CN107221659A - A kind of preparation method of composite cathode material for lithium ion cell - Google Patents
A kind of preparation method of composite cathode material for lithium ion cell Download PDFInfo
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Abstract
The invention discloses a kind of preparation method of composite cathode material for lithium ion cell, belong to technical field of lithium ion.The molecular formula of the composite cathode material for lithium ion cell is：BaNa2Ti6O14‑aLi3xLa2/3‑xTiO3(LLTO), wherein：0.1≤a≤0.4,0.05≤x≤0.15.Specifically preparation process is：Barium source, sodium source and titanium source are placed in ball grinder, ball milling, are then put in pre-burning in Muffle furnace, cooling, ball milling, sieving, place into Muffle kiln roasting, cooling, ball milling in ball mill, that is, negative material presoma is made；Lithium source, lanthanum source, titanium source and negative material presoma are dissolved in organic solvent, stirs, is then transferred into insulation, cooling, suction filtration, drying in closed reactor, gained mixture is put in into Muffle kiln roasting obtains BaNa2Ti6O14‑aLi3xLa2/3‑xTiO3(LLTO) composite negative pole material.Extensively, easy to operate, controllability is good, reappearance is high, and resulting material granule is smaller, particle diameter distribution is uniform, crystallinity is high for raw material sources of the present invention, so as to while material preparation cost is reduced, improve the chemical property of material.
Description
Technical field
The invention belongs to technical field of lithium ion, and in particular to a kind of high performance lithium ion battery composite cathode material
Material.
Background technology
While global economy fast development, our original main energy sources：Oil, coal, natural gas etc. are all not
Renewable resource, and these fossil energies can also produce pernicious gas while consumption, so as to cause environmental pollution increasingly
Seriously, exploitation novel energy and the environmentally friendly energy have vital meaning.Various electronic equipments and electric automobile,
The development of hybrid vehicle, higher requirement is proposed to the lithium ion battery that energy is provided for it.Lithium ion battery has
Output voltage is high, energy density and power density are big, have extended cycle life etc. a little, is acknowledged as most promising electrokinetic cell.
Current commercial li-ion cell negative electrode material uses various embedding lithium carbon graphite materials, still, the intercalation potential (0 of carbon material mostly
~0.26V) with the sedimentation potential of lithium metal very close to, when over-charging of battery, lithium metal may be separated out in carbon electrodes and
Li dendrite is formed, dendrite further growth may then pierce through barrier film, cause both positive and negative polarity to connect, so as to cause short circuit；In addition, carbon
Material also has that first charge-discharge efficiency is low, has an effect, there is obvious voltage delay phenomenon, large current density with electrolyte
The low shortcoming of electric energy power.Spinel type lithium titanate Li4Ti5O12It is a kind of " zero strain " material, the mistake deviate from Lithium-ion embeding
Crystal structure can keep the stability of height in journey, and make it have excellent cycle performance and stable discharge voltage.And
With of a relatively high electrode voltage (1.55V), be not in the precipitation of lithium metal in whole discharge process, substantially increase
The security that electrode material is used.But maximum deficiency is that its electronic conductance and ionic conductance are relatively low, so as to be filled in high current
Capacity attenuation is fast during electric discharge, high rate performance is poor.Therefore, the new titanate negative material of necessary exploitation.
The content of the invention
To overcome the deficiencies in the prior art, the technical problem to be solved in the present invention is to provide a kind of lithium ion battery Compound Negative
Pole material and preparation method thereof, to raw material sources extensively, the material that easy to operate, controllability is good, reappearance is high, resulting
The smaller, particle diameter distribution of grain is uniform, crystallinity is high, so as to while material preparation cost is reduced, improve the electrochemistry of material
Energy.
In order to solve the above technical problems, the present invention is achieved by the following technical programs.
The chemical formula of lithium ion battery negative material prepared by the present invention is： BaNa2Ti6O14-aLi3xLa2/3-xTiO3
(LLTO), wherein 0.1≤a≤0.4,0.05≤x≤0.15, the negative material is the particle diameter for having submicron order, with preferable
Chemical property.
