improve cyclical stability and the high rate performance of sodium-ion battery.
2) present invention prepares the method for nickel titanate material operation is simple and reliable, reproducible, environmental friendliness, with low cost, There is wide industrial applications prospect.
Accompanying drawing explanation
[Fig. 1] is the X-ray diffractogram (XRD) of the nickel titanate negative material that embodiment 1 prepares;
[Fig. 2] is the scanning electron microscope (SEM) photograph (SEM) of the nickel titanate negative material that embodiment 1 prepares;
[Fig. 3] is the transmission electron microscope picture (TEM) of the nickel titanate negative material that embodiment 1 prepares;
[Fig. 4] is the constant current charge-discharge performance map of the sodium-ion battery that the nickel titanate negative material that embodiment 1 prepares assembles;
[Fig. 5] is the high rate performance figure of the sodium-ion battery that the nickel titanate negative material that embodiment 1 prepares assembles.
[Fig. 6] is the scanning electron microscope (SEM) photograph (SEM) of the nickel titanate negative material that comparative example 1 prepares;
[Fig. 7] is the scanning electron microscope (SEM) photograph (SEM) of the nickel titanate negative material that comparative example 2 prepares;
[Fig. 8] is the constant current charge-discharge performance map of the sodium-ion battery that the nickel titanate negative material that comparative example 3 prepares assembles;
Detailed description of the invention
Following example are intended to be described in further details present invention;And the protection domain of the claims in the present invention It is not limited by the example.
Embodiment 1
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In the mixed solution of base Methanamide and 200ml methanol composition, then weigh 9.96g Isosorbide-5-Nitrae-p-phthalic acid at magnetic agitation bar It is slowly added under part in above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, Solvent thermal reaction is carried out under the conditions of 160 DEG C, after reaction 18h, gained precipitate is anti-through methanol and N ' dinethylformamide After backwashing is washed, and is dried and i.e. can get Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 150 DEG C, and be incubated 1.5h at this temperature;Subsequently, continue to be warming up to tube furnace 700 DEG C and fully oxidized 6h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain Nickel titanate nano material.
The sodium-ion battery nickelous carbonate nanometer anode material using the present embodiment to prepare is assembled into button cell with sodium sheet, its Material structure characterizes with chemical property as shown in the figure:
In Fig. 1 contrast standard diffracting spectrum explanation nickel titanate material in there is no other impurity, for single NiTiO3Brilliant Body.
Fig. 2, Fig. 3 can be seen that, the nickel titanate material prepared has loose porous disk like nanostructured, wherein Nickel titanate nanoparticle size is 200~400nm.
Fig. 4 shows the electrode using nickel titanate material to make, under the constant-current discharge density of 50mA/g, circulation 200 circle Specific discharge capacity may remain in 520mAh/g, shows good stable circulation performance.
Fig. 5 shows the electrode using nickel titanate negative material to make high rate performance under different discharge current densities Figure, as can be seen from the figure this composite has the high rate performance of excellence, even if under the conditions of the heavy-current discharge of 2A/g still Can keep the charge specific capacity of 180mAh/g, after electric current density is restored to 200mA/g, specific discharge capacity again can be again Reach 310mAh/g.
Embodiment 2
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 400mL N ' N-diformazan In base Methanamide, then weigh 6.64g Isosorbide-5-Nitrae-p-phthalic acid and be slowly added under the conditions of magnetic agitation in above-mentioned solution, After stirring, gained mixed solution is transferred in politef reactor, under the conditions of 160 DEG C, carries out solvent thermal anti- Should, by gained precipitate through methanol and N ' dinethylformamide cyclic washing after reaction 14h, it is dried and i.e. can get Ti-Ni Bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 180 DEG C, and be incubated 1.5h at this temperature;Subsequently, continue to be warming up to tube furnace 600 DEG C and fully oxidized 6h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain Nickel titanate nano material.
Nickel titanate material prepared by the method belongs to single NiTiO3.This material part pattern is rendered as loose porous Disk like, its nanoparticle size is 300~600nm.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity may remain in 470mAh/g.
Embodiment 3
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 400mL methanol solution In, then weigh 9.96g Isosorbide-5-Nitrae-p-phthalic acid and be slowly added under the conditions of magnetic agitation in above-mentioned solution, stir Afterwards gained mixed solution is transferred in politef reactor, under the conditions of 180 DEG C, carries out solvent thermal reaction, reaction By gained precipitate through methanol and N ' dinethylformamide cyclic washing after 18h, it is dried and i.e. can get Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 180 DEG C, and be incubated 1h at this temperature;Subsequently, continue tube furnace is warming up to 700 DEG C and fully oxidized 4h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain metatitanic acid Nickel nano material.
