CN107317004B - A kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material and preparation method - Google Patents
A kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material and preparation method Download PDFInfo
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Abstract
The present invention provides a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal materials and preparation method thereof, the lithium titanate-indium bismuth Binary liquid metals material is bulky grain, partial size is 50 μm -500 μm, and in bulky grain, indium bismuth alloy coats lithium titanate nano particle, phosphide element, bismuth element mass ratio be (0.55-0.8): 1, the mass ratio of indium bismuth alloy and lithium titanate is (5-20): (95-80).The preparation method is the following steps are included: be ground to nanoscale for lithium titanate；In mass ratio it is (0.55-0.8) by indium metal, bismuth metal: 1 mixing, and 120 DEG C -180 DEG C are heated to, form liquid alloy；Be in mass ratio by liquid alloy (5-20): (95-80) is mixed with nano lithium titanate, is subsequently placed in progress air-flow dispersion, lithium titanate-indium bismuth Binary liquid metals material in pneumatic spray drying device；The chamber temp of pneumatic spray drying device is 90-120 DEG C.
Description
Technical field
The invention belongs to technical field of lithium ion battery negative, are related to a kind of titanium applied to negative electrode of lithium ion battery
Sour lithium-indium bismuth Binary liquid metals material and preparation method.
Background technique
The energy is the important material base of human survival and development, is motive power and the society for being engaged in various economic activities
The important symbol of the meeting level of economic development.With fossil fuel peter out and the problems such as global warming brought by it, it is many
More researchers start gradually to pay close attention to New Energy Industry.Wherein, lithium ion battery is high with its operating voltage, specific energy is big, it is light-weight,
It is small in size, have extended cycle life, memory-less effect, can be quickly charged and discharged with a series of significant advantages such as non-environmental-pollution into being
The research hotspot of new energy field.
Lithium ion battery negative material is the important component of battery, and it is light that negative electrode material occupies act foot in battery development
The status of weight.Currently, commercialized negative electrode of lithium ion battery mainly uses carbon material, but with the easy shape of lithium battery that carbon does cathode
Cause first charge-discharge efficiency lower at SEI film, irreversible capacity is larger；Lower point for easily causing electrolyte of platform voltage
Solution, to bring security risk.Compared with the carbon negative pole material being commercialized at present, spinel lithium titanate has better electrochemistry
Performance and safety.This material has " zero strain " characteristic, hardly happens variation in charge and discharge process middle skeleton structure, embedding
Lithium current potential is high, the good characteristics such as lithium ion diffusion coefficient an order of magnitude higher than common carbon electrode, and has lithium-ion electric
Charging times necessary to pond are more, the characteristic of charging process faster, safer.It is expected that lithium titanate material will become lithium of new generation from
The negative electrode material of sub- battery is applied in new-energy automobile.But lithium titanate still has its deficiency.Lithium titanate is in charge and discharge cycles process
In be easy to produce gas, this is the major issue for influencing battery safety and chemical property.Lithium titanate is in charge and discharge process
Middle a part of titanium ion can change between trivalent and tetravalence, and trivalent titanium ion has very strong reproducibility, directly and electrolyte
Contact will lead to electrolyte and generate gas by catalytic decomposition, lithium titanate battery serious flatulence problem under high temperature environment, greatly
Constrain the large-scale promotion and application of lithium titanate.There are many method for inhibiting lithium titanate to produce gas, including material preparation process improvement,
Lithium battery electrolytes selection and lithium battery preparation process amelioration, structural design optimization etc., wherein mixing lithium titanate material
Miscellaneous modification and surface cladding are that lithium titanate is inhibited to produce the common method of gas.For example, Chinese Patent Application No. 201210511716.9,
The patent of invention of denomination of invention " a kind of carbon coating doping vario-property lithium titanate and preparation method thereof ".The invention is characterized in that general formula is
