CN106935827A - A kind of oxygen vacancy type lithium titanate composite material and preparation method thereof, lithium titanate battery - Google Patents
A kind of oxygen vacancy type lithium titanate composite material and preparation method thereof, lithium titanate battery Download PDFInfo
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- H01M4/00—Electrodes
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- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M10/05—Accumulators with non-aqueous electrolyte
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- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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Abstract
The invention discloses a kind of preparation method of oxygen vacancy type lithium titanate composite material, the method includes：The lithium titanate of pure lithium titanate or doped metallic elements M is placed in the mixed-gas atmosphere of organic gas and inert gas, 5min ~ 24h is incubated at 700 ~ 1000 DEG C, cooling obtains oxygen vacancy type lithium titanate composite material；The metallic element M is selected from least one in iron, cobalt, nickel, molybdenum, zirconium, copper, zinc, magnesium, aluminium, silicon, rare earth element；The organic gas is that, with the one kind in the alkane below seven carbon atoms and seven carbon atoms, alkene, alkynes or gaseous state alcohols, organic gas accounts for the 5 ~ 95% of mixed gas cumulative volume.The invention also discloses the oxygen vacancy type lithium titanate composite material that the above method is prepared, and using the lithium titanate battery of above-mentioned oxygen vacancy type lithium titanate composite material.
Description
Technical field
The invention belongs to field of lithium ion battery, and in particular to a kind of oxygen vacancy type lithium titanate composite material and its preparation side
Method, and using the lithium titanate battery of the oxygen vacancy type lithium titanate composite material.
Background technology
In secondary battery material, lithium titanate material crystal structure during Lithium-ion embeding is deviate from can keep height
Stability, volume hardly changes, and belongs to zero strain material, so that with excellent cycle performance and smoothly electric discharge electricity
Pressure；Lithium titanate material removal lithium embedded current potential is 1. 55V, will not cause the precipitation of dendrite lithium, safe；Lithium titanate material has
Three-dimensional lithium ion transport passage, lithium ion diffusion coefficient（It is 2*10-8 cm2/s）An order of magnitude higher than Carbon anode etc., can be real
Now multiple fast charging and discharging, therefore lithium titanate material is a kind of very important electrode material.But, lithium titanate material is led in itself
It is electrically poor（Conductance 10-13S/cm）, larger polarization is also easy to produce during high current charge-discharge, limit its high power charging-discharging
Energy.For this shortcoming, grinding for the ring structure conductive materials of carbene six such as substantial amounts of introducing Graphene, CNT has been carried out at present
Study carefully work.
Chinese invention patent CN201010531928.4 is by introducing graphene oxide and organic carbon source（Pyrrole monomer or its
In derivative, aniline monomer or derivatives thereof, thiophene monomer or derivatives thereof more than one）It is prepared for lithium titanate composite material；
Chinese invention patent CN201310105495.X is by introducing sulphate method Graphene and carbon source（Sucrose, glucose, citric acid,
One kind in aniline and polyvinyl chloride, Kynoar macromolecule resin）It is prepared for lithium titanate composite material.Above-mentioned lithium titanate is answered
Condensation material performance has some improvement, but preparation process introduces production process and has the graphene oxide and its graphite of severe contamination
Alkene, and technical process is harsh, conductive material is difficult and lithium titanate strong bonded, it is difficult to form the material of stable and uniform.
The content of the invention
The technical problems to be solved by the invention are directed to the deficiencies in the prior art, there is provided a kind of process is simple environmental protection, section
The preparation method of the oxygen vacancy type lithium titanate composite material that can be lowered consumption.
The technical problems to be solved by the invention are to additionally provide the oxygen vacancy type metatitanic acid prepared according to preceding method
Lithium composite material.
