CN108470903A - A kind of method of modifying of anode material of lithium-ion battery titanium dioxide - Google Patents
A kind of method of modifying of anode material of lithium-ion battery titanium dioxide Download PDFInfo
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- CN108470903A CN108470903A CN201810229179.6A CN201810229179A CN108470903A CN 108470903 A CN108470903 A CN 108470903A CN 201810229179 A CN201810229179 A CN 201810229179A CN 108470903 A CN108470903 A CN 108470903A
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The present invention provides a kind of method of modifying of anode material of lithium-ion battery titanium dioxide, and titanium source, structure directing agent are mixed to form titaniferous solution, nano-TiO 2 precursor is prepared by hydro-thermal reaction；The titanium source and the molar ratio of structure directing agent 1:0.1 1, the proportionate relationship of the titanium source and solvent is 0.01 0.5mol:1L；Nano-TiO 2 precursor obtained above is mixed with solid-state nitrogen source, the mass ratio of the titanium source and nitrogen source is 1:0.1 10, after stirring, grinding, mixture is calcined in protective gas to get anode material of lithium-ion battery titanium dioxide.In the method for the invention, the cladding of titanium nitride membrane can significantly enhance electron conduction, and then improve the storage sodium capacity and high rate performance of titanic oxide material；Nitrogen-doping can further effectively improve the electric conductivity of titanium dioxide simultaneously, to show excellent chemical property.
Description
Technical field
The invention belongs to technical field of chemical power, are related to a kind of sodium-ion battery, specifically a kind of sodium ion electricity
The method of modifying of pond negative material titanium dioxide.
Background technology
Sodium-ion battery has the characteristics that resourceful, of low cost, feed distribution is extensive, while sodium and lithium are member of the same clan
Element has similar physics and chemical property, therefore sodium-ion battery provides new possibility for energy storage technology.Due to sodium ion
RadiusThan lithium ion radiusIt is big by 35%, to hinder insertion and abjection in graphite platelet structure, because
This graphite for being commonly used for lithium ion battery negative material can not continue in sodium-ion battery, especially in high rate charge-discharge
In the case of, sodium ion deintercalation is more difficult, poor so as to cause high rate performance.Therefore, anode material of lithium-ion battery has become
The main reason for restricting sodium-ion battery development, it is extremely urgent to the research of negative material.
Titanium dioxide has the characteristics such as resourceful, environmental-friendly, non-toxic, of low cost, while as a kind of wide taboo
The semi-conducting material of band has received widespread attention in research fields such as photocatalysis, solar cells.In addition, researcher has found
Titanium dioxide has higher structural stability, smaller cubical expansivity and relatively mild voltage platform, therefore dioxy
Change titanium has potential application prospect in lithium, sodium-ion battery field.However, lower ion diffusion rates and poor electronics
Electric conductivity can not provide satisfactory high rate performance, and then limit its application in energy storage field.
In order to improve the chemical property of titanium dioxide, researcher has done many deeply significant works from many aspects
Make.Studies have shown that ion diffusion path can be shortened by reducing the grain size of titanic oxide material.For example, nano-titanium dioxide shows
Go out 200 mAh g-1The discharge capacity and good cycle performance (Journal of Materials Chemistry A of left and right
16(2015)8800).Meanwhile in order to further increase chemical property, conductive layer cladding and element doping are also recycled for a long time
Middle raising electron conduction, and consolidate crystal structure, such as graphene coated titanium dioxide (Journal of Materials
Chemistry A 31 (2014) 12449), nitrogen-doped titanium dioxide (Small 26 (2016) 3522).Conductive layer coats not only
The electron conduction of material can be improved, moreover it is possible to inhibit the volume change of material in cyclic process.However, due to the preparation of graphene
Method is relatively complicated and will produce a large amount of spent acid in the process, these problems restrict the development of sodium-ion battery and actually answer
With.