Li4-xMgxTi5-yAlyO12/ C, wherein 0.05≤x≤0.5,0.02≤y≤0.25；It successively prepares according to the following steps: by dioxy
Change titanium, soluble sugar and aluminium powder or iron powder to be scattered in dehydrated alcohol, stirs to obtain suspension, dry paste, heat treatment
Carbon coating titanium dioxide is obtained, is impregnated with hydrochloric acid or sulfuric acid, washed, the dry carbon for simultaneously grinding obtained clad and there is small hole
Cladding titanium dioxide；Weigh lithium source, carbon coating titanium dioxide, magnesium source and silicon source mixing；Mixed material calcining is kept the temperature；
It grinds and the carbon coating doping vario-property lithium titanate that is sieved to obtain.The deficiency of the invention is: making after titanium dioxide mixing source of iron and silicon source
With pickling, which can have security risk in production, while bring the liquid waste processing problem of higher cost；Magnesium is used simultaneously
Source and silicon source doping, can not accurately be doped in lithium position and titanium position respectively.Chinese Patent Application No. 201210536105.X, invention
The patent of invention of title " a kind of micro-nano lithium titanate anode material and preparation method of rare earth metal doping ".The invention provides one kind
The micro-nano lithium titanate anode material and preparation method of rare earth metal doping.The molecular formula of lithium titanate anode material is LixMpTiyOz,
M is doping vario-property metal ion in formula, wherein 0 < x≤8,0 < p < 5,0 < y≤6,1≤z≤12,1/2≤x:y≤2.One
The preparation method of the micro-nano lithium titanate anode material of kind rare earth metal doping, uses spherical tio2 for initial feed, with water
Or ethyl alcohol is reaction dissolvent, by hydro-thermal reaction and calcination processing, is prepared into the lithium titanate of rare earth metal doping.The invention makes
Use rare earth element as doped source, cost is excessively high, and the product competitiveness that will lead in large-scale production is insufficient.Chinese patent Shen
Please numbers 201110328000.0, a kind of invention of denomination of invention " preparation method of aluminum-oxide-coated nano lithium titanate composite material "
Patent.The invention discloses a kind of preparation methods of aluminum-oxide-coated nano lithium titanate composite material, under stirring conditions to
Li obtained by made above4Ti5O12Suspension in aluminum salt solution is added, the additional amount of aluminum salt solution is according to molar ratio Ti: Al
=5: x, x=0.01~0.55, while it is 8-11 that appropriate ammonium hydroxide, which is added, to adjust pH value, after being stirred to react 30-50min,
Stand 6 hours or so, be filtered, washed, be dried after obtain aluminum-oxide-coated nano lithium titanate composite material precursor, will
Aluminum-oxide-coated nano lithium titanate composite material precursor obtained 400-600 DEG C sintering 4-10 hours, naturally cool to
Room temperature obtains aluminum-oxide-coated nano lithium titanate composite material.This method in lithium titanate surface, does not change precipitation of alumina
Lithium titanate crystal structure, in practical applications, aluminium oxide cannot completely cut off completely lithium titanate in charge and discharge process and connect in electrolyte
Touching can not inherently change lithium titanate and produce mechanism of qi system.Chinese Patent Application No. CN201710011016.6 denomination of invention " one
The preparation method of the lithium titanate composite anode material of the salic doping of kind ", disclose a kind of lithium titanate of salic doping
The preparation method of composite negative pole material, first configuration titanium dioxide suspension, and it is kept stirring effect；Then into suspension
Soluble aluminum salting liquid is added and ammonia spirit obtains aqua oxidation aluminum precipitation, keeps pH value in the range of 7.1-9, by quiet
Electro Sorb effect makes hydrated alumina attachment and titanium dioxide surface；Finally lithium salts is mixed with titanium dioxide/hydrated alumina
Afterwards, the lithium titanate composite anode material Li of salic doping is made using multi-steps sintering method(4+X)AlXTi(5-X)O12, wherein
0.05≤x≤0.5.The present invention uses Al3+Ionic compartmentation surface portion Ti4+Ion realizes the purpose for inhibiting lithium titanate to produce gas.
Present invention employs the preparation of Electrostatic Absorption method, obtained material consistency is high, and low in cost, is easy to industrialization production.But
Its reaction temperature is high, and energy consumption is high, and complex process reduces the specific capacitance of lithium titanate.
Therefore, the new lithium titanate sill of one kind is found to meet the requirement of lithium ion battery negative material of new generation, is
The important topic of Study on Li-ion batteries bottleneck is broken through at present.