The technical problems to be solved by the invention are realized by following technical scheme.The present invention is that a kind of oxygen lacks
The preparation method of bit-type lithium titanate composite material, is characterized in, the method includes：By pure lithium titanate or doped metallic elements M
Lithium titanate be placed in the mixed-gas atmosphere of organic gas and inert gas, at 700 ~ 1000 DEG C be incubated 5min ~ 24h, it is cold
But, oxygen vacancy type lithium titanate composite material is obtained；
The metallic element M is selected from least one in iron, cobalt, nickel, molybdenum, zirconium, copper, zinc, magnesium, aluminium, silicon, rare earth element；
The organic gas is with the alkane below seven carbon atoms and seven carbon atoms, alkene, alkynes or gaseous state alcohols
One kind, organic gas accounts for the 5 ~ 95% of mixed gas cumulative volume.
The lithium titanate of pure lithium titanate of the present invention or doped metallic elements M be commercially available or prior art disclosed in
Any one can apply to the lithium titanate of the inventive method.
The technical problems to be solved by the invention can also further be realized by following technical scheme.Institute of the present invention
In the preparation method of the oxygen vacancy type lithium titanate composite material stated, described pure lithium titanate is prepared as follows：According to lithium
It is 3 ~ 6 with the mol ratio of titanium:5 weigh lithium source and titanium source, and lithium source and titanium source are directly mixed, and obtain mixture；Or by lithium source, titanium source
It is scattered in deionized water or organic solvent, stirs, spray drying treatment obtains mixed powder；By said mixture or mixing
Powder is placed at 600 ~ 1200 DEG C, and 2 ~ 24h is calcined in atmosphere, obtains final product the pure lithium titanate of titanium.It is further preferred that described is pure
Lithium titanate is prepared as follows：Mol ratio according to lithium and titanium is 3.5 ~ 5:5 weigh lithium source and titanium source, and lithium source and titanium source is straight
Mixing is connect, mixture is obtained；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, at spray drying
Reason, obtains mixed powder；Said mixture or mixed powder are placed at 800 ~ 1000 DEG C, 6 ~ 15h is calcined in atmosphere, obtain final product pure titanium
Sour lithium.
The technical problems to be solved by the invention can also further be realized by following technical scheme.Institute of the present invention
In the preparation method of the oxygen vacancy type lithium titanate composite material stated, the lithium titanate of described doped metallic elements M is as follows
Prepare：Mol ratio according to lithium, titanium, metal M is 3 ~ 6:5:0.01 ~ 10 salt for weighing lithium source, titanium source and metallic element M
Or the oxide of M, directly mix, obtain mixture；Or divide lithium source, titanium source, and the salt of metallic element M or the oxide of M
Dissipate in deionized water or organic solvent, stir, spray drying treatment obtains mixed powder；By said mixture or mixed powder
It is placed at 600 ~ 1200 DEG C, 2 ~ 24h is calcined in atmosphere, obtains final product the lithium titanate of doped metallic elements M.It is further preferred that institute
The lithium titanate of the doped metallic elements M for stating is prepared as follows：Mol ratio according to lithium, titanium, metal M is 3.5 ~ 5:5:0.1~
5 oxides for weighing lithium source, the salt of titanium source and metallic element M or M, directly mix, and obtain mixture；Or by lithium source, titanium
Source, and the salt of metallic element M or the oxide of M are scattered in deionized water or organic solvent, are stirred, spray drying
Treatment, obtains mixed powder；Said mixture or mixed powder are placed at 850 ~ 1100 DEG C, 8 ~ 20h is calcined in atmosphere, obtain final product doping
The lithium titanate of metallic element M.
The technical problems to be solved by the invention can also further be realized by following technical scheme.Institute of the present invention
The preparation method of the oxygen vacancy type lithium titanate composite material stated, is preparing the lithium titanate of pure lithium titanate and doped metallic elements M
During, described lithium source is lithium carbonate, lithium nitrate, lithium hydroxide, lithium chloride, lithium sulfate, lithium acetate, lithium phosphate, lithium fluoride,
One kind in lithium oxalate, lithium sulfide；Described titanium source is titanium dioxide, butyl titanate, metatitanic acid, isopropyl titanate, titanium oxyoxalate
In one kind.