Invention also provides the preparation method of above-mentioned composite cathode material for lithium ion cell, comprise the following steps that：
Barium source, sodium source and titanium source are placed in ball grinder, then ball milling 10-14h is put in Muffle furnace at 400-600 DEG C
Lower pre-burning 4-6h, is cooled to room temperature, the ball milling 3-4h in ball mill, sieving, places into Muffle furnace in burning at 900-1100 DEG C
10-15h, is cooled to room temperature, and ball milling 24h is made the lithium ion battery negative material BaNa of broad potential window2Ti6O14Forerunner
Body.By lithium source, lanthanum source, titanium source and synthetic BaNa2Ti6O14It is dissolved in organic solvent, stirs 3-5h, be then put in
It is transferred in closed reactor and is incubated 12h at 160-200 DEG C, cool down suction filtration, 12h is dried at 80-120 DEG C, gained is mixed
Thing is put in Muffle furnace, and 600-800 DEG C of roasting 10-12h obtains BaNa2Ti6O14- LLTO composite negative pole materials.
Described sodium source is one kind in sodium hydroxide, sodium acetate, sodium nitrate.
Described barium source is one kind in barium nitrate, barium carbonate.
The preparation BaNa2Ti6O14Titanium source be anatase titania, rutile titanium dioxide and unformed dioxy
Change one kind in titanium.
The preparation BaNa2Ti6O14-Li3xLa2/3-xTiO3Titanium source be anatase butyl titanate and isopropyl titanate in
One kind.
Described lithium source is one kind in lithium acetate, lithium hydroxide, lithium nitrate.
Described lanthanum source is one kind in lanthanum acetate, lanthanum nitrate.
The organic solvent is one kind in ethanol, ethylene glycol, phenmethylol, acetone, propyl alcohol, isopropanol, ascorbic acid.
The principles of science of the present invention：
Li3xLa2/3-xTiO3With many rooms, lithium ion is easier to movable within, shows at room temperature good
Ionic mobility, crystal grain lithium ion conductivity is up to 10 to this kind of polycrystalline electrolyte at room temperature-3~10-4S/cm, for
The electric conductivity for improving lithium ion battery plays an important role.Therefore, BaNa is utilized2Ti6O14-aLi3xLa2/3-xTiO3Composite
As lithium ion battery negative material, BaNa can be both avoided2Ti6O14Directly contact, can improve again with electrolyte
BaNa2Ti6O14Ionic mobility, so as to improve the chemical property of such negative material.
Compared with prior art, the present invention has following technique effect：
1st, BaNa prepared by the present invention2Ti6O14-aLi3xLa2/3-xTiO3Composite negative pole material controllability is good, and reappearance is high.
2nd, the material granule uniformity of the invention synthesized, good dispersion, crystallinity are high, and obtained material is submicron order
Particle diameter, be conducive to improve material chemical property.
3rd, the material that the present invention is obtained has considerable broad potential window reversible capacity, excellent high rate performance and stabilization
Cycle life so that the material has very high actual use value, can effectively meet the various applications of lithium ion battery
Actual requirement.
4th, the lithium ion battery negative material that the present invention is prepared has higher theoretical capacity and quick charge and discharge electrical
Can, the energy density and power density of lithium ion battery are improved, uses raw material cheap and easy to get.
5th, present invention reduces the usage amount of elemental lithium, so as to reduce cost.
Brief description of the drawings
Fig. 1 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3(a=0.1, x=0.11's)
XRD.
Fig. 2 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3(a=0.1, x=0.11's)
SEM schemes.
Fig. 3 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3(a=0.1, x=0.11) no
With circulation performance curve (discharge capacity).
Fig. 4 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3(a=0.1, x=0.11) no
With circulation performance curve (charging capacity).
Embodiment
The present invention is described in detail below in conjunction with the drawings and specific embodiments, but the present invention is not limited to following embodiments.
