CN106450255B - A kind of NiTiO of sodium-ion battery3/ C negative electrode material, preparation and application - Google Patents
A kind of NiTiO of sodium-ion battery3/ C negative electrode material, preparation and application Download PDFInfo
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- CN106450255B CN106450255B CN201610970093.XA CN201610970093A CN106450255B CN 106450255 B CN106450255 B CN 106450255B CN 201610970093 A CN201610970093 A CN 201610970093A CN 106450255 B CN106450255 B CN 106450255B
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- 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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- 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
- H01M4/1393—Processes of manufacture of electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
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- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
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Abstract
The invention discloses a kind of NiTiO of sodium-ion battery3/ C negative electrode material, for the micro-spherical particle assembled by the metatitanic acid nano nickel particles for being coated with carbon.In addition, by organic acid, titanium source, nickel source and dispersed carbon source dissolution and/or dispersing in a solvent the invention also discloses the preparation method of the material and being stirred to react to obtain mixed liquor；Again by mixed liquor be spray-dried presoma nano particle, the NiTiO then is made through calcination processing again3/ C negative electrode material.The invention also discloses the materials in the application for preparing sodium-ion battery cathode.NiTiO of the present invention3/ C negative electrode material has excellent chemical property；The NiTiO prepared using spray drying process combination high-temperature heat treatment3/ C negative electrode material, processability is good, and tap density is high, and the preparation method simple process, and high production efficiency, production capacity is big, low in cost, great industrialized production and application potentiality.
Description
Technical field
The present invention relates to anode material of lithium-ion battery preparation fields, and in particular to a kind of composite material of nickel titanate and carbon
And preparation method and application.
Background technique
Lithium ion battery due to height ratio capacity, high-energy density and be widely used in portable electronic device and ion
Popularization and application of the battery in large-scale energy-storage system field.Sodium-ion battery be considered as effective substitute of lithium ion battery at
For domestic and international research hotspot.Sodium have and lithium similar in physicochemical properties, and reserves of the sodium resource in the earth's crust are considerable
(crustal abundance of lithium is 0.006%, and the crustal abundance of sodium is 2.64%), thus in cost to have very big advantage, this
So that sodium-ion battery becomes a kind of most potential battery system that can be used for extensive energy storage commercial applications.
The ionic radius (1.02nm) of sodium ion is also bigger by 55% than lithium ion radius (0.76nm), traditional Carbon anode such as stone
Ink can not achieve the reversible deintercalation of sodium ion, therefore finds suitable anode material of lithium-ion battery and promote as sodium-ion battery
One step of key of application.
Summary of the invention
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to provide a kind of good dispersion, soilless sticking, shape is uniform
NiTiO3/ C negative electrode material (is also referred to as NiTiO in the present invention3/ C anode material or referred to as negative electrode material).
Another object of the present invention is to provide a kind of reproducible, strong operabilitys, environmental-friendly, low in cost, tool
There is a step spray drying process of wide industrial applications prospect to prepare sodium-ion battery NiTiO3The system of/C negative electrode material
Preparation Method.
Another object of the present invention is to provide one kind to be applied in sodium-ion battery with high charge-discharge specific capacity, well
High rate performance and stable circulation performance contain above-mentioned NiTiO3The cathode of/C negative electrode material.
The purpose of the present invention is achieved through the following technical solutions:
A kind of NiTiO of sodium-ion battery3/ C negative electrode material, to be assembled by the metatitanic acid nano nickel particles for being coated with carbon
Micro-spherical particle.
NiTiO of the present invention3/ C negative electrode material, by the NiTiO for being coated with carbon source3Nano particle through calcination processing
The microspheroidal structure being self-assembled into, the NiTiO3The material of/C and the negative electrode material of architectural characteristic have good electrical property
Energy.
Preferably, the NiTiO of the sodium-ion battery3/ C negative electrode material, the micro-spherical particle partial size are 0.5
~3 microns；Specific surface area is 30~200m2g-1。
Further preferably, the NiTiO3In/C negative electrode material, NiTiO3Mass fraction be 90%~95%.
The present invention also provides the NiTiO described in one kind3The preparation method of/C negative electrode material, by nickel source, titanium nickel, organic
Acid, dispersed carbon source is spray-dried, calcines.
