CN106299344B - A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof - Google Patents
A kind of sodium-ion battery nickel titanate negative electrode material and preparation method thereof Download PDFInfo
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- CN106299344B CN106299344B CN201610963046.2A CN201610963046A CN106299344B CN 106299344 B CN106299344 B CN 106299344B CN 201610963046 A CN201610963046 A CN 201610963046A CN 106299344 B CN106299344 B CN 106299344B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/36—Accumulators not provided for in groups H01M10/05-H01M10/34
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
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- 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
Abstract
The invention discloses a kind of sodium-ion battery nickel titanate negative electrode materials and preparation method thereof.Metatitanic acid nickel material of the present invention has loose porous structure, and microscopic appearance is disk like, and being used as anode material of lithium-ion battery has low potential, height ratio capacity and excellent cycle performance, and preparation method is simple, and it is low in cost, there is wide industrial applications prospect.
Description
Technical field
The present invention relates to a kind of novel anode material of lithium-ion battery and preparation method thereof, in particular to a kind of sodium ion electricity
Pond nickel titanate negative electrode material and preparation method, belong to sodium-ion battery field.
Background technique
Since the lithium ion battery eighties in last century comes out, high with specific energy as third generation rechargeable battery,
The advantages that memory-less effect, small long service life and environmental pollution and be concerned, and be widely used in electric car and
Laptop, the mobile electronic devices such as smart phone.However, since content of the elemental lithium in the earth's crust is relatively fewer,
It is necessary to develop a kind of novel secondary cell system.
Sodium-ion battery is considered as the ideal chose of next-generation energy storage and converting system.Sodium element is in nature
Reserves it is very rich, account for about the 2.74% of the earth's crust, and widely distributed, significantly reduce development of resources extraction cost.Together
When, sodium and elemental lithium are all periodic table of elements I major element, and the two has similar physicochemical characteristics.Therefore, sodium ion
Battery has reaction mechanism similar with lithium ion battery and energy storage advantage.
Currently, the more sodium ion negative electrode material of research is mainly various carbon-based materials, as graphite, carbonaceous mesophase spherules,
Hard carbon etc., the chemical property of carbon-based material are related with each self-structure.For example, graphite although lithium storage content with higher, but
It is that its ability for storing up sodium is very weak, is widely considered to be sodium ion radius and graphite layers away from caused by mismatch.And the stone of amorphous carbon
Blackization degree is low, and structure is mainly staggeredly to be accumulated by a large amount of unordered carbon crystallites, and graphite layers are away from big, and containing a large amount of
Nanometer micropore provides ideal active site for the storage of sodium ion, therefore amorphous carbon material is (carbonaceous mesophase spherules, hard
Carbon etc.) reversible storage sodium capacity with higher, but such material circulation stability is poor, capacity attenuation is fast, strongly limits it
It is applied in sodium-ion battery.According to document " Nickel-titanium oxide as a novel anode material
for rechargeable sodium-ion batteries[J].Journal of Materials Chemistry A,
2016,4 (44): 17419. " record, and transition metals Ti silicate system not only has negative with carbon as anode material of lithium-ion battery
The similar low take-off potential of pole material and long circulating performance, and there is the height ratio capacity better than carbon material.Further, since mistake
It is abundant to cross metalliferous mineral resource reserve, so the material system also has potential production cost advantage.
Metatitanic acid nickel material is potential sodium-ion battery/lithium ion battery negative material, but existing metatitanic acid nickel material
Without fixed pattern, crystal is not pure, does not have great advantage as its cycle performance of electrode material and high rate performance.
Summary of the invention
For defect existing for existing sodium ion battery electrode material, the present invention provides one kind to have loose porous disk like
The metatitanic acid nickel material of structure, which not only has insertion similar with carbon material-abjection storage sodium mechanism, but also has excellent
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 simple process, low in cost, environmental-friendly above-mentioned material
Preparation method.