Invention content
For above-mentioned technical problem in the prior art, the present invention provides a kind of anode material of lithium-ion battery titanium dioxides
The method of modifying of titanium, the method for modifying of this anode material of lithium-ion battery titanium dioxide will solve in the prior art
The relatively low technical problem of high rate performance caused by the poor electron conduction of titanium dioxide.
The present invention provides a kind of method of modifying of anode material of lithium-ion battery titanium dioxide, include the following steps：
(1) titanium source, structure directing agent, solvent are mixed to form titaniferous solution, nanometer titanium dioxide is prepared by hydro-thermal reaction
Titanium precursors；The titanium source and the molar ratio of structure directing agent 1:The ratio material ratio of 0.1-1, the titanium source and solvent is 0.01-
0.5mol:1L；
(2) nano-TiO 2 precursor that step (1) obtains is mixed with solid-state nitrogen source, the titanium source and nitrogen source
Mass ratio be 1:0.1-10 calcines mixture after stirring, grinding in protective gas, calcining heating speed
Rate is 2-10 DEG C/min, and calcination temperature is 350-800 DEG C, and calcination time is 2-10 hours to get anode material of lithium-ion battery
Titanium dioxide.
Further, the titanium source described in step (1) is selected from butyl titanate, tetraethyl titanate, tetraisopropyl titanate, sulfuric acid
The combination of one or more of titanium, titanyl sulfate, titanium tetrachloride.
Further, the structure directing agent described in step (1) is selected from hydrofluoric acid, ammonium fluoride, cetyl trimethyl bromination
The group of one or more of ammonium, neopelex, polyvinylpyrrolidone, 3- aminopropyl triethoxysilanes
It closes.
Further, the solvent described in step (1) is selected from one or more of ethyl alcohol, water, acetone, ethylene glycol
Combination.
Further, the solid-state nitrogen source described in step (2) be selected from biuret, glycine, urea, melamine, dicyandiamide,
The combination of one or more of ethylenediamine tetra-acetic acid.
Further, hydro-thermal method carries out in reaction kettle in step (1), and reaction temperature is 80-220 DEG C.
Further, step (2) described protective gas is that nitrogen, argon gas or nitrogen are argon-mixed.
Further, step (2) calcining heating rate is 2-5 DEG C/min, and calcination temperature is 500-750 DEG C.
Further, the anode material of lithium-ion battery titanium dioxide obtained is Detitanium-ore-type structure.
As more preferred scheme, the one kind of titanium source in butyl titanate, tetraethyl titanate, tetraisopropyl titanate
Or it is a variety of.
As more preferred scheme, structure directing agent be selected from hydrofluoric acid, 3- aminopropyl triethoxysilanes, ammonium fluoride,
One or more of cetyl trimethylammonium bromide.
The titanium source and the molar ratio of structure directing agent 1 as a preferred technical solution,:0.2-0.6, the titanium source and nitrogen
The mass ratio in source is 1:The proportionate relationship of 0.1-4, the titanium source and solvent is 0.05-0.3mol:1L.
As a preferred technical solution, in the titaniferous solution titanium a concentration of 0.1-1mol/L.
Hydro-thermal method carries out in reaction kettle in step (1) as a preferred technical solution, and reaction temperature is 100-200 DEG C.
Protective gas is preferably nitrogen as a preferred technical solution,.
Calcining heating rate is 2-5 DEG C/min as a preferred technical solution, and calcination temperature is 500-750 DEG C, when calcining
Between be 3-6 hour, more preferred technical solution, step (2) calcine heating rate be 3 DEG C/min, calcination temperature 500-750
DEG C, calcination time is 4-6 hours.
The present invention is prepared for titanium nitride thin using biuret as solid-state nitrogen source, by a kind of simple solid-phase sintering method
The nitrogen-doped titanium dioxide of film cladding.The cladding of titanium nitride membrane can not only significantly increase electron conduction, and then improve
The storage sodium capacity and high rate performance of titanic oxide material；Nitrogen-doping can further effectively improve titanium dioxide simultaneously
Electric conductivity to show excellent chemical property, and can inhibit the volume expansion in charge and discharge process, improve dioxy
Change the cyclical stability of titanium material；To improve storage sodium performance of the titanium dioxide under high magnification.