Preferably, the NiTiO of the sodium-ion battery3The preparation method of/C negative electrode material, by organic acid, titanium source,
Nickel source and dispersed carbon source dissolve and/or disperse in a solvent and be stirred to react to obtain mixed liquor；Mixed liquor is spray-dried again
Then the NiTiO is made through calcination processing again in the nano particle of presoma3/ C negative electrode material.
In preparation method of the present invention, help to be made the dispersed carbon source packet by the spray drying
Cover the presoma nano particle (nano particle) of nickel titanate inner core；Then again through calcination processing, and then make described
Nano-particles self assemble at the microspheroidal (micron order ball-type or class ball shape structure) NiTiO3/ C negative electrode material.
In the method for the present invention, in the spray-drying process and in conjunction with the heat treatment under the Parameter Conditions, it can be made
Pattern is the NiTiO of the micro-spherical particle formed by a nano-particles self assemble of coated with carbon3/ C negative electrode material, into
And improve material structure and electric conductivity.The method of the present invention helps to reduce and reunite, sphericity height and size tunable.Side of the present invention
Method processability is good, and tap density is high, and simple process, high-efficient, yield is big, is conducive to industrialization large-scale production, has extensive
Application prospect；And NiTiO obtained3/ C negative electrode material has high charge-discharge specific capacity and good cyclical stability.
The inventors discovered that helping to be made with before uniform morphology by the parameter area for regulating and controlling spray-drying process
Body is driven, and then facilitates the electric property for further improving calcined product.
Preferably, the entrance wind-warm syndrome of spray-drying process is 160~200 DEG C, the flow of mixed liquor is 400~
600mL/h.Under the preferred spray drying condition, help that the nickel titanate material with higher degree and specific morphology is made
Material, and can further promote final NiTiO obtained3The electric property of/C negative electrode material.
Further preferably, the entrance wind-warm syndrome of spray-drying process is 170~190 DEG C, the flow of mixed liquor is 450~
550mL/h。
Most preferably, the entrance wind-warm syndrome of spray-drying process is 170~180 DEG C, and the flow of mixed liquor is 500~550 mL/
h。
The cooperation spray drying parameters, preferably, the temperature of calcination process is 600~900 DEG C.
The inventors discovered that the electric property of material obtained is more excellent under the calcination condition.
Further preferably, the temperature of calcination process is 800~900 DEG C.
Facilitate that the NiTiO that pattern is uniform, electric property is excellent is made under the preferred calcination temperature3/ C cathode
Material.
The heating rate of calcination process is preferably 1~10 DEG C/min.
Calcination process carries out under protective atmosphere, and the protective atmosphere may be, for example, nitrogen atmosphere or indifferent gas
Body atmosphere (such as argon atmosphere).
Preferably, soaking time is 8~12h under the calcination temperature.
Dispersibility carbon source of the present invention serves not only as dispersing agent, also while being used as carbon source；It is existing that there is dispersibility
The Water Soluble Organic Carbon source of energy theoretically can be used.
Further preferably, the dispersed carbon source is at least one of polyethylene glycol, polystyrene, benzyl carbinol.
Preferably, the dispersed carbon source is polyethylene glycol, the molecular weight of preferred polyethylene glycol is less than or equal to
700。
The volume ratio of the dispersed carbon source and titanium source is 1: 2~16；Preferably 1: 4~8.
Titanium source, nickel source, organic acid and dispersed carbon source add proportionate relationship to guarantee obtained NiTiO3/ C cathode
In material, NiTiO3Mass fraction preferably between 90%~95%.
Preferably, the nickel source is water-soluble nickel compound and its hydrate.It is well known to those skilled in the art
Water-soluble inorganic nickel compound and its hydrate can be employed as nickel source.
Preferably, the nickel source is at least one of four water acetic acid nickel, nickel oxalate dihydrate, nickel acetylacetonate.
Further preferably, the nickel source is the water-soluble nickel compound with the crystallization water.
Most preferably, the nickel source is four water acetic acid nickel, nickel oxalate dihydrate.
In the present invention, what the titanium source can be well known to those skilled in the art is dissolvable in water the titanium in water or alcoholic solution
Organic compound.Preferably, the titanium source is at least one of butyl titanate, tetraethyl titanate, isopropyl titanate；Into
One step is preferably butyl titanate.
In the present invention, the Ti of titanium source4+With the Ni of nickel source2+Molar ratio be 1: 1.
In the present invention, the organic acid is added, helps that the uniform presoma nano material of pattern is further made.