The technical problems to be solved by the invention can also further be realized by following technical scheme.Institute of the present invention
The preparation method of the oxygen vacancy type lithium titanate composite material stated, is preparing the lithium titanate of pure lithium titanate and doped metallic elements M
During, described organic solvent is ethanol or isopropanol.
The technical problems to be solved by the invention can also further be realized by following technical scheme.Institute of the present invention
In the preparation method of the oxygen vacancy type lithium titanate composite material stated, described inert gas is in nitrogen, helium, argon gas
Kind.
The technical problems to be solved by the invention can also further be realized by following technical scheme.Institute of the present invention
In the preparation method of the oxygen vacancy type lithium titanate composite material stated, the flow velocity of described mixed gas is 0.1 ~ 100m/s.It is preferred that
Ground, the flow velocity of described mixed gas is 8 ~ 75m/s.It is further preferred that the flow velocity of described mixed gas is 30 ~ 60m/s.
Present invention also offers a kind of oxygen vacancy type lithium titanate composite material, the oxygen vacancy type lithium titanate composite material be by
Prepared according to the above method.By electro-chemical test, oxygen vacancy type lithium titanate composite material of the present invention shows excellent
Capacity and high rate performance and good stable circulation performance.
Present invention also offers a kind of lithium titanate battery, including negative pole, the material of the negative pole is above-mentioned oxygen vacancy type titanium
Sour lithium composite material.
Compared with prior art, the present invention with carbon containing organic gas, i.e., with seven carbon atoms and seven carbon atoms below
Alkane, alkene, alkynes or gaseous state alcohols be carbon source, its can at high operating temperatures with lithium titanate or the metatitanic acid of doped metallic elements
The surface of lithium is bonded.After through high-temperature roasting, hydrogen and carbon that carbon containing organic gas is cracked to form, hydrogen make lithium titanate in situ
Anoxic, carbon is deposited directly to lithium titanate particle surface, forms the lithium titanate composite material of oxygen vacancy and carbon doping/cladding,
The expensive conductive material such as addition carbon pipe, Graphene and its follow-up complex techniques process for preparing lithium titanate composite material are eliminated,
Process is simple environmental protection, it is energy-saving, it is adapted to large-scale production.The oxygen vacancy type metatitanic acid lithium composite that the inventive method is prepared
Material has high conductivity and high-lithium ion transport number, it is adaptable to prepare high-performance metatitanic acid lithium secondary battery, and, by metatitanic acid
Doping metals in lithium particulate, can further improve the electric conductivity of oxygen vacancy type lithium titanate composite material, greatly improve it and fill
Discharge-rate.
Brief description of the drawings
The battery performance test result that Fig. 1 is done using the oxygen vacancy type lithium titanate composite material of the embodiment of the present invention 20；
The battery performance test result that Fig. 2 is done using the oxygen vacancy type lithium titanate composite material of the embodiment of the present invention 21；
The battery performance test result that Fig. 3 is done using the oxygen vacancy type lithium titanate composite material of the embodiment of the present invention 22；
The battery performance test result that Fig. 4 is done using the oxygen vacancy type lithium titanate composite material of the embodiment of the present invention 23；
The battery performance test result that Fig. 5 is done using the oxygen vacancy type lithium titanate composite material of the embodiment of the present invention 24；
Fig. 6 is the battery performance test result done using the oxygen vacancy type lithium titanate composite material of the embodiment of the present invention 25.
Specific embodiment
Concrete technical scheme of the invention described further below, is further understood that in order to those skilled in the art
The present invention, without constituting the limitation to its right.