Using material made from this method when being used as sodium ion negative material, titanium nitride of the invention coats N doping two
The mass ratio of titania meterial, binder and conductive agent is 8:(0.5~2):(0.1~2)；Binder is hydroxymethyl cellulose
(CMC), one kind in PVDF, sodium alginate；Conductive agent is a kind of or more in acetylene black, Ketjen black, carbon black, super P
Kind；Collector is one kind among copper foil or nickel foam；Drying temperature is 60~120 DEG C；Drying mode be vacuum drying or
One kind of person's forced air drying.
Compared with prior art, the present invention its technological progress is significant.The preparation method of the present invention is simple, passes through solid phase
Sintering prepares the nitrogen-doped titanium dioxide material of titanium nitride cladding, and abundant raw materials are cheap, are produced on a large scale.This hair
Bright preparation process condition is mild, and hydrothermal reaction process not will produce pernicious gas or pollutant with high-temperature burning process, have
Environmental-friendly feature.Show the nitrogen-doped titanium dioxide conduct of titanium nitride cladding disclosed by the invention by electro-chemical test
Sodium ion negative material has more outstanding cycle performance and high rate performance, for the research and application of sodium-ion battery from now on
Provide method support.The method of the present invention is simple, is easy to mass produce.
Description of the drawings
Fig. 1 is the XRD diagram of the nitrogen-doped titanium dioxide material for the titanium nitride cladding that embodiment 1 is prepared；
The N 1s figures that Fig. 2 is the XPS of the nitrogen-doped titanium dioxide material for the titanium nitride cladding that embodiment 1 is prepared；
Fig. 3 is the TEM figures of the nitrogen-doped titanium dioxide material for the titanium nitride cladding that embodiment 1 is prepared；
Fig. 4 is the high rate performance figure of the nitrogen-doped titanium dioxide material for the titanium nitride cladding that embodiment 1 is prepared；
Fig. 5 is the EIS figures of the nitrogen-doped titanium dioxide material for the titanium nitride cladding that embodiment 1 is prepared.
Specific implementation mode
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.
The preparation of sodium-ion battery uses this field conventional means, i.e., is to electrode with metallic sodium；With being dissolved in for 1mol/L
Mass ratio is 1:NaClO in the mixed solution of 1 ethylene carbonate (EC)/dimethyl carbonate (DMC)4Salting liquid is as electrolysis
Liquid；It is assembled into button cell in the glove box of argon gas atmosphere protection.Using Wuhan Lan electricity companies CT2001A type cell testers
Carry out electrochemical property test, charging/discharging voltage ranging from 0.01V~2.5V (vs.Na+/ Na), test temperature is 25 DEG C.
Embodiment 1
3.4g butyl titanates are added into 20ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g biurets in a nitrogen atmosphere, with pipe
Formula stove is warming up to 500 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the N doping of titanium nitride cladding is made after natural cooling
Titanic oxide material.Fig. 1 is XRD diagram, and as seen from the figure, material prepared by the above method is anatase titanium dioxide (JCPDS：
No.21-1272)；With pure phase TiO2It compares, modified sample occurs more faint new diffraction maximum at 42.7 degree, right
It should be in TiN (JCPDS：No.87-0632 diffraction maximum), it was demonstrated that the presence of titanium nitride in composite material.Pass through Scherrer formula meter
The crystallite dimension of the N doping composite material of titanium nitride cladding is 16.9nm known to calculating, hence it is evident that is less than pure phase TiO2(20.4nm),
Prove that titanium nitride coating modification can reduce the crystallite dimension of titanium dioxide.