Embodiment 1
By 0.06mol anatase titania (TiO2), 0.02mol sodium acetates (CH3COONa), 0.01mol barium carbonates
(BaCO3) be placed in agate pot and add appropriate absolute ethyl alcohol ball milling 10h, agate pot is put into 60 DEG C of drying in baking oven, is cooled to
Room temperature, is then put in 400 DEG C of pre-burning 4h in Muffle furnace, is cooled to room temperature, 10h is calcined at 1000 DEG C, be cooled to room temperature, ball
24h is ground, negative material BaNa is obtained after sieving2Ti6O14Presoma.By 0.01mol BaNa2Ti6O14, 0.00033mol hydroxides
Lithium (LiOH), 0.00056mol lanthanum nitrates (La (NO3)3) and 0.001mol butyl titanates be dissolved in ethylene glycol, stir
3.5h, is then put in and is transferred in closed reactor in 180 DEG C of insulation 12h, cooling dries 12h at 100 DEG C, gained is mixed
Compound is put in Muffle furnace, 700 DEG C of roasting 12h, is cooled to room temperature and is obtained lithium ion battery negative material BaNa2Ti6O14-
0.1Li0.33La0.56TiO3Composite negative pole material.Resulting product obtained by X-ray powder diffraction (Fig. 1) analysis shows is
BaNa2Ti6O14-0.1Li0.33La0.56TiO3Compound, crystallinity is high.Gained is learnt from SEM (Fig. 2) analysis
The even particle size of product is consistent, and particle diameter is 200-500 nm.Using the product of gained as electrode material, full of argon gas
Experiment fastening lithium ionic cell is assembled into glove box, with 50mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.1Li0.33La0.56TiO3Discharge capacity is 164.7mAhg first-1(Fig. 3), charging capacity is
152.2mAh·g-1(Fig. 4).300mA·g-1The discharge capacity first of current density is 88.6mAhg-1(Fig. 3), charging is held
Measure as 87.3mAhg-1(Fig. 4), BaNa2Ti6O14-0.1Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 2
By 0.06mol rutile titanium dioxide (TiO2), 0.0201mol sodium hydroxides (NaOH), 0.01mol carbonic acid
Barium (BaCO3) be placed in agate pot and add appropriate absolute ethyl alcohol ball milling 10h, agate pot is put into 60 DEG C of drying in baking oven, cooling
To room temperatures, 600 DEG C of pre-burning 4h in Muffle furnace are then put in, room temperature is cooled to, 10h is calcined at 900 DEG C, is cooled to room temperature,
Negative material BaNa is obtained after ball milling 24h, sieving2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.000528mol lithium acetates
(CH3COOLi·2H2O), 0.000896mol lanthanum acetates and 0.0016mol butyl titanates are dissolved in ethanol, stir 5h, so
After be put in be transferred in closed reactor 160 DEG C be incubated 12h, cooling, at 80 DEG C dry 12h, gained mixture is put in
In Muffle furnace, 600 DEG C of roasting 12h are cooled to room temperature and obtain lithium ion battery negative material BaNa2Ti6O14-
0.16Li0.33La0.56TiO3Composite negative pole material.Resulting product obtained by X-ray powder diffraction analysis shows is
BaNa2Ti6O14-0.16Li0.33La0.56TiO3Compound, crystallinity is high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size it is consistent, particle diameter is 300-600nm.Using the product of gained as electrode material, in the gloves full of argon gas
Experiment fastening lithium ionic cell is assembled into case, with 50 mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.16Li0.33La0.56TiO3Discharge capacity is 160.2mAhg first-1, charging capacity is 148.7mAhg-1。300mA·g-1The discharge capacity first of current density is 84.6mAhg-1, charging capacity is 85.4mAhg-1,
BaNa2Ti6O14-0.16Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 3
By 0.06mol unformed titanium dioxide (TiO2), 0.02005mol sodium hydroxides (NaOH), 0.01mol nitric acid
Barium, which is placed in agate pot, adds appropriate absolute ethyl alcohol ball milling 10h, and agate pot is put into 60 DEG C of drying in baking oven, room temperature is cooled to,
Then 600 DEG C of pre-burning 6h in Muffle furnace are put in, room temperature is cooled to, 15h is calcined at 1100 DEG C, room temperature, ball milling is cooled to
Negative material BaNa is obtained after 24h, sieving2Ti6O14.By 0.01 mol BaNa2Ti6O14, 0.000792mol lithium hydroxides
(LiOH), 0.001344mol lanthanum nitrates and 0.0024mol isopropyl titanates are dissolved in phenmethylol, stir 3-5h, Ran Houfang
12h is incubated at 200 DEG C in being transferred in closed reactor, cooling dries 12h at 80 DEG C, gained mixture is put in into Muffle
In stove, 800 DEG C of roasting 12h are cooled to room temperature and obtain lithium ion battery negative material BaNa2Ti6O14-