A kind of embodiment 1, preparation method of oxygen vacancy type lithium titanate composite material, the method includes：By pure lithium titanate
Or the lithium titanate of doped metallic elements M is placed in the mixed-gas atmosphere of organic gas and inert gas, it is incubated at 1000 DEG C
5min, cooling, obtains oxygen vacancy type lithium titanate composite material；
The metallic element M is selected from least one in iron, cobalt, nickel, molybdenum, zirconium, copper, zinc, magnesium, aluminium, silicon, rare earth element；
The organic gas is with the alkane below seven carbon atoms and seven carbon atoms, alkene, alkynes or gaseous state alcohols
One kind, organic gas accounts for the 5% of mixed gas cumulative volume.
A kind of embodiment 2, preparation method of oxygen vacancy type lithium titanate composite material, the method includes：By pure lithium titanate
Or the lithium titanate of doped metallic elements M is placed in the mixed-gas atmosphere of organic gas and inert gas, it is incubated at 700 DEG C
24h, cooling, obtains oxygen vacancy type lithium titanate composite material；
The metallic element M is selected from least one in iron, cobalt, nickel, molybdenum, zirconium, copper, zinc, magnesium, aluminium, silicon, rare earth element；
The organic gas is with the alkane below seven carbon atoms and seven carbon atoms, alkene, alkynes or gaseous state alcohols
One kind, organic gas accounts for the 95% of mixed gas cumulative volume.
A kind of embodiment 3, preparation method of oxygen vacancy type lithium titanate composite material, the method includes：By pure lithium titanate
Or the lithium titanate of doped metallic elements M is placed in the mixed-gas atmosphere of organic gas and inert gas, it is incubated at 850 DEG C
12h, cooling, obtains oxygen vacancy type lithium titanate composite material；
The metallic element M is selected from least one in iron, cobalt, nickel, molybdenum, zirconium, copper, zinc, magnesium, aluminium, silicon, rare earth element；
The organic gas is with the alkane below seven carbon atoms and seven carbon atoms, alkene, alkynes or gaseous state alcohols
One kind, organic gas accounts for the 40% of mixed gas cumulative volume.
Embodiment 4, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-3 any one, institute
The inert gas stated is the one kind in nitrogen, helium, argon gas,
Embodiment 5, it is described in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-3 any one
The flow velocity of mixed gas is 0.1m/s.
Embodiment 6, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-3 any one, institute
The flow velocity of the mixed gas stated is 100m/s.
Embodiment 7, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-3 any one, institute
The flow velocity of the mixed gas stated is 50m/s.
Embodiment 8, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The pure lithium titanate stated is prepared as follows：Mol ratio according to lithium and titanium is 3:5 weigh lithium source and titanium source, by lithium source and titanium
Source directly mixes, and obtains mixture；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, it is spray-dried
Treatment, obtains mixed powder；Said mixture or mixed powder are placed at 600 DEG C, 24h is calcined in atmosphere, obtain final product pure lithium titanate.
Embodiment 9, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The pure lithium titanate stated is prepared as follows：Mol ratio according to lithium and titanium is 6:5 weigh lithium source and titanium source, by lithium source and titanium
Source directly mixes, and obtains mixture；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, it is spray-dried
Treatment, obtains mixed powder；Said mixture or mixed powder are placed at 1200 DEG C, 2h is calcined in atmosphere, obtain final product pure lithium titanate.
Embodiment 10, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The pure lithium titanate stated is prepared as follows：Mol ratio according to lithium and titanium is 4:5 weigh lithium source and titanium source, by lithium source and titanium
Source directly mixes, and obtains mixture；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, it is spray-dried
Treatment, obtains mixed powder；Said mixture or mixed powder are placed at 1100 DEG C, 14h is calcined in atmosphere, obtain final product pure metatitanic acid
Lithium.