In order to achieve the above technical purposes, the present invention provides a kind of sodium-ion battery nickel titanate negative electrode material, the materials
Loose porous saucer-like configuration is presented.
Preferred scheme, the nickel titanate is nano particle, having a size of 200~800nm.
The present invention also provides a kind of method for preparing the sodium-ion battery nickel titanate negative electrode material, will contain nickel salt and
The transition metal salt and organic ligand of the composition containing titanium salt in organic solvent, in 150-200 DEG C, pass through the double gold of solvent structure
Belong to MOFs presoma；Then, it is passed through oxygen into bimetallic MOFs presoma, is first heated to 100~200 DEG C and carries out at preheating
Reason, is again heated to 500~800 DEG C and is heat-treated；Finally, by gained heat-treated products successively by washing, it is dry to get.
Preferred scheme, in the solvent-thermal method, the reaction time is 12~for 24 hours.
The molar ratio of preferred scheme, the transition metal salt and organic ligand is 1:3~1:9.
The molar ratio of preferred scheme, the transition metal salt and organic solvent is 1:200~1:700.
Preferred scheme, described containing nickel salt and the molar ratio containing titanium salt is 2:1~1:2.
Preferred scheme, the nickel salt that contains is at least one of nickel nitrate, nickel sulfate, nickel acetate or nickel chloride；It is described
It is at least one of butyl titanate, tetraisopropyl titanate or tetraethyl titanate containing titanium salt.
Preferred scheme, the organic ligand are Isosorbide-5-Nitrae-terephthalic acid (TPA) or 1, at least one in 3,5- trimesic acids
Kind.
Preferred scheme, the organic solvent are at least one of methanol, N ' dinethylformamide or ethyl alcohol.
Preferred scheme, the pre-heat treatment time are 1~2h；The heat treatment time is 3~9h.
Preferred scheme is placed in 50~80 DEG C after the heat treatment reaction product is washed repeatedly using dilute acid soln and water
Under the conditions of temperature, it is dried in vacuo 8~12h.
Dilute acid soln is dilute acid soln well known in the art, is alternately and repeatedly washed using diluted acid and water, can be by remaining gold
Belong to the impurity removal generated in oxide and carbonisation.
More preferably scheme, the dilute acid soln are at least one of dilute hydrochloric acid, dilute sulfuric acid or dust technology.
In preparation method of the invention, transiting metal nickel, the bimetallic MOFs forerunner of titanium ion are contained by high-temperature process
Body, bimetallic MOFs (Metal Organic Frameworks- metal-organic framework material) presoma are keeping its original
It is carbonized under the premise of basic cellular structure and microscopic appearance, has obtained the loose porous titanium with disk like nanostructure
Sour nickel material.
In specific preparation process, by the pre-heat treatment, promotes organic solvent volatilization in cellular structure, sufficiently open double
Cellular structure inside metal MOFs presoma, after bonding continuous heat treatment, carries out high temperature cabonization, makes metal titanium ion and nickel
Ion generation is fully oxidized, under the premise of keeping its stable appearance, retains the cellular structure that bimetallic MOFs presoma has,
The disk like metatitanic acid nickel material with loose and porous structure is finally obtained.Loose porous nickel titanate negative electrode material can not only increase
Add the wetting contact area of electrode material and electrolyte, and can effectively alleviate electrode material in sodium ion intercalation/deintercalation
Caused volume change in the process, to be conducive to improve the cyclical stability and high rate performance of sodium-ion battery.
Bimetallic MOFs presoma of the invention is by transition metal salt, organic ligand and organic solvent according to certain ratio
After example mixing, prepared by solvent-thermal method.
Disk like nano barium titanate nickel material of the invention is by bimetallic MOFs presoma by low-temperature prewarming and high temperature cabonization two
A step generates.