0.24Li0.33La0.56TiO3Composite negative pole material.Resulting product obtained by X-ray powder diffraction analysis shows is
BaNa2Ti6O14-0.24Li0.33La0.56TiO3Compound, crystallinity is high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size it is consistent, particle diameter is 200-700nm.Using the product of gained as electrode material, in the gloves full of argon gas
Experiment fastening lithium ionic cell is assembled into case, with 50mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.24Li0.33La0.56TiO3Discharge capacity is 160.2mAhg first-1, charging capacity is 149.1mAh
g-1。300mA·g-1The discharge capacity first of current density is 85.5mAhg-1, charging capacity is 84.1mAhg-1,
BaNa2Ti6O14-0.24Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 4
By 0.06mol anatase titania (TiO2), 0.02mol sodium acetates (CH3COONa), 0.01mol barium nitrates
It is placed in agate pot and adds appropriate absolute ethyl alcohol ball milling 10h, agate pot is put into 60 DEG C of drying in baking oven, room temperature is cooled to, so
After be put in 400 DEG C of pre-burning 4h in Muffle furnace, be cooled to room temperature, 10h calcined at 1000 DEG C, be cooled to room temperature, ball milling 24h,
Negative material BaNa is obtained after sieving2Ti6O14.By 0.01 mol BaNa2Ti6O14, 0.001056mol lithium acetates
(CH3COOLi·2H2O), 0.001792mol lanthanum nitrates and 0.0032mol isopropyl titanates are dissolved in acetone, stir 4h, so
After be put in be transferred in closed reactor 180 DEG C be incubated 12h, cooling, at 110 DEG C dry 12h, gained mixture is put in
In Muffle furnace, 1050 DEG C of roasting 12h are cooled to room temperature and obtain lithium ion battery negative material BaNa2Ti6O14-
0.32Li0.33La0.56TiO3Composite negative pole material.Resulting product obtained by X-ray powder diffraction analysis shows is
BaNa2Ti6O14-0.32Li0.33La0.56TiO3Composite negative pole material compound, crystallinity is high.From scanning electron microscope analysis
Learn that the even particle size of products therefrom is consistent, particle diameter is 300-700 nm.Using the product of gained as electrode material, filling
Experiment fastening lithium ionic cell is assembled into the glove box of full argon gas, with 50mAg-1Current density charge and discharge is carried out between 0-3V
Electricity circulation, BaNa2Ti6O14-0.32Li0.33La0.56TiO3Discharge capacity is 155.9mAhg first-1, charging capacity is
146.2 mAh·g-1。300mA·g-1The discharge capacity first of current density is 84.6mAhg-1, charging capacity is 81.5
mAh·g-1, BaNa2Ti6O14-0.32Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 5
By 0.06mol rutile titanium dioxide (TiO2), 0.02mol sodium hydroxides (NaOH), 0.01mol barium carbonates put
Appropriate absolute ethyl alcohol ball milling 13h is added in agate pot, agate pot is put into 60 DEG C of drying in baking oven, room temperature is cooled to, then
500 DEG C of pre-burning 5h in Muffle furnace are put in, room temperature is cooled to, 13h is calcined at 950 DEG C, room temperature, ball milling 24h, sieving is cooled to
After obtain negative material BaNa2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.00132mol lithium hydroxides (LiOH),
0.00224mol lanthanum nitrates and 0.004mol butyl titanates are dissolved in propyl alcohol, stir 5h, be then put in be transferred to it is closed anti-
Answer and be incubated 12 h in kettle at 190 DEG C, cooling dries 12h at 110 DEG C, gained mixture is put in Muffle furnace, 650 DEG C of roastings
12h is burnt, room temperature is cooled to and obtains lithium ion battery negative material BaNa2Ti6O14-0.4Li0.33La0.56TiO3Composite negative pole material
Material.Resulting product obtained by X-ray powder diffraction analysis shows is BaNa2Ti6O14-0.4Li0.33La0.56TiO3It is compound
Thing, crystallinity is high.Learn that the even particle size of products therefrom is consistent from scanning electron microscope analysis, particle diameter is 400-
800nm.Using the product of gained as electrode material, experiment fastening lithium ionic cell is assembled into the glove box full of argon gas,
With 50mAg-1Current density charge and discharge cycles, BaNa are carried out between 0-3V2Ti6O14-0.4Li0.33La0.56TiO3Put first
Capacitance is 154.5mAhg-1, charging capacity is 142.6mAhg-1。300mA·g-1The discharge capacity first of current density
For 80.6mAhg-1(Fig. 3), charging capacity is 77.9mAhg-1, BaNa2Ti6O14-0.4Li0.33La0.56TiO3Show excellent
Different high rate performance.