Nickel titanate material prepared by the method belongs to single NiTiO3.The microscopic appearance of this material is loose porous nothing Shaped, does not find obvious saucer-like configuration, and its nanoparticle size is 400~700nm.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity may remain in 400mAh/g.
Embodiment 4
First 1.42g isopropyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In base Methanamide and 200ml methanol, then weigh 11.62g Isosorbide-5-Nitrae-p-phthalic acid and be slowly added under the conditions of magnetic agitation In above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, enters under the conditions of 160 DEG C Row solvent thermal reaction, by gained precipitate through methanol and N ' dinethylformamide cyclic washing after reaction 18h, is dried Obtain Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 160 DEG C, and be incubated 2h at this temperature;Subsequently, continue tube furnace is warming up to 800 DEG C and fully oxidized 4h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain metatitanic acid Nickel nano material.
Nickel titanate material prepared by the method belongs to single NiTiO3.This nickel titanate material has loose porous disk like Nanostructured, wherein nickel titanate nanoparticle size is 300~500nm.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity may remain in 500mAh/g.
Embodiment 5
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In base Methanamide and 200ml methanol, then weigh 13.28g Isosorbide-5-Nitrae-p-phthalic acid and be slowly added under the conditions of magnetic agitation In above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, enters under the conditions of 160 DEG C Row solvent thermal reaction, by gained precipitate through methanol and N ' dinethylformamide cyclic washing after reaction 15h, is dried Obtain Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 150 DEG C, and be incubated 2h at this temperature;Subsequently, continue tube furnace is warming up to 500 DEG C and fully oxidized 6h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain metatitanic acid Nickel nano material.
Nickel titanate material prepared by the method belongs to single NiTiO3.This material morphology is rendered as loose porous dish Shape, its nanoparticle size is 500~800nm.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity may remain in 450mAh/g.
Comparative example 1
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In base Methanamide and 200ml methanol, then weigh 9.96g Isosorbide-5-Nitrae-p-phthalic acid and be slowly added under the conditions of magnetic agitation In above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, enters under the conditions of 160 DEG C Row solvent thermal reaction, by gained precipitate through methanol and N ' dinethylformamide cyclic washing after reaction 18h, is dried Obtain Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is directly warming up to 700 DEG C and fully oxidized 6h.Finally, by gained oxidation product dilute sulfuric acid and Deionized water is repeated washing, is drying to obtain nickelous carbonate nano material.
Nickel titanate material prepared by the method belongs to single NiTiO3.The microscopic appearance of this material does not find loose many The structure in hole, does not the most find obvious saucer-like configuration, and its nanoparticle size is 600~800nm.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity is maintained at 300mAh/g.
Comparative example 2
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In base Methanamide and 200ml methanol, then weigh 9.96g Isosorbide-5-Nitrae-p-phthalic acid and be slowly added under the conditions of magnetic agitation In above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, enters under the conditions of 160 DEG C Row solvent thermal reaction, by gained precipitate through methanol and N ' dinethylformamide cyclic washing after reaction 10h, is dried Obtain Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 150 DEG C, and be incubated 1.5h at this temperature;Subsequently, continue to be warming up to tube furnace 700 DEG C and fully oxidized 6h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain Nickel titanate nano material.
Nickel titanate material prepared by the method is not single NiTiO3.This material morphology is disorderly and unsystematic, the most fixing Nano-particle distributed area.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity is maintained at 250mAh/g.
Comparative example 3
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 100ml ethylene glycol, After stirring, gained mixed solution is transferred in politef hydrothermal reaction kettle, under the conditions of 180 DEG C, carries out hydro-thermal Reaction, by gained precipitate through ethanol and deionized water cyclic washing after reaction 24h, is dried and i.e. can get nickel titanate material.
In order to obtain the purest nickel titanate material, put it into inside corundum porcelain boat, and in dislocation vacuum tube furnace, Tube furnace is directly warming up to 600 DEG C and fully calcined 2h.Finally, gained oxidation product deionized water is repeated washes Wash, be drying to obtain pure nickel titanate nano material.
Nickel titanate material prepared by the method belongs to single NiTiO3.This material does not has specific microscopic appearance, does not has yet Being found loose porous structure, its nanoparticle size is 800~1000nm.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity is maintained at 280mAh/g.
Comparative example 4
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In the mixed solution of base Methanamide and 200ml methanol composition, then weigh 9.96g Isosorbide-5-Nitrae-p-phthalic acid at magnetic agitation bar It is slowly added under part in above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, Solvent thermal reaction is carried out under the conditions of 140 DEG C, after reaction 18h, gained precipitate is anti-through methanol and N ' dinethylformamide After backwashing is washed, and is dried and i.e. can get Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 150 DEG C, and be incubated 1.5h at this temperature;Subsequently, continue to be warming up to tube furnace 700 DEG C and fully oxidized 6h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain Nickel titanate nano material.