Embodiment 11, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The pure lithium titanate stated is prepared as follows：Mol ratio according to lithium and titanium is 3.5:5 weigh lithium source and titanium source, by lithium source and
Titanium source directly mixes, and obtains mixture；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, spraying is dry
Dry treatment, obtains mixed powder；Said mixture or mixed powder are placed at 800 DEG C, 15h is calcined in atmosphere, obtain final product pure metatitanic acid
Lithium.
Embodiment 12, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The pure lithium titanate stated is prepared as follows：Mol ratio according to lithium and titanium is 1:1 weighs lithium source and titanium source, by lithium source and titanium
Source directly mixes, and obtains mixture；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, it is spray-dried
Treatment, obtains mixed powder；Said mixture or mixed powder are placed at 1000 DEG C, 6h is calcined in atmosphere, obtain final product pure lithium titanate.
Embodiment 13, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The lithium titanate of the doped metallic elements M for stating is prepared as follows：Mol ratio according to lithium, titanium, metal M is 3:5:0.01 weighs
The oxide of lithium source, the salt of titanium source and metallic element M or M, directly mixes, and obtains mixture；Or by lithium source, titanium source, and
The salt of metallic element M or the oxide of M are scattered in deionized water or organic solvent, are stirred, and spray drying treatment is obtained
Mixed powder；Said mixture or mixed powder are placed at 600 DEG C, 24h is calcined in atmosphere, obtain final product the titanium of doped metallic elements M
Sour lithium.
Embodiment 14, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The lithium titanate of the doped metallic elements M for stating is prepared as follows：Mol ratio according to lithium, titanium, metal M is 6:5:10 weigh lithium
The oxide in source, the salt of titanium source and metallic element M or M, directly mixes, and obtains mixture；Or by lithium source, titanium source, Yi Jijin
The oxide of the salt or M that belong to element M is scattered in deionized water or organic solvent, is stirred, and spray drying treatment obtains mixed
Close powder；Said mixture or mixed powder are placed at 600 DEG C, 2h is calcined in atmosphere, obtain final product the metatitanic acid of doped metallic elements M
Lithium.
Embodiment 15, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The lithium titanate of the doped metallic elements M for stating is prepared as follows：Mol ratio according to lithium, titanium, metal M is 4:5:5 weigh lithium
The oxide in source, the salt of titanium source and metallic element M or M, directly mixes, and obtains mixture；Or by lithium source, titanium source, Yi Jijin
The oxide of the salt or M that belong to element M is scattered in deionized water or organic solvent, is stirred, and spray drying treatment obtains mixed
Close powder；Said mixture or mixed powder are placed at 800 DEG C, 12h is calcined in atmosphere, obtain final product the metatitanic acid of doped metallic elements M
Lithium.
Embodiment 16, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The lithium titanate of the doped metallic elements M for stating is prepared as follows：Mol ratio according to lithium, titanium, metal M is 3.5:5:0.1 claims
The oxide of lithium source, the salt of titanium source and metallic element M or M is taken, is directly mixed, obtain mixture；Or by lithium source, titanium source, with
And the salt of metallic element M or the oxide of M are scattered in deionized water or organic solvent, are stirred, spray drying treatment,
Obtain mixed powder；Said mixture or mixed powder are placed at 1100 DEG C, 20h is calcined in atmosphere, obtain final product doped metallic elements M's
Lithium titanate.
Embodiment 17, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 1-7 any one, institute
The lithium titanate of the doped metallic elements M for stating is prepared as follows：Mol ratio according to lithium, titanium, metal M is 3.5:5:5 weigh
The oxide of lithium source, the salt of titanium source and metallic element M or M, directly mixes, and obtains mixture；Or by lithium source, titanium source, and
The salt of metallic element M or the oxide of M are scattered in deionized water or organic solvent, are stirred, and spray drying treatment is obtained
Mixed powder；Said mixture or mixed powder are placed at 850 DEG C, 20h is calcined in atmosphere, obtain final product the titanium of doped metallic elements M
Sour lithium.