The organic acid is preferably at least one of formic acid, acetic acid, oxalic acid.
Still more preferably, the organic acid is acetic acid.
Preferably, the volume ratio of organic acid and titanium source is 0.04~0.06: 0.15~0.35.
In the present invention, preferably, the solvent is at least one of water, the alcohol of C1~4.
The alcohol of the C1~4 is the unit and/or polyalcohol of 1~4 carbon number, such as methanol, ethyl alcohol, ethylene glycol, glycerine
Deng.
Further preferably, the solvent is at least one of water, ethyl alcohol.
In the present invention, using preferred solvent the material is dissolved and/or is dispersed, be stirred to react be made compared with
For clear mixed liquor；Subsequent spray-dried, calcination processing again.
Titanium source, nickel source, organic acid and dispersed carbon source are mixed 2~4h of reaction and obtain mixed liquor.It is stirred under the system
Reaction institute's preferred time is mixed, the mutual abundant reaction of material is facilitated, and then it is higher and have specific to help to be made purity
Nickel titanate presoma.
In the present invention, preferentially each material is individually dissolved, remixes spray drying.
Solution A is obtained preferably, organic acid, titanium source are dispersed in solvent a；Nickel source is dissolved in the water to obtain solution B；It will
Dispersed carbon source, which is dissolved in solvent b, obtains solution C；Then solution A, solution B, solution C are mixed, is stirred to react to obtain described
Mixed liquor；The solvent a and solvent b is independently chosen from the alcohol of C1~4.
Further preferably, the volume ratio of organic acid and solvent a are 1: 15~25 in solution A；The volume of titanium source and solvent a
Than being 1: 3~6；More preferably, the organic acid is acetic acid, solvent a is ethyl alcohol.
Further preferably, in solution B, the concentration of nickel source is 0.05~0.2g/mL；More preferably 0.05~0.15 g/mL.
Further preferably, in solution C, the volume ratio of dispersed carbon source and solvent b are 1: 50~150；It is further preferred that solvent b
For ethyl alcohol.
In the present invention, one kind more preferably NiTiO3The preparation method of/C negative electrode material, comprising the following steps:
Step (a): acetic acid, butyl titanate dissolution are obtained into titanium solution in ethanol, wherein the volume ratio of acetic acid and ethyl alcohol
It is 1: 15~25；The volume ratio of butyl titanate and ethyl alcohol is 1: 3~6；
Nickel acetate is dissolved in the water to obtain nickel solution, wherein the concentration of nickel acetate is 0.05~0.15g/mL；
Polyethylene glycol by molecular weight less than or equal to 700, which is dissolved in ethyl alcohol, must disperse carbon solution, wherein polyethylene glycol
Volume ratio with ethyl alcohol is 1: 50~150；Then dispersion carbon solution is added in titanium solution and nickel solution simultaneously under agitation
In, it is stirred to react 2~4h and obtains mixed liquor；
Step (b): the presoma of carbon-coated nickel titanate is made in the spray-dried processing of mixed liquor described in step (a)
Nano particle, the entrance wind-warm syndrome of spray-drying process are 160~200 DEG C, and the flow of mixed liquor is 400~600mL/h；
Step (c): presoma nano particle made from step (b) is warming up to 600 under the heating rate of 1~10 DEG C/min
~900 DEG C and 8~12h of heat preservation；The NiTiO is made3/ C negative electrode material.
First passage spray drying process combination high-temperature heat treatment of the present invention obtains a nano particle by coated with carbon
The microspheroidal NiTiO being self-assembly of3/ C negative electrode material.The material is for showing good electrochemistry in sodium-ion battery
Performance.
In the present invention, NiTiO made from the preparation method3/ C negative electrode material, to be received by the nickel titanate for being coated with carbon
The micro-spherical particle that rice grain assembles；The micro-spherical particle partial size is 0.5~3 micron；Specific surface area be 30~
200m2g-1；NiTiO3Mass fraction be 90%~95%.
It originally further include the NiTiO3The application of/C negative electrode material, by the NiTiO3/ C negative electrode material is used to prepare sodium
The cathode of ion battery.
For example, in the present invention, by NiTiO made from the preparation method3/ C negative electrode material prepares sodium-ion battery
Cathode.
The application, such as by the NiTiO3After/C negative electrode material is mixed with conductive agent and binder, pass through painting
It overlays on copper foil, sodium-ion battery cathode is made.Used conductive agent, binder can be used well known to those skilled in the art
Material.Assembling prepares the method for anode material of lithium-ion battery see also existing method.
