CN107221659B - 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 methods 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 are as follows: BaNa2Ti6O14‑aLi3xLa2/3‑xTiO3(LLTO), in which: 0.1≤a≤0.4,0.05≤x≤0.15.Specific preparation step is: barium source, sodium source and titanium source being placed in ball grinder, ball milling, is then put in pre-burning in Muffle furnace, cooling, ball milling, sieving, place into Muffle kiln roasting, cooling, ball milling, obtain negative electrode material presoma in ball mill；Lithium source, lanthanum source, titanium source and negative electrode material presoma are dissolved in organic solvent, stirred, is then transferred into closed reactor and keeps the temperature, is cooling, filtering, is dry, gained mixture is put in Muffle kiln roasting and obtains BaNa2Ti6O14‑aLi3xLa2/3‑xTiO3(LLTO) composite negative pole material.Raw material sources of the present invention are extensive, easy to operate, controllability is good, reproducibility is high, and obtained material granule is smaller, particle diameter distribution is uniform, crystallinity is high, to improve the chemical property of material while reducing material preparation cost.
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 technique
While global economy is grown rapidly, our original main energy sources: petroleum, coal, natural gas etc. are all not
Renewable resource, and these fossil energies can also generate pernicious gas while consumption, increasingly so as to cause environmental pollution
Seriously, developing new energy and the environmentally friendly energy has vital meaning.Various electronic equipments and electric car,
The development of hybrid vehicle, to the lithium ion battery for providing energy for it, more stringent requirements are proposed.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 power battery.
Commercial li-ion cell negative electrode material mostly uses greatly various embedding lithium carbon graphite materials, still, the intercalation potential (0 of carbon material at present
~0.26V) with the sedimentation potential of lithium metal very close to, when over-charging of battery, lithium metal may be precipitated in carbon electrodes and
Li dendrite is formed, dendrite further growth may then pierce through diaphragm, positive and negative anodes is caused to connect, so as to cause short circuit；In addition, carbon
That there is also first charge-discharge efficiencies is low for material, with electrolyte is had an effect, there are apparent voltage delay phenomenons, large current density
The disadvantages such as electric energy power is low.Spinel type lithium titanate Li4Ti5O12It is a kind of " zero strain " material, in the mistake of lithium ion insertion abjection
Crystal structure is able to maintain the stability of height in journey, and makes it have excellent cycle performance and stable discharge voltage.And
With relatively high electrode voltage (1.55V), is not in the precipitation of lithium metal in entire discharge process, substantially increases
The safety that electrode material uses.But being the largest deficiency is that its electronic conductance and ionic conductance are lower, to fill in high current
Capacity attenuation is fast when electric discharge, high rate performance is poor.Therefore, it is necessary to develop novel titanate negative electrode material.
Summary of the invention
In order to overcome the deficiencies of the prior art, the technical problem to be solved in the present invention is to provide a kind of lithium ion battery Compound Negatives
Pole material and preparation method thereof, it is extensive to raw material sources, it is easy to operate, controllability is good, reproducibility is high, obtained material
Grain is smaller, particle diameter distribution is uniform, crystallinity is high, to improve the electrochemistry of material while reducing material preparation cost
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 are as follows: BaNa2Ti6O14-aLi3xLa2/3-xTiO3
(LLTO), wherein 0.1≤a≤0.4,0.05≤x≤0.15, the negative electrode material are the partial sizes for having submicron order, have preferable
Chemical property.
Invention also provides the preparation methods of above-mentioned composite cathode material for lithium ion cell, the specific steps are as follows:
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, and sieving is placed into Muffle furnace and burnt at 900-1100 DEG C
10-15h is cooled to room temperature, and ball milling for 24 hours, obtains 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 and turn
It moves on in 160-200 DEG C of heat preservation 12h in closed reactor, cooling to filter, the dry 12h at 80-120 DEG C, by gained mixture
It is put in Muffle furnace, 600-800 DEG C of roasting 10-12h obtains BaNa2Ti6O14- LLTO composite negative pole material.