Further preferably prepare nickel titanate negative electrode material method comprising the following specific steps
1) transition metal salt containing nickel salt and the composition containing titanium salt is completely dissolved in organic solvent, be added has while stirring
Machine ligand；
2) it after mixing evenly, moves to and carries out solvent thermal reaction in ptfe autoclave liner, be centrifuged, washed, done
After dry, Ti-Ni bimetallic MOFs presoma can be obtained；
3) gained bimetallic MOFs presoma is placed in vacuum tube furnace, under oxygen atmosphere, first carries out low-temperature prewarming
Processing, then carry out high temperature cabonization；
4) step 3) products therefrom dilute sulfuric acid and deionized water are washed repeatedly, it is dry to get nickel titanate negative electrode material.
The sodium-ion battery performance test methods of nickel titanate negative electrode material prepared by the present invention: weighing above-mentioned material, is added
For 10wt.%Super P as conductive agent, 10wt.% sodium carboxymethylcellulose (CMC) is used as binder, it is ground sufficiently after
A small amount of deionized water is added and is mixed to form uniform black paste slurry, slurry is coated in copper foil current collector as test electricity
Pole, with metallic sodium piece, electrode assembling becomes 2025 button cells as a comparison, uses electrolyte system for 1M NaClO4/EC:
DEC (1:1)+5%FEC, for Celgard 2400, charging and discharging currents density used in test loop performance is the diaphragm used
50mA/g。
Compared with the prior art, technical solution of the present invention bring the utility model has the advantages that
1) nickel titanate negative electrode material of the invention has loose porous saucer-like configuration, and it is living that this architecture provides storage sodium abundant
Property site and sodium ion transmission channel.Meanwhile the porous structure of nano material can not only increase the wetting of material and electrolyte
Contact area, and the volume expansion generated in electrode material and sodium ion reaction process can be effectively relieved, and then be conducive to
Improve the cyclical stability and high rate performance of sodium-ion battery.
2) operation is simple and reliable for the method for the invention for preparing metatitanic acid nickel material, reproducible, environmental-friendly, low in cost,
With wide industrial applications prospect.
Detailed description of the invention
[Fig. 1] is the X-ray diffractogram (XRD) of nickel titanate negative electrode material made from embodiment 1；
[Fig. 2] is the scanning electron microscope (SEM) photograph (SEM) of nickel titanate negative electrode material made from embodiment 1；
[Fig. 3] is the transmission electron microscope picture (TEM) of nickel titanate negative electrode material made from embodiment 1；
[Fig. 4] is the constant current charge-discharge performance map of the sodium-ion battery of the assembling of nickel titanate negative electrode material made from embodiment 1；
[Fig. 5] is the high rate performance figure of the sodium-ion battery of the assembling of nickel titanate negative electrode material made from embodiment 1.
[Fig. 6] is the scanning electron microscope (SEM) photograph (SEM) of nickel titanate negative electrode material made from comparative example 1；
[Fig. 7] is the scanning electron microscope (SEM) photograph (SEM) of nickel titanate negative electrode material made from comparative example 2；
[Fig. 8] is the constant current charge-discharge performance map of the sodium-ion battery of the assembling of nickel titanate negative electrode material made from comparative example 3；
Specific embodiment
Following embodiment is intended to be described in further details the content of present invention；And the protection scope of the claims in the present invention
It is not limited by the example.
Embodiment 1
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In the mixed solution of base formamide and 200ml methanol composition, 9.96g Isosorbide-5-Nitrae-terephthalic acid (TPA) is then weighed in magnetic agitation item
It is slowly added under part in above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly,
Solvent thermal reaction being carried out under the conditions of 160 DEG C, by gained sediment through methanol and N after reaction 18h ' dinethylformamide is anti-
After backwashing is washed, and Ti-Ni bimetallic MOFs presoma can be obtained in drying.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 1.5h at this temperature；Then, continue for tube furnace to be warming up to
700 DEG C and fully oxidized 6h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain
Nickel titanate nano material.