Fig. 2 is that the XPS of composite material tests N 1s collection of illustrative plates, 3 peaks occurs from the N 1s spectrums found out on figure, is located at
In conjunction with that can be 395.4,397.2 and 399.5eV, correspond to Ti-O-N keys, Ti-N keys and Ti-N-O keys.Wherein it is located at 397.2eV
Ti-N keys be proved to be the formation due to TiN.And the Ti-O-N keys positioned at 395.4eV are since part N atoms are instead of part O
Atom is formed by.In conjunction with can be caused by N atoms by partial adsorbates for the Ti-N-O keys of 399.5eV.Therefore illustrate multiple
The constituent of condensation material is the compound of titanium nitride and nitrogen-doped titanium dioxide.Fig. 3 is that the TEM of composite material schemes, as seen from the figure,
The granular size of the nitrogen-doped titanium dioxide material of titanium nitride cladding is about 30nm, this is conducive to shorten ion diffusion path, from
And improve the chemical property of material.
It is prepared by cathode：By titanium nitride cladding nitrogen-doped titanium dioxide negative material, conductive carbon black and the bonding of above-mentioned preparation
Agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, electrode slice is struck out after dry, in 100
DEG C vacuum drying 12h.
Fig. 4 is the high rate performance figure of the button cell of above-mentioned cathode the assembling, (1C=under the different multiplying of 0.1C-10C
335mA g-1) 10 charge-discharge tests are carried out respectively.As seen from the figure under 0.1C, 0.2C., 0.5C, 1C, 2C, 5C and 10C multiplying power
The N doping TiO of titanium nitride cladding2The reversible specific capacity that the capacity of composite material is is respectively 226.9mA h g–1, 212.7mA
h g–1, 198.3mA h g–1, 190.7mA h g–1, 180.2mA h g–1With 166.6mA h g–1；Meanwhile in 10C (3350mA
g–1) high magnification under reversible specific capacity reach 158.3mA h g–1, in contrast, pure phase TiO2Ratio under identical multiplying power
Capacity is only 183.8mA h g–1, 169.4mA h g–1, 153.9mA h g–1, 144.3mA h g–1, 134.9mA h g–1,
124.4mA h g–1, 116.7mA h g–1.In addition, after 70 cycles under the multiplying power by being sequentially increased, by charge and discharge times
Rate is restored to 0.1C, and the reversible specific capacity of composite material still has 206.7mA h g–1, and pure phase TiO2Capacity be only 173.5mA
h g–1.The N doping TiO of titanium nitride cladding2Possess high rate performance excellent in this way, be mainly due to titanium nitride membrane cladding with
The synergistic effect of nitrogen-doping improves the electron conduction of titanic oxide material.
Fig. 5 is button cell electrochemical impedance spectrogram prepared by above-mentioned cathode, as shown, the N doping of titanium nitride cladding
TiO2Charge-transfer resistance be about 77 Ω, hence it is evident that be less than pure phase TiO2(330 Ω), it was demonstrated that titanium nitride membrane cladding and nitrogen
The synergistic effect of element doping significantly improves the electron conduction of titanic oxide material, to improve the forthright again of material
Energy.
Embodiment 2
3.4g butyl titanates are added into 20ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g melamines in a nitrogen atmosphere, is used
Tube furnace is warming up to 700 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the nitrogen that titanium nitride cladding is made after natural cooling is mixed
Miscellaneous titanic oxide material.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Embodiment 3
3.4g butyl titanates are added into 50ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g urea in a nitrogen atmosphere, uses tubular type
Stove is warming up to 700 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the N doping two of titanium nitride cladding is made after natural cooling
Titania meterial.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Embodiment 4
3.4g butyl titanates are added into 50ml absolute ethyl alcohols, the hydrofluoric acid that 3ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g biurets in a nitrogen atmosphere, with pipe
Formula stove is warming up to 700 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the N doping of titanium nitride cladding is made after natural cooling
Titanic oxide material.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Embodiment 5
3.4g butyl titanates are added into 50ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g biurets in a nitrogen atmosphere, with pipe
Formula stove is warming up to 750 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the N doping of titanium nitride cladding is made after natural cooling
Titanic oxide material.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Embodiment 6
3.4g butyl titanates are added into 50ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g glycine in a nitrogen atmosphere, with pipe
Formula stove is warming up to 700 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the N doping of titanium nitride cladding is made after natural cooling
Titanic oxide material.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Embodiment 7
3.4g butyl titanates are added into 50ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, after being mixed with 1g dicyandiamides in a nitrogen atmosphere, with pipe
Formula stove is warming up to 700 DEG C with the rate of 3 DEG C/min and constant temperature keeps 4h, and the N doping of titanium nitride cladding is made after natural cooling
Titanic oxide material.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Embodiment 8
3.4g butyl titanates are added into 50ml absolute ethyl alcohols, the hydrofluoric acid that 5ml a concentration of 40% is then added is molten
Liquid is sufficiently stirred, and for 24 hours, presoma is collected by centrifugation in 180 DEG C of hydro-thermal reactions, in nitrogen atmosphere after being mixed with 1g ethylenediamine tetra-acetic acids
Under, 700 DEG C being warming up to the rate of 3 DEG C/min with tube furnace and constant temperature keeping 4h, titanium nitride cladding is made after natural cooling
Nitrogen-doped titanium dioxide material.