Embodiment 6
By 0.06mol unformed titanium dioxide (TiO2), 0.02mol sodium hydroxides (NaOH), 0.010mol barium carbonates
It is placed in agate pot and adds appropriate absolute ethyl alcohol ball milling 14h, agate pot is put into 60 DEG C of drying in baking oven, room temperature is cooled to, so
After be put in 400 DEG C of pre-burning 4h in Muffle furnace, be cooled to room temperature, 14h calcined at 1050 DEG C, be cooled to room temperature, ball milling 24h,
Negative material BaNa is obtained after sieving2Ti6O14.By 0.01 mol BaNa2Ti6O14, 0.00132mol lithium acetates (CH3COOLi·
2H2O), 0.00224mol lanthanum nitrates (La (NO3)3) and 0.004mol butyl titanates be dissolved in isopropanol, stir 3.5h,
Then it is put in be transferred in closed reactor and is incubated 12h at 160 DEG C, cool down suction filtration, 12h is dried at 80 DEG C, gained is mixed
Thing is put in Muffle furnace, 800 DEG C of roasting 12h, is cooled to room temperature and is obtained lithium ion battery negative material BaNa2Ti6O14-
0.4Li0.33La0.56TiO3Composite negative pole material.Resulting product obtained by X-ray powder diffraction analysis shows is
BaNa2Ti6O14-0.4Li0.33La0.56TiO3Compound, crystallinity is high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size is consistent, and particle diameter is 200-600nm.Using the product of gained as electrode material, in the glove box full of argon gas
In be assembled into experiment fastening lithium ionic cell, with 50 mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.4Li0.33La0.56TiO3Discharge capacity is 151.2mAhg first-1, charging capacity is 147.3mAhg-1。
300mA·g-1The discharge capacity first of current density is 80.2mAhg-1(Fig. 3), charging capacity is 75.2mAhg-1(figure
4), BaNa2Ti6O14-0.4Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 7
By 0.06mol unformed titanium dioxide (TiO2), 0.02mol sodium hydroxides (NaOH), 0.01mol barium carbonates put
Appropriate absolute ethyl alcohol ball milling 12h is added in agate pot, agate pot is put into 60 DEG C of drying in baking oven, room temperature is cooled to, then
450 DEG C of pre-burning 5h in Muffle furnace are put in, room temperature is cooled to, 10h is calcined at 1100 DEG C, room temperature, ball milling 24h, mistake is cooled to
Negative material BaNa is obtained after sieve2Ti6O14.By 0.01 mol BaNa2Ti6O14, 0.0006mol lithium acetates (CH3COOLi·
2H2O), 0.002468mol lanthanum acetates and 0.004mol isopropyl titanates are dissolved in ascorbic acid, stir 3-5h, Ran Houfang
12h is incubated at 160 DEG C in being transferred in closed reactor, suction filtration is cooled down, 12h is dried at 80 DEG C, gained mixture is put in
In Muffle furnace, 800 DEG C of roasting 12h are cooled to room temperature and obtain lithium ion battery negative material BaNa2Ti6O14-
0.4Li0.15La0.617TiO3Composite negative pole material.Resulting product obtained by X-ray powder diffraction analysis shows is
BaNa2Ti6O14-0.4Li0.15La0.517TiO3Compound, crystallinity is high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size is consistent, and particle diameter is 300-800nm.Using the product of gained as electrode material, in the glove box full of argon gas
In be assembled into experiment fastening lithium ionic cell, with 50 mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.4Li0.15La0.617TiO3Discharge capacity is 149.7mAhg first-1, charging capacity is 132.8mAhg-1。300mA·g-1The discharge capacity first of current density is 78.4mAhg-1, charging capacity is 73.5mAhg-1,
BaNa2Ti6O14-0.4Li0.15La0.617TiO3Show excellent high rate performance.