The sodium source is one of sodium hydroxide, sodium acetate, sodium nitrate.
The barium source is one of barium nitrate, barium carbonate.
The preparation BaNa2Ti6O14Titanium source be anatase titania, rutile titanium dioxide and unformed dioxy
Change one of titanium.
The preparation BaNa2Ti6O14-Li3xLa2/3-xTiO3Titanium source be anatase butyl titanate and isopropyl titanate in
One kind.
The lithium source is one of lithium acetate, lithium hydroxide, lithium nitrate.
The lanthanum source is one of lanthanum acetate, lanthanum nitrate.
The organic solvent is one of ethyl alcohol, ethylene glycol, benzyl alcohol, acetone, propyl alcohol, isopropanol, ascorbic acid.
The principles of science of the present invention:
Li3xLa2/3-xTiO3With many vacancy, 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 material
It, both can be to avoid BaNa as lithium ion battery negative material2Ti6O14It directly contacts, and can be improved with electrolyte
BaNa2Ti6O14Ionic mobility, to improve the chemical property of such negative electrode material.
Compared with prior art, the present invention has following technical effect that
1, BaNa prepared by the present invention2Ti6O14-aLi3xLa2/3-xTiO3Composite negative pole material controllability is good, and reproducibility is high.
2, the material granule uniformity of the invention synthesized, good dispersion, crystallinity are high, and obtained material is submicron order
Partial size, be conducive to improve material chemical property.
3, the obtained material of the present invention has considerable broad potential window reversible capacity, excellent high rate performance and stable
Cycle life can effectively meet the various applications of lithium ion battery so that the material is worth with very high actual use
Actual requirement.
4, the lithium ion battery negative material theoretical capacity with higher and quick charge and discharge that the present invention prepares are electrical
Can, the energy density and power density of lithium ion battery are improved, used raw material are cheap and easy to get.
5, present invention reduces the usage amounts of elemental lithium, to reduce costs.
Detailed description of the invention
Fig. 1 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3The XRD of (a=0.1, x=0.11)
Figure.
Fig. 2 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3The SEM of (a=0.1, x=0.11)
Figure.
Fig. 3 is gained BaNa in the embodiment of the present invention 12Ti6O14-aLi3xLa2/3-xTiO3(a=0.1, x=0.11) no
Same multiplying cycle 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
Same multiplying cycle performance curve (charging capacity).
Specific 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 the anatase titania (TiO of 0.06mol2), 0.02mol sodium acetate (CH3COONa), 0.01mol barium carbonate
(BaCO3) be placed in agate pot appropriate dehydrated alcohol ball milling 10h is added, agate pot is put into 60 DEG C of drying in baking oven, is cooled to
Then room temperature is put in 400 DEG C of pre-burning 4h in Muffle furnace, is cooled to room temperature, calcines 10h at 1000 DEG C, be cooled to room temperature, ball
Mill obtains negative electrode material BaNa for 24 hours, after sieving2Ti6O14Presoma.By 0.01mol BaNa2Ti6O14, 0.00033mol hydroxide
Lithium (LiOH), 0.00056mol lanthanum nitrate (La (NO3)3) and 0.001mol butyl titanate be dissolved in ethylene glycol, stir
Then 3.5h is put in and is transferred in closed reactor in 180 DEG C of heat preservation 12h, cooling, and dry 12h, gained is mixed at 100 DEG C
It closes object to be put in Muffle furnace, 700 DEG C of roasting 12h are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-
0.1Li0.33La0.56TiO3Composite negative pole material.X-ray powder diffraction (Fig. 1) is analysis shows resulting obtained product is