Summary of the invention
The shortcomings that in view of the above-mentioned prior art, the purpose of the present invention is to provide a kind of cathode of lithium battery lithium titanate-indium bismuths
Liquid metal material and preparation method.In the cathode of lithium battery lithium titanate-indium bismuth liquid metal material, indium bismuth liquid metal is with liquid
State form is inserted into the lithium titanate of three-dimension-framework, forms bulky grain, the closely knit lithium titanate connected by indium bismuth liquid metal.The metatitanic acid
Lithium-indium bismuth liquid metal material can thoroughly prevent the flatulence problem of lithium titanate, make lithium titanate battery in more than 100 DEG C high temperature rings
Stable operation under border, and preparation method is simple, is suitble to large-scale production.For cathode of lithium battery preferred material.Especially in automobile
In lithium battery, there is good safety guarantee and lasting charge-discharge performance.
In order to reach foregoing purpose, the present invention provides a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material,
In, the lithium titanate-indium bismuth liquid metal material is bulky grain, and the partial size of the bulky grain is 50 μm -500 μm,
And in the bulky grain, indium bismuth alloy coats lithium titanate nano particle, phosphide element, bismuth element mass ratio be
(0.55-0.8): 1, the mass ratio of the indium bismuth alloy and lithium titanate is (5-20): (95-80).
In above-mentioned lithium titanate-indium bismuth Binary liquid metals material, it is preferable that the pattern of the lithium titanate include stratiform,
The combination of one or more of microspheroidal, petal-shaped and sheet.
In above-mentioned lithium titanate-indium bismuth liquid metal material, it is preferable that the partial size of the lithium titanate nano particle is
50nm-500nm。
In above-mentioned lithium titanate-indium bismuth liquid metal material, it is preferable that the lithium titanate-indium bismuth liquid metal material
Raw material includes indium metal, bismuth metal and lithium titanate, and the mass ratio of the indium metal and the bismuth metal is (0.55-0.8): 1, institute
The mass ratio of the gross mass and the lithium titanate of stating indium metal and the bismuth metal is (5-20): (95-80).
In above-mentioned lithium titanate-indium bismuth liquid metal material, it is preferable that the lithium titanate-indium bismuth liquid metal material
Raw material includes indium bismuth alloy and lithium titanate, and in the indium bismuth alloy, the mass ratio of phosphide element and bismuth element is (0.55-0.8): 1,
The mass ratio of the indium bismuth alloy and the lithium titanate is (5-20): (95-80).
The present invention also provides above-mentioned lithium titanate-indium bismuth liquid metal material preparation methods comprising following steps:
Step 1: being ground to nanoscale for lithium titanate, forms the nano lithium titanate that partial size is 50nm-500nm；
Step 2: being (0.55-0.8) by indium metal, bismuth metal in mass ratio: 1 mixing, and is heated to 120 DEG C -180 DEG C,
It forms liquid alloy or indium bismuth alloy is heated to 120 DEG C -180 DEG C, form liquid alloy；
Step 3: being (5-20) by the liquid alloy in mass ratio: (95-80) is mixed with the nano lithium titanate, so
It is placed on progress air-flow dispersion in pneumatic spray drying device, obtains a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material
Material；The chamber temp of the pneumatic spray drying device is 90-120 DEG C.
In the above preparation method, it is preferable that the step 2 and step 3 carry out in protection gas, the protection gas bag
Include nitrogen or inert gas.
In the above preparation method, it is preferable that the air velocity of the pneumatic spray drying device is 4-6m/s.
In the above preparation method, it is preferable that the charging rate of the pneumatic spray drying device is 100-200g/min.
Material slowly enters in pneumatic spray drying device chamber, guarantees that the indium bismuth alloy package on nano lithium titanate surface is uniform.
In the above preparation method, it is preferable that the lithium titanate is prepared by following steps:
In the glycerine of volume ratio 0.05-0.2:1 and the in the mixed solvent of ethyl alcohol, bismuth nitrate dissolution is added, then titanium is added dropwise
Sour four butyl esters drop, reacts 18-24h at a temperature of 110 DEG C -150 DEG C after mixing, cooling, filtering, drying, and 500 DEG C -
600 DEG C of temperature lower calcination 1-3h；The molar ratio of the bismuth nitrate and the four fourth ethyl ester of metatitanic acid is 0.2-0.5:1.