Embodiment 8
By 0.06mol rutile titanium dioxide (TiO2), 0.02mol sodium hydroxides (NaOH), 0.01mol barium carbonates put
Appropriate absolute ethyl alcohol ball milling 10h is added in agate pot, agate pot is put into 60 DEG C of drying in baking oven, room temperature is cooled to, then
400 DEG C of pre-burning 4h in Muffle furnace are put in, room temperature is cooled to, 10h, ball milling 24h are calcined at 1000 DEG C, room temperature, mistake is cooled to
Negative material BaNa is obtained after sieve2Ti6O14.By 0.01 mol BaNa2Ti6O14, 0.0018mol lithium hydroxides (LiOH),
0.002068mol lanthanum nitrates and 0.004mol butyl titanates are dissolved in ethylene glycol, are stirred 3-5h, are then put in and are transferred to
12h is incubated at 160 DEG C in closed reactor, suction filtration is cooled down, 12h is dried at 80 DEG C, gained mixture is put in Muffle furnace,
1100 DEG C of roasting 12h, are cooled to room temperature and obtain lithium ion battery negative material BaNa2Ti6O14-0.4Li0.45La0.517TiO3It is compound
Negative material.Resulting product obtained by X-ray powder diffraction analysis shows is BaNa2Ti6O14-
0.4Li0.45La0.517TiO3Compound, crystallinity is high.Learn that the granular size of products therefrom is equal from scanning electron microscope analysis
Even consistent, particle diameter is 400-900nm.Using the product of gained as electrode material, reality is assembled into the glove box full of argon gas
Fastening lithium ionic cell is tested, with 50mAg-1Current density charge and discharge cycles, BaNa are carried out between 0-3V2Ti6O14-
0.4Li0.45La0.517TiO3Discharge capacity is 148.6mAhg first-1, charging capacity is 142.3mAhg-1。300mA·g-1The discharge capacity first of current density is 76.4mAhg-1, charging capacity is 73.1mAhg-1, BaNa2Ti6O14-
0.4Li0.45La0.517TiO3Show excellent high rate performance.
Claims (2)
1. a kind of preparation method of composite cathode material for lithium ion cell, it is characterised in that comprise the following steps：
(1) barium source, sodium source and titanium source are placed in ball grinder, ball milling 10-14h, are then put in Muffle furnace at 400-600 DEG C
Pre-burning 4-6h, is cooled to room temperature, the ball milling 3-4h in ball mill, sieving, places into Muffle furnace in burning 10- at 900-1100 DEG C
15h, is cooled to room temperature, and ball milling 24h is made lithium ion battery negative material BaNa2Ti6O14Presoma；
(2) BaNa for synthesizing lithium source, lanthanum source, titanium source and step (1)2Ti6O14It is dissolved in organic solvent, stirs 3-5h, so
After be transferred in closed reactor at 160-200 DEG C and be incubated 12h, cool down suction filtration, 12h dried at 80-120 DEG C, by gained
Mixture is put in Muffle furnace, is calcined 10-12h at 600-800 DEG C, is obtained BaNa2Ti6O14-aLi3xLa2/3-xTiO3(LLTO) it is multiple
Close negative material；Wherein：0.05≤x≤0.15；0.1≤a≤0.4；
The sodium source is one kind in sodium hydroxide, sodium acetate, sodium nitrate；
The barium source is one kind in barium nitrate, barium carbonate；
The preparation BaNa2Ti6O14Titanium source be anatase titania, rutile titanium dioxide and unformed titanium dioxide
In one kind；
The preparation Li3xLa2/3-xTiO3Titanium source be butyl titanate and isopropyl titanate in one kind；
The lithium source is one kind in lithium acetate, lithium hydroxide, lithium nitrate；
The lanthanum source is one kind in lanthanum acetate, lanthanum nitrate；
The organic solvent is one kind in ethanol, ethylene glycol, phenmethylol, acetone, propyl alcohol, isopropanol, ascorbic acid.