Embodiment 18, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 8-17 any one,
Described lithium source be lithium carbonate, lithium nitrate, lithium hydroxide, lithium chloride, lithium sulfate, lithium acetate, lithium phosphate, lithium fluoride, lithium oxalate,
One kind in lithium sulfide；Described titanium source is in titanium dioxide, butyl titanate, metatitanic acid, isopropyl titanate, titanium oxyoxalate
Kind.
Embodiment 19, in the preparation method of the oxygen vacancy type lithium titanate composite material described in embodiment 8-18 any one,
Described organic solvent is ethanol or isopropanol.
A kind of embodiment 20, preparation method of oxygen vacancy type lithium titanate composite material, the method includes：Will be commercially available pure
Lithium titanate 120g is placed in the mixed-gas atmosphere of methane and argon gas, and 1h is incubated at 850 DEG C, and oxygen vacancy type metatitanic acid is collected in cooling
Lithium composite material；Wherein, methane volumetric accounts for the 30% of mixed gas cumulative volume, mixed gas flow velocity 0.1m/s.
A kind of embodiment 21, preparation method of oxygen vacancy type lithium titanate composite material, the method comprises the following steps：
（1）Mol ratio according to lithium and titanium is 3:5 weigh lithium hydroxide and titanium dioxide, and lithium hydroxide and titanium dioxide are disperseed
In deionized water, stir, spray drying treatment obtains mixed powder；Mixed powder is placed at 850 DEG C, is calcined in atmosphere
10h, obtains pure lithium titanate；
（2）The pure lithium titanate that will be obtained is placed in the mixed-gas atmosphere of ethane and nitrogen, and 750 DEG C of insulation 5h, cooling is collected
Oxygen vacancy type lithium titanate composite material；Wherein, ethane volume accounts for the 50% of mixed gas cumulative volume, and the flow velocity of mixed gas is
80m/s。
A kind of embodiment 22, preparation method of oxygen vacancy type lithium titanate composite material, the method comprises the following steps：
（1）According to lithium：Titanium：The mol ratio 4 of iron：5：0.02 weighs lithium carbonate, titanium dioxide and ferric nitrate, by lithium carbonate, dioxy
Change titanium and ferric nitrate is scattered in absolute ethyl alcohol, stir, spray drying treatment obtains mixed powder；Mixed powder is placed in 1200
At DEG C, 5h is calcined in atmosphere, the lithium titanate of the ferro element that must adulterate；
（2）The lithium titanate of the ferro element that adulterates is placed in the mixed-gas atmosphere of ethene and argon gas, 900 DEG C of insulation 4h, cooling is received
Collection oxygen vacancy type lithium titanate composite material；Wherein, volume of ethylene accounts for the 80% of mixed gas cumulative volume, and the flow velocity of mixed gas is
30m/s。
A kind of embodiment 23, preparation method of oxygen vacancy type lithium titanate composite material, the method comprises the following steps：
（1）According to lithium：Titanium：Iron：The mol ratio 4 of magnesium：5：0.01：0.02 weighs lithium hydroxide, titanium dioxide, ferric nitrate and nitric acid
Magnesium, lithium carbonate, titanium dioxide, ferric nitrate and magnesium nitrate are scattered in absolute ethyl alcohol, are stirred, and spray drying treatment is obtained
Mixed powder；Mixed powder is placed at 700 DEG C, 8h is calcined in atmosphere, the lithium titanate of must adulterate ferro element and magnesium elements；
（2）The lithium titanate of adulterate ferro element and magnesium elements is placed in the mixed-gas atmosphere of acetylene and nitrogen, 650 DEG C of insulations
Oxygen vacancy type lithium titanate composite material is collected in 20h, cooling；Wherein, acetylene volume accounts for the 10% of mixed gas cumulative volume, gaseous mixture
The flow velocity of body is 40m/s.