Nickel titanate material prepared by the method is not single NiTiO3.Pattern that this material is not fixed and nanometer Grain distributed area.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity may remain in 260mAh/g.
Comparative example 5
First 1.7g butyl titanate and 1.45g six water nickel nitrate are weighed so that it is be completely dissolved in 200ml N ' N-diformazan In the mixed solution of base Methanamide and 200ml methanol composition, then weigh 9.96g Isosorbide-5-Nitrae-p-phthalic acid at magnetic agitation bar It is slowly added under part in above-mentioned solution, after stirring, gained mixed solution is transferred in politef reactor, Solvent thermal reaction is carried out under the conditions of 160 DEG C, after reaction 18h, gained precipitate is anti-through methanol and N ' dinethylformamide After backwashing is washed, and is dried and i.e. can get Ti-Ni bimetallic MOFs presoma.
Weigh appropriate Ti-Ni bimetallic MOFs presoma, put it into inside corundum porcelain boat, and dislocation vacuum tube furnace In.It is passed through oxygen and tube furnace is warming up to 150 DEG C, and be incubated 1.5h at this temperature;Subsequently, continue to be warming up to tube furnace 400 DEG C and fully oxidized 6h.Finally, gained oxidation product dilute sulfuric acid and deionized water are repeated washing, are drying to obtain Nickel titanate nano material.
Nickel titanate material prepared by the method is not single NiTiO3.Inside this material, metallic nickel oxidation is insufficient, makees It is blended in inside nickel titanate material for impurity, there is no obvious disk like pattern.
The anode material of lithium-ion battery using the present embodiment to prepare is assembled into button cell, in the perseverance of 50mA/g with sodium sheet Under stream power-discharging density, circulation 200 circle specific discharge capacity may remain in 270mAh/g.

Claims (10)

1. a sodium-ion battery nickel titanate negative material, it is characterised in that: described nickel titanate material presents loose porous dish Shape structure.
Sodium-ion battery nickel titanate negative material the most according to claim 1, it is characterised in that: described nickel titanate material is Nano-particle, they are a diameter of 200~800nm years old.
3. the method for preparation sodium-ion battery nickel titanate negative material described in claim 1 or 2, it is characterised in that: by nickeliferous Salt and the transition metal salt containing titanium salt composition with organic ligand in organic solvent, in 150-200 DEG C, pass through solvent structure Bimetallic MOFs presoma;Then, in bimetallic MOFs presoma, it is passed through oxygen, is first heated to 100~200 DEG C and preheats Process, be again heated to 500~800 DEG C and carry out heat treatment;Finally, by gained heat-treated products through washing, being dried, to obtain final product.
The method preparing sodium-ion battery nickel titanate negative material the most according to claim 3, it is characterised in that: described molten In agent full-boiled process, the response time is 12~24h.
The method preparing sodium-ion battery nickel titanate negative material the most according to claim 3, it is characterised in that: described mistake The mol ratio crossing slaine and organic ligand is 1:3~1:9;Described transition metal salt is 1:200 with the mol ratio of organic solvent ~1:700.
6. according to the method preparing sodium-ion battery nickel titanate negative material described in claim 3 or 5, it is characterised in that: institute Stating containing nickel salt and the mol ratio containing titanium salt is 2:1~1:2.
The method preparing sodium-ion battery nickel titanate negative material the most according to claim 3, it is characterised in that: described contain Nickel salt is at least one in nickel nitrate, nickel sulfate, nickel acetate or Nickel dichloride.;Described is butyl titanate, metatitanic acid four containing titanium salt At least one in isopropyl ester or tetraethyl titanate;Described organic ligand is 1,4-p-phthalic acid or 1,3,5-trimesic acid In at least one;Described organic solvent is at least one in methanol, N ' dinethylformamide or ethanol.
The method preparing sodium-ion battery nickel titanate negative material the most according to claim 3, it is characterised in that: described pre- Heat treatment time is 1~2h;Heat treatment time is 3~9h.
9. according to the method preparing sodium-ion battery nickel titanate negative material described in claim 3 or 8, it is characterised in that: institute After stating heat-treated products employing dilute acid soln and deionized water cyclic washing, under the conditions of 50~80 DEG C, it is vacuum dried 8~12h.
The method preparing sodium-ion battery nickel titanate negative material the most according to claim 9, it is characterised in that: described Dilute acid soln be at least one in dilute hydrochloric acid, dilute sulfuric acid or dust technology.
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