BaNa2Ti6O14-0.1Li0.33La0.56TiO3Compound, crystallinity are high.Gained is learnt from scanning electron microscope (Fig. 2) analysis
The even particle size of product is consistent, partial size 200-500nm.Using resulting product as electrode material, it is being 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 for the first time-1(Fig. 3), charging capacity are
152.2mAh·g-1(Fig. 4).300mA·g-1The discharge capacity for the first time of current density is 88.6mAhg-1(Fig. 3), charging capacity
For 87.3mAhg-1(Fig. 4), BaNa2Ti6O14-0.1Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 2
By the rutile titanium dioxide (TiO of 0.06mol2), 0.0201mol sodium hydroxide (NaOH), 0.01mol barium carbonate
(BaCO3) be placed in agate pot appropriate dehydrated alcohol ball milling 10h is added, agate pot is put into 60 DEG C of drying in baking oven, is cooled to
Then room temperature is put in 600 DEG C of pre-burning 4h in Muffle furnace, is cooled to room temperature, calcines 10h at 900 DEG C, be cooled to room temperature, ball
Mill obtains negative electrode material BaNa for 24 hours, after sieving2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.000528mol lithium acetate
(CH3COOLi·2H2O), 0.000896mol lanthanum acetate and 0.0016mol butyl titanate are dissolved in ethyl alcohol, stir 5h, so
After be put in and be transferred in closed reactor in 160 DEG C of heat preservation 12h, cooling, dry 12h, gained mixture is put at 80 DEG C
In Muffle furnace, 600 DEG C of roasting 12h are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-
0.16Li0.33La0.56TiO3Composite negative pole material.X-ray powder diffraction is analysis shows resulting obtained product is
BaNa2Ti6O14-0.16Li0.33La0.56TiO3Compound, crystallinity are high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size it is consistent, partial size 300-600nm.Using resulting product as electrode material, in the gloves for being 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,
BaNa2Ti6O14-0.16Li0.33La0.56TiO3Discharge capacity is 160.2mAhg for the first time-1, charging capacity 148.7mAhg-1。300mA·g-1The discharge capacity for the first time of current density is 84.6mAhg-1, charging capacity 85.4mAhg-1,
BaNa2Ti6O14-0.16Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 3
By the unformed titanium dioxide (TiO of 0.06mol2), 0.02005mol sodium hydroxide (NaOH), 0.01mol nitric acid
Barium, which is placed in agate pot, is added appropriate dehydrated alcohol ball milling 10h, and agate pot is put into 60 DEG C of drying in baking oven, is cooled to room temperature,
Then 600 DEG C of pre-burning 6h in Muffle furnace are put in, are cooled to room temperature, 15h is calcined at 1100 DEG C, is cooled to room temperature, ball milling
For 24 hours, negative electrode material BaNa is obtained after sieving2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.000792mol lithium hydroxide
(LiOH), 0.001344mol lanthanum nitrate and 0.0024mol isopropyl titanate are dissolved in benzyl alcohol, are stirred 3-5h, are then put in
It is transferred in closed reactor in 200 DEG C of heat preservation 12h, cooling, dry 12h, is put in Muffle furnace for gained mixture at 80 DEG C
In, 800 DEG C of roasting 12h are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-0.24Li0.33La0.56TiO3
Composite negative pole material.X-ray powder diffraction is analysis shows resulting obtained product is BaNa2Ti6O14-
0.24Li0.33La0.56TiO3Compound, crystallinity are high.Learn that the granular size of products therefrom is equal from scanning electron microscope analysis
It is even consistent, partial size 200-700nm.Using resulting product 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-
0.24Li0.33La0.56TiO3Discharge capacity is 160.2mAhg for the first time-1, charging capacity 149.1mAhg-1。300mA·g-1