A kind of embodiment 24, preparation method of oxygen vacancy type lithium titanate composite material, the method comprises the following steps：
（1）According to lithium：Titanium：Nickel：The mol ratio 6 of cerium:5:0.02:0.01 weighs lithium carbonate, titanium dioxide, nickel nitrate, cerous sulfate,
Lithium carbonate, titanium dioxide, nickel nitrate, cerous sulfate are well mixed, are placed at 900 DEG C, 10h is calcined in atmosphere, obtain doping nickel
The lithium titanate of element and Ce elements；
（2）The lithium titanate of adulterate nickel element and Ce elements is placed in the mixed-gas atmosphere of propane and nitrogen, 950 DEG C of insulations
Oxygen vacancy type lithium titanate composite material is collected in 18h, cooling；Wherein, propane volume accounts for the 50% of mixed gas cumulative volume, gaseous mixture
The flow velocity of body is 6m/s.
A kind of embodiment 25, preparation method of oxygen vacancy type lithium titanate composite material, the method comprises the following steps：
（1）According to lithium：Titanium：Cobalt：Magnesium：The mol ratio 3.5 of praseodymium:5:0.05:0.06:0.005 weigh lithium hydroxide, titanium dioxide,
Cobalt nitrate, magnesia, praseodymium oxide are scattered in absolute ethyl alcohol, are stirred, and spray drying treatment obtains mixed powder；By mixed powder
It is placed at 1100 DEG C, 6h is calcined in atmosphere, the lithium titanate of must adulterate cobalt element, magnesium elements and praseodymium element；
（2）The lithium titanate of adulterate cobalt element, magnesium elements and praseodymium element is placed in the mixed-gas atmosphere of methane and argon gas, 850
DEG C insulation 15h, cooling, collect oxygen vacancy type lithium titanate composite material；Wherein, methane volumetric accounts for the 90% of mixed gas cumulative volume,
The flow velocity of mixed gas is 12m/s.
Embodiment 26, using the battery performance test that oxygen vacancy type lithium titanate composite material of the present invention is prepared.
1st, the preparation of Battery pack is tested：According to mass ratio 90:5:5:100 oxygen for respectively preparing embodiment 20-25
Omission type lithium titanate composite material and conductive black, organic binder bond（PVDF）, 1-METHYLPYRROLIDONE（NMP）After being sufficiently stirred for
Slurry is formed, gained slurry is coated uniformly on corrosive aluminum foil, cathode pole piece is obtained after drying, roll-in, cutting, punching, will
The pairing of cathode pole piece and metal lithium sheet is assembled into 2032 button half-cells, and by the oxygen vacancy type metatitanic acid of Application Example 20-25
Battery prepared by lithium composite material is respectively labeled as experimental group 1-6.
2nd, the preparation of Battery pack is compareed：The preparation of control Battery pack is identical with the preparation method of experiment Battery pack, difference
Place is that the lithium titanate electrode material of application is prepared as follows and obtains：By lithium：Mol ratio=4 of titanium:5 weigh lithium carbonate
And titanium dioxide, lithium carbonate and titanium dioxide are scattered in absolute ethyl alcohol, stir, spray drying treatment obtains presoma,
Presoma is placed at 850 DEG C, 8h is calcined in atmosphere, natural cooling is obtained final product.
3rd, performance test：Use battery ability meter（LAND2000 testers）500 loop tests of 1C/3C discharge and recharges,
Result is shown in Fig. 1-6.
As seen from the figure, the battery that embodiment of the present invention 20-25 oxygen vacancies type lithium titanate composite material is prepared is in test
Process performance stabilization, specific capacity is held essentially constant and maintains higher level, and up to more than 120mAh/g, cycle performance is bright
It is aobvious to be better than control group.