It is prepared by cathode：By the nitrogen-doped titanium dioxide negative material of the titanium nitride cladding of above-mentioned preparation, conductive carbon black and glue
Tie agent carboxymethyl cellulose (CMC) in mass ratio 8:1:1 is uniformly mixed, and is coated on copper foil, and electrode slice is struck out after dry, in
100 DEG C of vacuum drying 12h.
Claims (9)
1. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide, it is characterised in that：Include the following steps：
(1) titanium source, structure directing agent dispersion are mixed to form titaniferous solution in a solvent, nano-silica is prepared by hydro-thermal reaction
Change titanium precursors；The titanium source and the molar ratio of structure directing agent 1:The material ratio of 0.1-1, the titanium source and solvent is 0.01-
0.5mol:1L；
(2) nano-TiO 2 precursor that step (1) obtains is mixed with solid-state nitrogen source, the matter of the titanium source and nitrogen source
Amount is than being 1:0.1-10 calcines mixture after stirring, grinding in protective gas, and calcining heating rate is
2-10 DEG C/min, calcination temperature is 350-800 DEG C, and calcination time is 2-10 hours to get anode material of lithium-ion battery dioxy
Change titanium.
2. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide according to claim 1, it is characterised in that：
Titanium source described in step (1) is selected from butyl titanate, tetraethyl titanate, tetraisopropyl titanate, titanium sulfate, titanyl sulfate, tetrachloro
Change the combination of one or more of titanium.
3. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide according to claim 1, it is characterised in that：
Structure directing agent described in step (1) is selected from hydrofluoric acid, ammonium fluoride, cetyl trimethylammonium bromide, dodecyl benzene sulfonic acid
The combination of one or more of sodium, polyvinylpyrrolidone, 3- aminopropyl triethoxysilanes.
4. a kind of preparation method of anode material of lithium-ion battery titanium dioxide according to claim 1, which is characterized in that
Solvent described in step (1) is selected from the combination of one or more of ethyl alcohol, water, acetone, ethylene glycol.
5. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide according to claim 1, it is characterised in that：
Solid-state nitrogen source described in step (2) is in biuret, glycine, urea, melamine, dicyandiamide, ethylenediamine tetra-acetic acid
A combination of one or more.
6. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide according to claim 1, it is characterised in that：
Hydro-thermal method carries out in reaction kettle in step (1), and reaction temperature is 80-220 DEG C.
7. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide according to claim 1, it is characterised in that：
Step (2) described protective gas is that nitrogen, argon gas or nitrogen are argon-mixed.
8. a kind of method of modifying of anode material of lithium-ion battery titanium dioxide according to claim 1, it is characterised in that：
It is 2-5 DEG C/min that step (2), which calcines heating rate, and calcination temperature is 500-750 DEG C.
9. a kind of modification of anode material of lithium-ion battery titanium dioxide according to any one of claim 1-8 claims
Method, it is characterised in that：The anode material of lithium-ion battery titanium dioxide obtained is Detitanium-ore-type structure.
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