Button cell is assembled into using sodium-ion battery nickelous carbonate nanometer anode material manufactured in the present embodiment and sodium piece,
Material structure characterization and chemical property are as shown in the figure:
In Fig. 1 contrast standard diffracting spectrum illustrate in metatitanic acid nickel material without other impurities, be single NiTiO3It is brilliant
Body.
It can be seen that the metatitanic acid nickel material prepared has loose porous disk like nanostructure in Fig. 2, Fig. 3, wherein
Nickel titanate nanoparticle size is 200~400nm.
Show the electrode using the production of metatitanic acid nickel material in Fig. 4, under the constant-current discharge density of 50mA/g, 200 circle of circulation
Specific discharge capacity may remain in 520mAh/g, show good stable circulation performance.
Show the high rate performance using the electrode of nickel titanate negative electrode material production under different discharge current densities in Fig. 5
Figure, as can be seen from the figure the composite material has excellent high rate performance, even if under the conditions of the heavy-current discharge of 2A/g still
The charge specific capacity that can keep 180mAh/g, after current density is restored to 200mA/g, specific discharge capacity again can be again
Reach 310mAh/g.
Embodiment 2
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 400mL N ' N- diformazan
In base formamide, then weighs 6.64g Isosorbide-5-Nitrae-terephthalic acid (TPA) and is slowly added into above-mentioned solution under the conditions of magnetic agitation,
Gained mixed solution is transferred in ptfe autoclave after stirring evenly, it is anti-that solvent heat is carried out under the conditions of 160 DEG C
Answer, by gained sediment through methanol and N after reaction 14h ' dinethylformamide washs repeatedly, and Ti-Ni can be obtained in drying
Bimetallic MOFs presoma.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 1.5h at this temperature；Then, continue for tube furnace to be warming up to
600 DEG C and fully oxidized 6h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain
Nickel titanate nano material.
The metatitanic acid nickel material of this method preparation belongs to single NiTiO3.The material part pattern is rendered as loose porous
Disk like, nanoparticle size are 300~600nm.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation may remain in 470mAh/g.
Embodiment 3
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 400mL methanol solution
In, it then weighs 9.96g Isosorbide-5-Nitrae-terephthalic acid (TPA) and is slowly added into above-mentioned solution under the conditions of magnetic agitation, stirred evenly
Gained mixed solution is transferred in ptfe autoclave later, solvent thermal reaction is carried out under the conditions of 180 DEG C, is reacted
By gained sediment through methanol and N after 18h ' dinethylformamide washs repeatedly, and Ti-Ni bimetallic can be obtained in drying
MOFs presoma.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 1h at this temperature；Then, continue tube furnace being warming up to 700
DEG C and fully oxidized 4h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain metatitanic acid
Nickel nano material.
The metatitanic acid nickel material of this method preparation belongs to single NiTiO3.The microscopic appearance of the material is loose porous nothing
Shape shape, does not find apparent saucer-like configuration, and nanoparticle size is 400~700nm.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation may remain in 400mAh/g.
Embodiment 4
Six water nickel nitrate of 1.42g isopropyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In base formamide and 200ml methanol, then weighs 11.62g Isosorbide-5-Nitrae-terephthalic acid (TPA) and be slowly added under the conditions of magnetic agitation
In above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly, under the conditions of 160 DEG C into
Row solvent thermal reaction, by gained sediment through methanol and N after reaction 18h ' dinethylformamide washs repeatedly, and it is dry
Obtain Ti-Ni bimetallic MOFs presoma.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 2h at this temperature；Then, continue tube furnace being warming up to 800
DEG C and fully oxidized 4h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain metatitanic acid
Nickel nano material.
The metatitanic acid nickel material of this method preparation belongs to single NiTiO3.The metatitanic acid nickel material has loose porous disk like
Nanostructure, wherein nickel titanate nanoparticle size is 300~500nm.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation may remain in 500mAh/g.