For example, NiTiO produced by the present invention3The method that/C negative electrode material prepares sodium-ion battery cathode pole piece: first will
NiTiO3Material according to 8: 1: 1 mass ratio and conductive black (SP conductive agent) and sodium carboxymethylcellulose (CMC binder)
It is fully ground mixing, is then added dropwise after a small amount of deionized water is fully ground mixing and forms homogeneous liquid paste, apply
It overlays on as test electrode on copper foil matrix, with metallic sodium, button cell, electrolyte 1M is made in electrode as a comparison
NaClO4/ EC: DMC (1: 1)+5wt%FEC.
NiTiO3Electric conductivity is insufficient, is easy to appear a degree of volume expansion in cyclic process and makes the forthright again of material
It can not good enough, serious polarization under high current.NiTiO provided by the present invention3/ C negative electrode material can effectively solve the problems, such as described, tool
Have it is following the utility model has the advantages that
The beneficial effects of the present invention are: NiTiO is obtained by spray drying process combination high-temperature heat treatment3/ C cathode material
Material.The material morphology is the micro-spherical particle formed by a nano-particles self assemble of coated with carbon.By in the solution
Dispersed carbon source, which is added, makes material surface enclose one layer of organic carbon source, is effectively inhibiting material reunion to ask using spray drying process
Advantage in topic prepares the nano particle that surface is coated with carbon source.After high-temperature process, surface is coated with the one of carbon source
Secondary nano-particles self assemble becomes micro-spherical particle pattern.The microspheroidal formed by a nano-particles self assemble of carbon coated
Particle shape looks have biggish specific surface area, help to increase contact of the negative electrode material with electrolyte, and then be conducive to improve material
High rate performance.Meanwhile a nano particle of surface packet carbon, that is, the electric conductivity of material is increased, and material charge and discharge can be alleviated
Volume expansion problem in the process, further increases the high rate performance of material and cyclical stability.
NiTiO of the present invention3/ C anode material be made sodium-ion battery cathode in sodium-ion battery, show compared with
High reversible specific capacity and good cyclical stability and high rate performance.
NiTiO of the present invention3/ C negative electrode material processability is good, and tap density is high, and preparation process is simple, high-efficient, yield
Greatly, environmental-friendly, be conducive to industrialization large-scale production.
Detailed description of the invention
[Fig. 1] is NiTiO made from embodiment 13The X ray diffracting spectrum (XRD) of/C negative electrode material；
[Fig. 2] is NiTiO made from embodiment 13The scanning electron microscope (SEM) photograph (SEM) of/C negative electrode material；
[Fig. 3] is NiTiO made from embodiment 13Under the sodium-ion battery 50mA/g discharge current of/C negative electrode material assembling
Cycle performance figure；
[Fig. 4] is NiTiO made from embodiment 13The high rate performance figure of the sodium-ion battery of/C negative electrode material assembling；
[Fig. 5] is NiTiO made from embodiment 23The scanning electron microscope (SEM) photograph (SEM) of/C negative electrode material；
[Fig. 6] is NiTiO made from embodiment 23Under the sodium-ion battery 50mA/g discharge current of/C negative electrode material assembling
Cycle performance figure；
[Fig. 7] is NiTiO made from comparative example 13The scanning electron microscope (SEM) photograph (SEM) of/C negative electrode material.
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
2.5mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g (titanium/nickel molar ratio 1: 1), which is dissolved in 70mL deionized water, obtains solution B；Take 2mL polyethylene glycol
(600) it is added in 150mL dehydrated alcohol and obtains solution C.Then solution A and solution B are delayed simultaneously under the conditions of magnetic agitation
It is slow to be added in suspension C, 3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, peristaltic pump
Flow velocity is 500mL/h.Mixing suspension obtains precursor powder by spray drying, to precursor powder further progress high temperature
Heat treatment, temperature are 800 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.Specific surface area is 187m2/ g, particle diameter distribution are 0.5~2.5 micron.
Button cell, material table are assembled into using sodium-ion battery composite negative pole material manufactured in the present embodiment and sodium piece
Chemical property of seeking peace is as shown in the picture:
Fig. 1 is NiTiO3The X ray diffracting spectrum of/C negative electrode material.
It can be seen that NiTiO in Fig. 23The pattern of/C negative electrode material is microspheroidal.