The discharge capacity for the first time of current density is 85.5mAhg-1, charging capacity 84.1mAhg-1, BaNa2Ti6O14-
0.24Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 4
By the anatase titania (TiO of 0.06mol2), 0.02mol sodium acetate (CH3COONa), 0.01mol barium nitrate
It is placed in agate pot and appropriate dehydrated alcohol ball milling 10h is added, agate pot is put into 60 DEG C of drying in baking oven, is cooled to room temperature, so
After be put in 400 DEG C of pre-burning 4h in Muffle furnace, be cooled to room temperature, calcine 10h at 1000 DEG C, be cooled to room temperature, ball milling for 24 hours,
Negative electrode material BaNa is obtained after sieving2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.001056mol lithium acetate (CH3COOLi·
2H2O), 0.001792mol lanthanum nitrate and 0.0032mol isopropyl titanate are dissolved in acetone, are stirred 4h, are then put in transfer
Cooling into closed reactor in 180 DEG C of heat preservation 12h, dry 12h, gained mixture is put in Muffle furnace at 110 DEG C,
1050 DEG C of roasting 12h, are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-0.32Li0.33La0.56TiO3It is multiple
Close negative electrode material.X-ray powder diffraction is analysis shows resulting obtained product is BaNa2Ti6O14-
0.32Li0.33La0.56TiO3Composite negative pole material compound, crystallinity are high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size it is consistent, partial size 300-700nm.Using resulting product as electrode material, in the gloves for being 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,
BaNa2Ti6O14-0.32Li0.33La0.56TiO3Discharge capacity is 155.9mAhg for the first time-1, charging capacity 146.2mAhg-1。300mA·g-1The discharge capacity for the first time of current density is 84.6mAhg-1, charging capacity 81.5mAhg-1,
BaNa2Ti6O14-0.32Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 5
By the rutile titanium dioxide (TiO of 0.06mol2), 0.02mol sodium hydroxide (NaOH), 0.01mol barium carbonate set
Appropriate dehydrated alcohol ball milling 13h is added in agate pot, agate pot is put into 60 DEG C of drying in baking oven, is cooled to room temperature, then
500 DEG C of pre-burning 5h in Muffle furnace are put in, are cooled to room temperature, 13h is calcined at 950 DEG C, is cooled to room temperature, ball milling for 24 hours, is sieved
After obtain negative electrode material BaNa2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.00132mol lithium hydroxide (LiOH),
0.00224mol lanthanum nitrate and 0.004mol butyl titanate are dissolved in propyl alcohol, stir 5h, be then put in be transferred to it is closed anti-
It answers in 190 DEG C of heat preservation 12h in kettle, cooling, dry 12h, gained mixture is put in Muffle furnace at 110 DEG C, 650 DEG C of roastings
12h is cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-0.4Li0.33La0.56TiO3Composite negative pole material.X
Ray powder diffraction analysis shows that resulting obtained product is BaNa2Ti6O14-0.4Li0.33La0.56TiO3Compound, knot
Brilliant degree is high.Learn that the even particle size of products therefrom is consistent from scanning electron microscope analysis, partial size 400-800nm.It will
Resulting product is assembled into experiment fastening lithium ionic cell in the glove box full of argon gas, with 50mA as electrode material
g-1Current density charge and discharge cycles, BaNa are carried out between 0-3V2Ti6O14-0.4Li0.33La0.56TiO3Discharge capacity is for the first time
154.5mAh·g-1, charging capacity 142.6mAhg-1。300mA·g-1The discharge capacity for the first time of current density is
80.6mAh·g-1(Fig. 3), charging capacity 77.9mAhg-1, BaNa2Ti6O14-0.4Li0.33La0.56TiO3It shows excellent
High rate performance.