2. the preparation method of composite cathode material for lithium ion cell as claimed in claim 1, it is characterised in that the sodium source is
Sodium acetate；The barium source is barium carbonate；The titanium source for preparing BaNa2Ti6O14 is anatase titania；It is described to prepare
Li3xLa2/3-xTiO3 titanium source is butyl titanate；The lithium source is lithium hydroxide；The lanthanum source is lanthanum nitrate；It is described to have
Machine solvent is ethylene glycol.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749471A (en) * | 2017-10-18 | 2018-03-02 | 安徽工业大学 | A kind of preparation method of lithium ion battery multilevel hierarchy titanate negative material |
| CN107768635A (en) * | 2017-10-18 | 2018-03-06 | 安徽工业大学 | A kind of preparation method of lithium ion battery barium titanate sodium composite negative pole material |
| CN110148728A (en) * | 2019-05-24 | 2019-08-20 | 隆能科技(南通)有限公司 | A kind of ternary material and preparation method thereof of surface cladding LLTO |
| CN112018333A (en) * | 2019-05-28 | 2020-12-01 | 吉林大学 | Preparation method of negative active material, negative electrode and preparation method thereof, and lithium ion battery |
| CN113991088A (en) * | 2021-10-29 | 2022-01-28 | 中国科学技术大学 | Novel lithium ion battery cathode material and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602052A (en) * | 2016-12-28 | 2017-04-26 | 宁波大学 | Anode material for lithium ion batteries and preparation method thereof |
-
2017
- 2017-06-14 CN CN201710449705.5A patent/CN107221659B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106602052A (en) * | 2016-12-28 | 2017-04-26 | 宁波大学 | Anode material for lithium ion batteries and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| DAMIEN DAMBOURNET，ET AL.: ""MLi2Ti6O14 (M = Sr, Ba, 2Na) Lithium Insertion Titanate Materials: A Comparative Study"", 《INORG. CHEM.》 * |
| TING-FENG YI，ET AL.: "（"Synthesis and application of a novel Li4Ti5O12 composite as anode material with enhanced fast charge-discharge performance forlithium-ion battery"", 《ELECTROCHIMICA ACTA》 * |
| XIAOTING LIN，ET AL.: ""Improved the lithium storage capability of BaLi2Ti6O14 by electroless silver coating"", 《ELECTROCHIMICA ACTA》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107749471A (en) * | 2017-10-18 | 2018-03-02 | 安徽工业大学 | A kind of preparation method of lithium ion battery multilevel hierarchy titanate negative material |
| CN107768635A (en) * | 2017-10-18 | 2018-03-06 | 安徽工业大学 | A kind of preparation method of lithium ion battery barium titanate sodium composite negative pole material |
| CN107768635B (en) * | 2017-10-18 | 2020-05-05 | 安徽工业大学 | Preparation method of barium sodium titanate composite negative electrode material for lithium ion battery |
| CN110148728A (en) * | 2019-05-24 | 2019-08-20 | 隆能科技(南通)有限公司 | A kind of ternary material and preparation method thereof of surface cladding LLTO |
| CN112018333A (en) * | 2019-05-28 | 2020-12-01 | 吉林大学 | Preparation method of negative active material, negative electrode and preparation method thereof, and lithium ion battery |
| CN113991088A (en) * | 2021-10-29 | 2022-01-28 | 中国科学技术大学 | Novel lithium ion battery cathode material and preparation method thereof |
| CN113991088B (en) * | 2021-10-29 | 2022-12-30 | 中国科学技术大学 | Lithium ion battery cathode material and preparation method thereof |
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