Show in Fig. 3 using NiTiO3Electrode made of/C negative electrode material follows at room temperature in 50mA/g constant-current discharge
Ring 200, which encloses specific capacity, may remain in 470mAh/g；Show good cycle performance.
Show in Fig. 4 using NiTiO3Times of the corresponding battery of electrode made of/C negative electrode material under different discharge-rates
Rate performance map, it can be found that the composite material has excellent high rate performance, at big 1000 mA/g of multiplying power, capacity can still be protected
It holds in 310mAh/g, capacity is returned to 470mAh/g again after current density slowly returns to 100mA/g by high current.
Embodiment 2
2mL acetic acid is taken, 10mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；Weigh 7.3126g
Four water acetic acid nickel (titanium/nickel molar ratio 1: 1), which are dissolved in 100mL deionized water, obtains solution B；Take 2mL polyethylene glycol (600)
It is added in 150mL dehydrated alcohol and obtains solution C.Then solution A and solution B are slowly added to simultaneously under the conditions of magnetic agitation
In suspension C, 3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, and the flow velocity of peristaltic pump is
500mL/h.Mixing suspension obtains precursor powder by spray drying, at precursor powder further progress high warm
Reason, temperature are 800 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material (SEM figure is shown in Fig. 5).Specific surface area is 148m2/ g particle diameter distribution is 1~2.5 micron；
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, from constant current charge-discharge
In performance map 6 as can be seen that under the constant-current discharge density of 50mA/g, there are also 450mA/g for 200 circle specific discharge capacity of circulation.
Embodiment 3
2mL acetic acid is taken, 10mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；Weigh 7.3126g
Four water acetic acid nickel (titanium/nickel molar ratio 1: 1), which are dissolved in 100mL deionized water, obtains solution B；Take 2.5mL polyethylene glycol
(600) it is added in 150mL dehydrated alcohol and obtains solution C.Then solution A and solution B are delayed simultaneously under the conditions of magnetic agitation
It is slow to be added in suspension C, 3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, peristaltic pump
Flow velocity is 500mL/h.Mixing suspension obtains precursor powder by spray drying, to precursor powder further progress high temperature
Heat treatment, temperature are 700 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, from constant current charge-discharge
In performance map as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation be may remain in
420mAh/g。
Embodiment 4
3mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g (titanium/nickel molar ratio 1: 1), which is dissolved in 100mL deionized water, obtains solution B；Take the poly- second two of 2.5mL
Alcohol (600), which is added in 150mL dehydrated alcohol, obtains solution C.Then under the conditions of magnetic agitation by solution A and solution B simultaneously
It is slowly added in suspension C, 3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, peristaltic pump
Flow velocity be 500mL/h.Mixing suspension obtains precursor powder by spray drying, high to precursor powder further progress
Warm processing, temperature are 800 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.Finally
To NiTiO3/ C negative electrode material.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, from constant current charge-discharge
In performance map as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation be may remain in
460mAh/g。
Embodiment 5
3mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g (titanium/nickel molar ratio 1: 1), which is dissolved in 60mL deionized water, obtains solution B；Take 2mL polyethylene glycol
(600) it is added in 150mL dehydrated alcohol and obtains solution C.Then solution A and solution B are delayed simultaneously under the conditions of magnetic agitation
It is slow to be added in suspension C, 4h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, peristaltic pump
Flow velocity is 500mL/h.Mixing suspension obtains precursor powder by spray drying, to precursor powder further progress high temperature
Heat treatment, temperature are 900 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, from constant current charge-discharge
In performance map as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation be may remain in
450mAh/g。
Embodiment 6
3mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g (titanium/nickel molar ratio 1: 1), which is dissolved in 60mL deionized water, obtains solution B；Take 2mL polyethylene glycol
(600) it is added in 150mL dehydrated alcohol and obtains solution C.Then solution A and solution B are delayed simultaneously under the conditions of magnetic agitation
It is slow to be added in suspension C, 4h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 160 DEG C, peristaltic pump
Flow velocity is 400mL/h.Mixing suspension obtains precursor powder by spray drying, to precursor powder further progress high temperature
Heat treatment, temperature are 800 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.