Embodiment 6
By the unformed titanium dioxide (TiO of 0.06mol2), 0.02mol sodium hydroxide (NaOH), 0.010mol barium carbonate
It is placed in agate pot and appropriate dehydrated alcohol ball milling 14h is added, agate pot is put into 60 DEG C of drying in baking oven, is cooled to room temperature, so
After be put in 400 DEG C of pre-burning 4h in Muffle furnace, be cooled to room temperature, calcine 14h at 1050 DEG C, be cooled to room temperature, ball milling for 24 hours,
Negative electrode material BaNa is obtained after sieving2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.00132mol lithium acetate (CH3COOLi·
2H2O), 0.00224mol lanthanum nitrate (La (NO3)3) and 0.004mol butyl titanate be dissolved in isopropanol, stir 3.5h, so
After be put in and be transferred in closed reactor in 160 DEG C of heat preservation 12h, cooling to filter, the dry 12h at 80 DEG C, by gained mixture
It is put in Muffle furnace, 800 DEG C of roasting 12h are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-
0.4Li0.33La0.56TiO3Composite negative pole material.X-ray powder diffraction is analysis shows resulting obtained product is
BaNa2Ti6O14-0.4Li0.33La0.56TiO3Compound, crystallinity are high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size is consistent, partial size 200-600nm.Using resulting product as electrode material, in the glove box for being full of argon gas
In be assembled into experiment fastening lithium ionic cell, with 50mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.4Li0.33La0.56TiO3Discharge capacity is 151.2mAhg for the first time-1, charging capacity 147.3mAhg-1。
300mA·g-1The discharge capacity for the first time of current density is 80.2mAhg-1(Fig. 3), charging capacity 75.2mAhg-1(figure
4), BaNa2Ti6O14-0.4Li0.33La0.56TiO3Show excellent high rate performance.
Embodiment 7
By the unformed titanium dioxide (TiO of 0.06mol2), 0.02mol sodium hydroxide (NaOH), 0.01mol barium carbonate set
Appropriate dehydrated alcohol ball milling 12h is added in agate pot, agate pot is put into 60 DEG C of drying in baking oven, is cooled to room temperature, then
Be put in 450 DEG C of pre-burning 5h in Muffle furnace, be cooled to room temperature, calcine 10h at 1100 DEG C, be cooled to room temperature, ball milling for 24 hours, mistake
Negative electrode material BaNa is obtained after sieve2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.0006mol lithium acetate (CH3COOLi·
2H2O), 0.002468mol lanthanum acetate and 0.004mol isopropyl titanate are dissolved in ascorbic acid, are stirred 3-5h, are then put in
It is transferred in closed reactor in 160 DEG C of heat preservation 12h, cooling to filter, dry 12h, is put in horse for gained mixture at 80 DEG C
Not in furnace, 800 DEG C of roasting 12h are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-
0.4Li0.15La0.617TiO3Composite negative pole material.X-ray powder diffraction is analysis shows resulting obtained product is
BaNa2Ti6O14-0.4Li0.15La0.517TiO3Compound, crystallinity are high.Products therefrom is learnt from scanning electron microscope analysis
Even particle size is consistent, partial size 300-800nm.Using resulting product as electrode material, in the glove box for being full of argon gas
In be assembled into experiment fastening lithium ionic cell, with 50mAg-1Current density charge and discharge cycles are carried out between 0-3V,
BaNa2Ti6O14-0.4Li0.15La0.617TiO3Discharge capacity is 149.7mAhg for the first time-1, charging capacity 132.8mAhg-1。300mA·g-1The discharge capacity for the first time of current density is 78.4mAhg-1, charging capacity 73.5mAhg-1,
BaNa2Ti6O14-0.4Li0.15La0.617TiO3Show excellent high rate performance.