Compared with prior art, in a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material provided by the invention, indium
Bismuth liquid metal is inserted into the lithium titanate of three-dimension-framework in liquid form, forms the bulky grain connected by indium bismuth liquid metal, closely knit
Lithium titanate.Phase transformation of the indium bismuth liquid metal at 90-120 DEG C in the lithium titanate-indium bismuth Binary liquid metals material thoroughly prevents
The flatulence problem of lithium titanate, so that operation of the lithium titanate battery under more than 100 DEG C hot environments be made to become stable.The present invention
The lithium titanate of offer-indium bismuth Binary liquid metals material preparation method, is ground to nanoscale for the lithium titanate of sintering, then plus
Enter indium bismuth liquid metal, adjusts temperature to 120-180 DEG C, indium bismuth liquid metal is made to be inserted into the metatitanic acid of three-dimension-framework in liquid form
Lithium, and reduce temperature by pneumatic spray drying device, air-flow dispersion form the bulky grain connected by indium bismuth liquid metal, close
Real lithium titanate, this method is simple, easy, is suitble to low cost large-scale production.
Specific embodiment
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
Present embodiments provide a kind of preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material comprising
Following steps:
Step 1: by volume it is that 0.05:1 is mixed by glycerine and ethyl alcohol, after stirring is mixed thoroughly, nitric acid is added
Bismuth solid simultaneously makes it completely dissolved, and butyl titanate is slowly added drop-wise in mixed liquor, is vigorously stirred 30min, then will mixing
It is transferred in reaction kettle after liquid ultrasonic treatment 15min；Wherein the molar ratio of bismuth nitrate and butyl titanate is 0.2:1；It will reaction
Kettle, which is placed in 120 DEG C of constant temperature oven, to react for 24 hours；Mixture filtering drying in kettle is placed in temperature programmed control furnace after cooling
3h is calcined at 600 DEG C, and the product of calcining is ground into evengranular powder after cooling, obtains nano lithium titanate；
Step 2: in mass ratio it is that 0.55:1 is mixed, and is heated to 150 DEG C by indium metal, bismuth metal, forms liquid and close
Gold；
Step 3: in mass ratio it is that 10:90 is mixed with nano lithium titanate by liquid alloy, is subsequently placed in air-flowing type and does by spraying
Air-flow dispersion is carried out in dry device, obtains lithium titanate-indium bismuth Binary liquid metals material；
The charging rate of pneumatic spray drying device is 100-200g/min, and chamber temp is 90-120 DEG C, air velocity
For 4-6m/s；
Step 2 and step 3 are carried out in glove box, and 99.9% argon gas is connected in glove box.
After tested, the partial size of nano lithium titanate made from the present embodiment is 50nm-100nm, and pattern is microspheroidal, obtained
Lithium titanate-indium bismuth Binary liquid metals material is closely knit bulky grain of the partial size at 50 μm -100 μm.
By lithium titanate-indium bismuth Binary liquid metals material, it is assembled into experimental cell test, initial charge capacity 180mAh/
G, cycle performance is excellent, and 10C circulation 600 times, capacity saves 95% or more.
Embodiment 2
Present embodiments provide a kind of preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material comprising
Following steps:
Step 1: by volume it is that 0.1:1 is mixed by glycerine and ethyl alcohol, after stirring is mixed thoroughly, nitric acid is added
Bismuth solid simultaneously makes it completely dissolved, and butyl titanate is slowly added drop-wise in mixed liquor, is vigorously stirred 30min, then will mixing
It is transferred in reaction kettle after liquid ultrasonic treatment 15min；Wherein the molar ratio of bismuth nitrate and butyl titanate is 0.2:1；It will reaction
Kettle, which is placed in 120 DEG C of constant temperature oven, to react for 24 hours；Mixture filtering drying in kettle is placed in temperature programmed control furnace after cooling
3h is calcined at 600 DEG C, and the product of calcining is ground into evengranular powder after cooling, obtains nano lithium titanate；
Step 2: in mass ratio it is that 0.55:1 is mixed, and is heated to 150 DEG C by indium metal, bismuth metal, forms liquid and close
Gold；
Step 3: in mass ratio it is that 10:90 is mixed with nano lithium titanate by liquid alloy, is subsequently placed in air-flowing type and does by spraying
Air-flow dispersion is carried out in dry device, obtains lithium titanate-indium bismuth Binary liquid metals material；
The charging rate of pneumatic spray drying device is 100-200g/min, and chamber temp is 90-120 DEG C, air velocity
For 4-6m/s；
Step 2 and step 3 are carried out in glove box, and 99.9% argon gas is connected in glove box.