Button cell is assembled into using anode material of lithium-ion battery manufactured in the present embodiment and sodium piece, from constant current charge-discharge
In performance map as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation be may remain in
415mAh/g。
Embodiment 7
3mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL ethylene glycol；Weigh 9.1340g
Four water acetic acid nickel (titanium/nickel molar ratio 1: 1), which are dissolved in 60mL deionized water, obtains solution B；2mL polyethylene glycol (600) is taken to add
It is added in 150mL ethylene glycol and obtains solution C.Then solution A and solution B are slowly added to simultaneously under the conditions of magnetic agitation suspended
In liquid C, 4h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 200 DEG C, and the flow velocity of peristaltic pump is
600mL/h.Mixing suspension obtains precursor powder by spray drying, at precursor powder further progress high warm
Reason, temperature are 800 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, is filled from constant current
In discharge performance figure as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation be may remain in
420mAh/g。
Embodiment 8
3mL oxalic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g (titanium/nickel molar ratio 1: 1), which is dissolved in 60mL deionized water, obtains solution B；2mL benzyl carbinol is taken to add
It is added in 150mL dehydrated alcohol and obtains solution C.Then under the conditions of magnetic agitation solution A and solution B are slowly added to hang simultaneously
In turbid C, 4h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, and the flow velocity of peristaltic pump is
500mL/h.Mixing suspension obtains precursor powder by spray drying, at precursor powder further progress high warm
Reason, temperature are 600 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.
Button cell is assembled into using sodium-ion battery anode material manufactured in the present embodiment and sodium piece, is filled from constant current
In discharge performance figure as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation be may remain in
395mAh/g。
Comparative example 1
0.5mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g (titanium/nickel molar ratio 1: 1), which is dissolved in 100mL deionized water, obtains solution B；Take 2mL polyethylene glycol
(600) it is added in 150mL dehydrated alcohol and obtains solution C.Then solution A and solution B are delayed simultaneously under the conditions of magnetic agitation
It is slow to be added in suspension C, 3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 120 DEG C, peristaltic pump
Flow velocity is 500mL/h.Mixing suspension obtains precursor powder by spray drying, to precursor powder further progress high temperature
Heat treatment, temperature are 800 DEG C, and heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.It finally obtains
NiTiO3/ C negative electrode material.
Reunited seriously it can be seen from SEM figure using material made from comparative example 1, does not synthesize feature of interest.Using this
The sodium-ion battery anode material and sodium piece of comparative example preparation are assembled into button cell, can from constant current charge-discharge performance map
To find out, under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation is only 175mAh/g.
Comparative example 2
1mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 5.243g, which is dissolved in 80mL deionized water, obtains solution B；Take 2mL polyethylene glycol (600) be added to 150mL without
Solution C is obtained in water-ethanol.Then solution A and solution B are slowly added in suspension C under the conditions of magnetic agitation simultaneously, are filled
Stirring 3h is divided to obtain mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, and the flow velocity of peristaltic pump is 500mL/h.Mixing
Suspension obtains precursor powder by spray drying, to precursor powder further progress high-temperature heat treatment, temperature 800
DEG C, heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.Finally obtain NiTiO3/ C negative electrode material.
Pure phase substance is not detected with XRD in the material.
Comparative example 3
2.5mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g, which is dissolved in 100mL deionized water, obtains solution B；1mL polyethylene glycol (600) is taken to be added to
Solution C is obtained in 150mL dehydrated alcohol.Then solution A and solution B are slowly added to suspension simultaneously under the conditions of magnetic agitation
In C, 3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, and the flow velocity of peristaltic pump is 500mL/
h.Mixing suspension obtains precursor powder by spray drying, to precursor powder further progress high-temperature heat treatment, temperature
It is 500 DEG C, heating rate is 5 DEG C/min, then soaking time 10h is down to room temperature naturally.Finally obtain NiTiO3/ C is negative
Pole material.Pure phase substance is not detected with XRD in the material.
Comparative example 4
2.5mL acetic acid is taken, 12.5mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g, which is dissolved in 70mL deionized water, obtains solution B；2mL polyethylene glycol (600) is taken to be added to 150mL
Solution C is obtained in dehydrated alcohol.Then solution A and solution B are slowly added in suspension C simultaneously under the conditions of magnetic agitation,
3h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, and the flow velocity of peristaltic pump is 350mL/h.It is mixed
It closes suspension and obtains precursor powder by spray drying, to precursor powder further progress high-temperature heat treatment, temperature 700
DEG C, heating rate is 5 DEG C/min, then soaking time 6h is down to room temperature naturally.Finally obtain NiTiO3/ C negative electrode material.