Claims (10)
1. a kind of preparation method of oxygen vacancy type lithium titanate composite material, it is characterised in that the method includes：By pure lithium titanate
Or the lithium titanate of doped metallic elements M is placed in the mixed-gas atmosphere of organic gas and inert gas, at 700 ~ 1000 DEG C
Insulation 5min ~ 24h, cooling obtains oxygen vacancy type lithium titanate composite material；
The metallic element M is selected from least one in iron, cobalt, nickel, molybdenum, zirconium, copper, zinc, magnesium, aluminium, silicon, rare earth element；
The organic gas is with the alkane below seven carbon atoms and seven carbon atoms, alkene, alkynes or gaseous state alcohols
One kind, organic gas accounts for the 5 ~ 95% of mixed gas cumulative volume.
2. the preparation method of oxygen vacancy type lithium titanate composite material according to claim 1, it is characterised in that described is pure
Lithium titanate be prepared as follows：Mol ratio according to lithium and titanium is 3 ~ 6:5 weigh lithium source and titanium source, and lithium source and titanium source is straight
Mixing is connect, mixture is obtained；Or during lithium source, titanium source are scattered in into deionized water or organic solvent, stir, at spray drying
Reason, obtains mixed powder；Said mixture or mixed powder are placed at 600 ~ 1200 DEG C, 2 ~ 24h is calcined in atmosphere, obtain final product pure titanium
Sour lithium.
3. the preparation method of oxygen vacancy type lithium titanate composite material according to claim 1, it is characterised in that described mixes
The lithium titanate of miscellaneous metallic element M is prepared as follows：Mol ratio according to lithium, titanium, metal M is 3 ~ 6:5:0.01 ~ 10 weighs
The oxide of lithium source, the salt of titanium source and metallic element M or M, directly mixes, and obtains mixture；Or by lithium source, titanium source, and
The salt of metallic element M or the oxide of M are scattered in deionized water or organic solvent, are stirred, and spray drying treatment is obtained
Mixed powder；Said mixture or mixed powder are placed at 600 ~ 1200 DEG C, 2 ~ 24h is calcined in atmosphere, obtain final product doping metals unit
The lithium titanate of plain M.
4. the preparation method of the oxygen vacancy type lithium titanate composite material according to Claims 2 or 3, it is characterised in that described
Lithium source be lithium carbonate, lithium nitrate, lithium hydroxide, lithium chloride, lithium sulfate, lithium acetate, lithium phosphate, lithium fluoride, lithium oxalate, vulcanization
One kind in lithium；Described titanium source is the one kind in titanium dioxide, butyl titanate, metatitanic acid, isopropyl titanate, titanium oxyoxalate.
5. the preparation method of the oxygen vacancy type lithium titanate composite material according to Claims 2 or 3, it is characterised in that described
Organic solvent be ethanol or isopropanol.
6. the preparation method of oxygen vacancy type lithium titanate composite material according to claim 2, it is characterised in that described titanium
Source and lithium source are 3.5 ~ 5 according to the mol ratio of lithium and titanium:5 are mixed.
7. the preparation method of oxygen vacancy type lithium titanate composite material according to claim 3, it is characterised in that described titanium
The oxide in source, the salt of lithium source and metallic element M or M is 3.5 ~ 5 according to the mol ratio of lithium, titanium, metal M:5:0.1 ~ 5 is carried out
Mixing.
8. the preparation method of oxygen vacancy type lithium titanate composite material according to claim 1, it is characterised in that described is lazy
Property gas be one kind in nitrogen, helium, argon gas, the flow velocity of described mixed gas is 0.1 ~ 100m/s.
9. a kind of oxygen vacancy type lithium titanate composite material, it is characterised in that it is according to described in claim 1-8 any one
What method was prepared.
10. a kind of lithium titanate battery, including negative pole, it is characterised in that the material of the negative pole is such as claim 1-8 any
The oxygen vacancy type lithium titanate described in the oxygen vacancy type lithium titanate composite material for preparing of method or claim 9 described in
Composite.
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