After tested, the partial size of nano lithium titanate made from the present embodiment is 80nm-150nm, and pattern is petal-shaped, obtained
Lithium titanate-indium bismuth Binary liquid metals material is closely knit bulky grain of the partial size at 100 μm -500 μm.
By lithium titanate-indium bismuth Binary liquid metals material, it is assembled into experimental cell test, initial charge capacity 1730mAh/
G, cycle performance is excellent, and 10C circulation 600 times, capacity saves 96% or more.
Embodiment 3
Present embodiments provide a kind of preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material comprising
Following steps:
Step 1: by volume it is that 0.2:1 is mixed by glycerine and ethyl alcohol, after stirring is mixed thoroughly, nitric acid is added
Bismuth solid simultaneously makes it completely dissolved, and butyl titanate is slowly added drop-wise in mixed liquor, is vigorously stirred 30min, then will mixing
It is transferred in reaction kettle after liquid ultrasonic treatment 15min；Wherein the molar ratio of bismuth nitrate and butyl titanate is 0.2:1；It will reaction
Kettle, which is placed in 120 DEG C of constant temperature oven, to react for 24 hours；Mixture filtering drying in kettle is placed in temperature programmed control furnace after cooling
3h is calcined at 500 DEG C, and the product of calcining is ground into evengranular powder after cooling, obtains nano lithium titanate；
Step 2: in mass ratio it is that 0.6:1 is mixed, and is heated to 150 DEG C by indium metal, bismuth metal, forms liquid alloy；
Step 3: in mass ratio it is that 10:90 is mixed with nano lithium titanate by liquid alloy, is subsequently placed in air-flowing type and does by spraying
Air-flow dispersion is carried out in dry device, obtains lithium titanate-indium bismuth Binary liquid metals material；
The charging rate of pneumatic spray drying device is 100-200g/min, and chamber temp is 90-120 DEG C, air velocity
For 4-6m/s；
Step 2 and step 3 are carried out in glove box, and 99.9% argon gas is connected in glove box.
After tested, the partial size of nano lithium titanate made from the present embodiment is 60nm-100nm, and pattern is 3 dimension stratiforms, is made
Lithium titanate-indium bismuth Binary liquid metals material be closely knit bulky grain of the partial size at 100 μm -400 μm.
By lithium titanate-indium bismuth Binary liquid metals material, it is assembled into experimental cell test, initial charge capacity 186mAh/
G, cycle performance is excellent, and 10C circulation 600 times, capacity saves 91% or more.
Embodiment 4
Present embodiments provide a kind of preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material comprising
Following steps:
Step 1: by volume it is that 0.2:1 is mixed by glycerine and ethyl alcohol, after stirring is mixed thoroughly, nitric acid is added
Bismuth solid simultaneously makes it completely dissolved, and butyl titanate is slowly added drop-wise in mixed liquor, is vigorously stirred 30min, then will mixing
It is transferred in reaction kettle after liquid ultrasonic treatment 15min；Wherein the molar ratio of bismuth nitrate and butyl titanate is 0.2:1；It will reaction
Kettle, which is placed in 120 DEG C of constant temperature oven, to react for 24 hours；Mixture filtering drying in kettle is placed in temperature programmed control furnace after cooling
3h is calcined at 600 DEG C, and the product of calcining is ground into evengranular powder after cooling, obtains nano lithium titanate；
Step 2: in mass ratio it is that 0.8:1 is mixed, and is heated to 150 DEG C by indium metal, bismuth metal, forms liquid alloy；
Step 3: in mass ratio it is that 10:90 is mixed with nano lithium titanate by liquid alloy, is subsequently placed in air-flowing type and does by spraying
Air-flow dispersion is carried out in dry device, obtains lithium titanate-indium bismuth Binary liquid metals material；
The charging rate of pneumatic spray drying device is 100-200g/min, and chamber temp is 90-120 DEG C, air velocity
For 4-6m/s；
Step 2 and step 3 are carried out in glove box, and 99.9% argon gas is connected in glove box.