The XRD of the material shows that the nickel titanate prepared has more miscellaneous peak.
Button cell is assembled into using the sodium-ion battery anode material and sodium piece of this comparative example preparation, is filled from constant current
In discharge performance figure as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation is only 130mAh/
g。
Comparative example 5
2.5mL acetic acid is taken, 6mL butyl titanate is added sequentially to obtain solution A in 50mL dehydrated alcohol；It weighs
Tetra- water acetic acid nickel of 9.1340g, which is dissolved in 70mL deionized water, obtains solution B；2mL polyethylene glycol (600) is taken to be added to 150mL
Solution C is obtained in dehydrated alcohol.Then solution A and solution B are slowly added in suspension C simultaneously under the conditions of magnetic agitation,
0.5h is sufficiently stirred and obtains mixed liquor.The entrance wind-warm syndrome that spray dryer is arranged is 180 DEG C, and the flow velocity of peristaltic pump is 500mL/h.
Mixing suspension obtains precursor powder by spray drying, and to precursor powder further progress high-temperature heat treatment, temperature is
500 DEG C, heating rate is 5 DEG C/min, then soaking time 6h is down to room temperature naturally.Finally obtain NiTiO3/ C cathode material
Material.The XRD of the material shows that the nickel titanate prepared has more miscellaneous peak.
Button cell is assembled into using the sodium-ion battery anode material and sodium piece of this comparative example preparation, is filled from constant current
In discharge performance figure as can be seen that under the constant-current discharge density of 50mA/g, 200 circle specific discharge capacity of circulation is only 85mAh/g.
Claims (6)
1. a kind of NiTiO of sodium-ion battery3The preparation method of/C negative electrode material, which is characterized in that the sodium-ion battery
NiTiO3/ C negative electrode material is the micro-spherical particle assembled by the metatitanic acid nano nickel particles for being coated with carbon；Wherein, described
Micro-spherical particle partial size is 0.5 ~ 3 micron；Specific surface area is 30~200m2 g−1；
The NiTiO3The preparation process of/C negative electrode material are as follows: by organic acid, titanium source, nickel source and dispersed carbon source dissolution and/or dispersion
In a solvent and it is stirred to react to obtain mixed liquor；Again by mixed liquor be spray-dried presoma nano particle, then again through calcining
The NiTiO is made in processing3/ C negative electrode material；
The dispersed carbon source is at least one of polyethylene glycol, polystyrene, benzyl carbinol；
The organic acid is at least one of formic acid, acetic acid, oxalic acid.
2. the NiTiO of sodium-ion battery as described in claim 13The preparation method of/C negative electrode material, which is characterized in that spraying
The entrance wind-warm syndrome of drying process is 160 ~ 200 DEG C, and the flow of mixed liquor is 400~600 mL/h.
3. the NiTiO of sodium-ion battery as claimed in claim 23The preparation method of/C negative electrode material, which is characterized in that calcining
The temperature of process is 600 ~ 900 DEG C；Soaking time is 8~12 h.
4. the NiTiO of sodium-ion battery as described in claim 13The preparation method of/C negative electrode material, which is characterized in that described
Solvent be at least one of water, the alcohol of C1 ~ 4.
5. such as the NiTiO of the described in any item sodium-ion batteries of claim 1 ~ 43The preparation method of/C negative electrode material, feature exist
In organic acid, titanium source are dispersed in solvent a to obtain solution A；Nickel source is dissolved in the water to obtain solution B；Dispersed carbon source is dissolved
Solution C is obtained in solvent b；Then solution A, solution B, solution C are mixed, is stirred to react to obtain the mixed liquor；Described
Solvent a and solvent b is independently chosen from the alcohol of C1 ~ 4.
6. the NiTiO of sodium-ion battery as claimed in claim 53The preparation method of/C negative electrode material, which is characterized in that solution A
In, the volume ratio of organic acid and solvent a are 1:15 ~ 25；Titanium source and the volume ratio of solvent a are 1:3 ~ 6；In solution B, nickel source it is dense
Degree is 0.05 ~ 0.2 g/mL；In solution C, the volume ratio of dispersed carbon source and solvent b are 1:50 ~ 150；The time being stirred to react
For 2 ~ 4h；The titanium source is at least one of butyl titanate, tetraethyl titanate, isopropyl titanate；The nickel source is water
The nickel compound of dissolubility.
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