Embodiment 5
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In base formamide and 200ml methanol, then weighs 13.28g Isosorbide-5-Nitrae-terephthalic acid (TPA) and be slowly added under the conditions of magnetic agitation
In above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly, under the conditions of 160 DEG C into
Row solvent thermal reaction, by gained sediment through methanol and N after reaction 15h ' dinethylformamide washs repeatedly, and it is dry
Obtain Ti-Ni bimetallic MOFs presoma.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 2h at this temperature；Then, continue tube furnace being warming up to 500
DEG C and fully oxidized 6h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain metatitanic acid
Nickel nano material.
The metatitanic acid nickel material of this method preparation belongs to single NiTiO3.The material morphology is rendered as loose porous dish
Shape, nanoparticle size are 500~800nm.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation may remain in 450mAh/g.
Comparative example 1
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In base formamide and 200ml methanol, then weighs 9.96g Isosorbide-5-Nitrae-terephthalic acid (TPA) and be slowly added under the conditions of magnetic agitation
In above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly, under the conditions of 160 DEG C into
Row solvent thermal reaction, by gained sediment through methanol and N after reaction 18h ' dinethylformamide washs repeatedly, and it is dry
Obtain Ti-Ni bimetallic MOFs presoma.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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
Washing is repeated in deionized water, is drying to obtain nickelous carbonate nano material.
The metatitanic acid nickel material of this method preparation belongs to single NiTiO3.The microscopic appearance of the material does not find loose more
The structure in hole, also without finding apparent saucer-like configuration, nanoparticle size is 600~800nm.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation is maintained at 300mAh/g.
Comparative example 2
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In base formamide and 200ml methanol, then weighs 9.96g Isosorbide-5-Nitrae-terephthalic acid (TPA) and be slowly added under the conditions of magnetic agitation
In above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly, under the conditions of 160 DEG C into
Row solvent thermal reaction, by gained sediment through methanol and N after reaction 10h ' dinethylformamide washs repeatedly, and it is dry
Obtain Ti-Ni bimetallic MOFs presoma.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 1.5h at this temperature；Then, continue for tube furnace to be warming up to
700 DEG C and fully oxidized 6h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain
Nickel titanate nano material.
The metatitanic acid nickel material of this method preparation is not single NiTiO3.The material morphology is disorderly and unsystematic, unfixed
Nano particle distributed area.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation is maintained at 250mAh/g.
Comparative example 3
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, is completely dissolved in it in 100ml ethylene glycol,
Gained mixed solution is transferred in polytetrafluoroethylene (PTFE) hydrothermal reaction kettle after stirring evenly, carries out hydro-thermal under the conditions of 180 DEG C
Reaction washs gained sediment through ethyl alcohol and deionized water after reaction for 24 hours repeatedly, and metatitanic acid nickel material can be obtained in drying.
More pure metatitanic acid nickel material in order to obtain is 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.It is washed finally, gained oxidation product is repeated with deionized water
It washs, is drying to obtain pure nickel titanate nano material.
The metatitanic acid nickel material of this method preparation belongs to single NiTiO3.The material does not have specific microscopic appearance, does not have yet
It is found loose porous structure, nanoparticle size is 800~1000nm.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation is maintained at 280mAh/g.
Comparative example 4
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In the mixed solution of base formamide and 200ml methanol composition, 9.96g Isosorbide-5-Nitrae-terephthalic acid (TPA) is then weighed in magnetic agitation item
It is slowly added under part in above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly,
Solvent thermal reaction being carried out under the conditions of 140 DEG C, by gained sediment through methanol and N after reaction 18h ' dinethylformamide is anti-
After backwashing is washed, and Ti-Ni bimetallic MOFs presoma can be obtained in drying.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 1.5h at this temperature；Then, continue for tube furnace to be warming up to
700 DEG C and fully oxidized 6h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain
Nickel titanate nano material.