Embodiment 8
By the rutile titanium dioxide (TiO of 0.06mol2), 0.02mol sodium hydroxide (NaOH), 0.01mol barium carbonate set
Appropriate dehydrated alcohol ball milling 10h is added in agate pot, agate pot is put into 60 DEG C of drying in baking oven, is cooled to room temperature, then
400 DEG C of pre-burning 4h in Muffle furnace are put in, are cooled to room temperature, 10h is calcined at 1000 DEG C, ball milling for 24 hours, is cooled to room temperature, mistake
Negative electrode material BaNa is obtained after sieve2Ti6O14.By 0.01mol BaNa2Ti6O14, 0.0018mol lithium hydroxide (LiOH),
0.002068mol lanthanum nitrate and 0.004mol butyl titanate are dissolved in ethylene glycol, stir 3-5h, be then put in be transferred to it is close
It closes in 160 DEG C of heat preservation 12h in reaction kettle, cooling to filter, dry 12h, gained mixture is put in Muffle furnace at 80 DEG C,
1100 DEG C of roasting 12h, are cooled to room temperature to obtain lithium ion battery negative material BaNa2Ti6O14-0.4Li0.45La0.517TiO3It is compound
Negative electrode material.X-ray powder diffraction is analysis shows resulting obtained product is BaNa2Ti6O14-0.4Li0.45La0.517TiO3
Compound, crystallinity are high.Learn that the even particle size of products therefrom is consistent from scanning electron microscope analysis, partial size 400-
900nm.Using resulting product as electrode material, it is assembled into experiment fastening lithium ionic cell in the glove box full of argon gas,
With 50mAg-1Current density charge and discharge cycles, BaNa are carried out between 0-3V2Ti6O14-0.4Li0.45La0.517TiO3It puts for the first time
Capacitance is 148.6mAhg-1, charging capacity 142.3mAhg-1。300mA·g-1The discharge capacity for the first time of current density
For 76.4mAhg-1, charging capacity 73.1mAhg-1, BaNa2Ti6O14-0.4Li0.45La0.517TiO3It shows 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 the following steps are included:
(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, and sieving places into Muffle furnace and burns 10- at 900-1100 DEG C
15h is cooled to room temperature, and ball milling for 24 hours, obtains 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 keep the temperature 12h, cooling to filter, the dry 12h at 80-120 DEG C, by gained
Mixture is put in Muffle furnace, is roasted 10-12h at 600-800 DEG C, is obtained BaNa2Ti6O14-aLi3xLa2/3-xTiO3(LLTO) multiple
Close negative electrode material；Wherein: 0.05≤x≤0.15；0.1≤a≤0.4；
The sodium source is one of sodium hydroxide, sodium acetate, sodium nitrate；
The barium source is one of barium nitrate, barium carbonate；
The preparation BaNa2Ti6O14Titanium source be anatase titania, rutile titanium dioxide and unformed titanium dioxide
One of；
The preparation Li3xLa2/3-xTiO3Titanium source be one of butyl titanate and isopropyl titanate；
The lithium source is one of lithium acetate, lithium hydroxide, lithium nitrate；
The lanthanum source is one of lanthanum acetate, lanthanum nitrate；
The organic solvent is one of ethyl alcohol, ethylene glycol, benzyl alcohol, acetone, propyl alcohol, isopropanol, ascorbic acid.
2. the preparation method of composite cathode material for lithium ion cell as described in claim 1, which is characterized in that the sodium source is
Sodium acetate；The barium source is barium carbonate；The titanium source for preparing BaNa2Ti6O14 is anatase titania；The preparation
The titanium source of Li3xLa2/3-xTiO3 is butyl titanate；The lithium source is lithium hydroxide；The lanthanum source is lanthanum nitrate；It is described to have
Solvent is ethylene glycol.
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| Title |
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| （"Synthesis and application of a novel Li4Ti5O12 composite as anode material with enhanced fast charge-discharge performance forlithium-ion battery";Ting-Feng Yi，et al.;《Electrochimica Acta》;20140509;第377-383页 |
| "Improved the lithium storage capability of BaLi2Ti6O14 by electroless silver coating";Xiaoting Lin，et al.;《Electrochimica Acta》;20151101;第24-33页 |
| "MLi2Ti6O14 (M = Sr, Ba, 2Na) Lithium Insertion Titanate Materials: A Comparative Study";Damien Dambournet，et al.;《Inorg. Chem.》;20100217;第2822-2826页 |
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