The metatitanic acid nickel material of this method preparation is not single NiTiO3.The pattern and nanometer that the material is not fixed
Grain distributed area.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation may remain in 260mAh/g.
Comparative example 5
Six water nickel nitrate of 1.7g butyl titanate and 1.45g is weighed first, it is made to be completely dissolved in 200ml N ' N- diformazan
In the mixed solution of base formamide and 200ml methanol composition, 9.96g Isosorbide-5-Nitrae-terephthalic acid (TPA) is then weighed in magnetic agitation item
It is slowly added under part in above-mentioned solution, gained mixed solution is transferred in ptfe autoclave after stirring evenly,
Solvent thermal reaction being carried out under the conditions of 160 DEG C, by gained sediment through methanol and N after reaction 18h ' dinethylformamide is anti-
After backwashing is washed, and Ti-Ni bimetallic MOFs presoma can be obtained in drying.
Appropriate Ti-Ni bimetallic MOFs presoma is weighed, is 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 keep the temperature 1.5h at this temperature；Then, continue for tube furnace to be warming up to
400 DEG C and fully oxidized 6h.Finally, washing is repeated in gained oxidation product dilute sulfuric acid and deionized water, it is drying to obtain
Nickel titanate nano material.
The metatitanic acid nickel material of this method preparation is not single NiTiO3.Metallic nickel oxidation is insufficient inside the material, makees
It is blended in inside metatitanic acid nickel material for impurity, without obvious disk like pattern.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, in the perseverance of 50mA/g
It flows under power-discharging density, 200 circle specific discharge capacity of circulation may remain in 270mAh/g.
Claims (10)
1. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material, it is characterised in that: nickel salt will be contained and formed containing titanium salt
Transition metal salt and organic ligand in organic solvent, in 150-200 DEG C, pass through solvent structure bimetallic MOFs forerunner
Body；Then, it is passed through oxygen into bimetallic MOFs presoma, is first heated to 100~200 DEG C of progress the pre-heat treatments, is again heated to
500~800 DEG C are heat-treated；Finally, by gained heat-treated products by washing, it is dry to get.
2. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1, it is characterised in that: institute
State in solvent-thermal method, the reaction time be 12~for 24 hours.
3. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1, it is characterised in that: institute
The molar ratio for stating transition metal salt and organic ligand is 1:3~1:9；The molar ratio of the transition metal salt and organic solvent is 1:
200~1:700.
4. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1 or 3, feature exist
In: described containing nickel salt and the molar ratio containing titanium salt is 2:1~1:2.
5. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1, it is characterised in that: institute
Stating containing nickel salt is at least one of nickel nitrate, nickel sulfate, nickel acetate or nickel chloride；The titanium salt that contains is butyl titanate, titanium
At least one of sour tetra-isopropyl or tetraethyl titanate；The organic ligand is 1,4- terephthalic acid (TPA) or the equal benzene three of 1,3,5-
At least one of formic acid；The organic solvent is at least one of methanol, N ' dinethylformamide or ethyl alcohol.
6. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1, it is characterised in that: described
The pre-heat treatment time is 1~2h；Heat treatment time is 3~9h.
7. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1 or 3, feature exist
In: after the heat-treated products are washed repeatedly using dilute acid soln and deionized water, under the conditions of 50~80 DEG C, vacuum drying 8
~12h.
8. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 7, it is characterised in that: institute
The dilute acid soln stated is at least one of dilute hydrochloric acid, dilute sulfuric acid or dust technology.
9. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1, it is characterised in that: institute
It states metatitanic acid nickel material and loose porous round saucer-like configuration is presented.
10. a kind of preparation method of sodium-ion battery nickel titanate negative electrode material according to claim 1, it is characterised in that:
The metatitanic acid nickel material is nano particle, a diameter of 200~800nm.
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