After tested, the partial size of nano lithium titanate made from the present embodiment is 80nm-120nm, and pattern is sheet, titanium obtained
Sour lithium-indium bismuth Binary liquid metals material is closely knit bulky grain of the partial size at 100 μm -450 μm.
By lithium titanate-indium bismuth Binary liquid metals material, it is assembled into experimental cell test, initial charge capacity 185mAh/
G, cycle performance is excellent, and 10C circulation 600 times, capacity saves 92% or more.
Embodiment 5
Present embodiments provide a kind of preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material comprising
Following steps:
Step 1: by volume it is that 0.05:1 is mixed by glycerine and ethyl alcohol, after stirring is mixed thoroughly, nitric acid is added
Bismuth solid simultaneously makes it completely dissolved, and butyl titanate is slowly added drop-wise in mixed liquor, is vigorously stirred 30min, then will mixing
It is transferred in reaction kettle after liquid ultrasonic treatment 15min；Wherein the molar ratio of bismuth nitrate and butyl titanate is 0.2:1；It will reaction
Kettle, which is placed in 120 DEG C of constant temperature oven, to react for 24 hours；Mixture filtering drying in kettle is placed in temperature programmed control furnace after cooling
3h is calcined at 600 DEG C, and the product of calcining is ground into evengranular powder after cooling, obtains nano lithium titanate；
Step 2: in mass ratio it is that 0.8:1 is mixed, and is heated to 150 DEG C by indium metal, bismuth metal, forms liquid alloy；
Step 3: in mass ratio it is that 10:90 is mixed with nano lithium titanate by liquid alloy, is subsequently placed in air-flowing type and does by spraying
Air-flow dispersion is carried out in dry device, obtains lithium titanate-indium bismuth Binary liquid metals material；
The charging rate of pneumatic spray drying device is 100-200g/min, and chamber temp is 90-120 DEG C, air velocity
For 4-6m/s；
Step 2 and step 3 are carried out in glove box, and 99.9% argon gas is connected in glove box.
After tested, the partial size of nano lithium titanate made from the present embodiment is 50nm-100nm, and pattern is microspheroidal, obtained
Lithium titanate-indium bismuth Binary liquid metals material is closely knit bulky grain of the partial size at 100 μm -500 μm.
By lithium titanate-indium bismuth Binary liquid metals material, it is assembled into experimental cell test, initial charge capacity 191mAh/
G, cycle performance is excellent, and 10C circulation 600 times, capacity saves 90% or more.
Embodiment 6
Present embodiments provide a kind of preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material comprising
Following steps:
Step 1: by volume it is that 0.2:1 is mixed by glycerine and ethyl alcohol, after stirring is mixed thoroughly, nitric acid is added
Bismuth solid simultaneously makes it completely dissolved, and butyl titanate is slowly added drop-wise in mixed liquor, is vigorously stirred 30min, then will mixing
It is transferred in reaction kettle after liquid ultrasonic treatment 15min；Wherein the molar ratio of bismuth nitrate and butyl titanate is 0.2:1；It will reaction
Kettle, which is placed in 120 DEG C of constant temperature oven, to react for 24 hours；Mixture filtering drying in kettle is placed in temperature programmed control furnace after cooling
3h is calcined at 500 DEG C, and the product of calcining is ground into evengranular powder after cooling, obtains nano lithium titanate；
Step 2: in mass ratio it is that 0.7:1 is mixed, and is heated to 150 DEG C by indium metal, bismuth metal, forms liquid alloy；
Step 3: in mass ratio it is that 10:90 is mixed with nano lithium titanate by liquid alloy, is subsequently placed in air-flowing type and does by spraying
Air-flow dispersion is carried out in dry device, obtains lithium titanate-indium bismuth Binary liquid metals material；
The charging rate of pneumatic spray drying device is 100-200g/min, and chamber temp is 90-120 DEG C, air velocity
For 4-6m/s；
Step 2 and step 3 are carried out in glove box, and 99.9% argon gas is connected in glove box.
After tested, the partial size of nano lithium titanate made from the present embodiment is 60nm-100nm, and pattern is microspheroidal, obtained
Lithium titanate-indium bismuth Binary liquid metals material is closely knit bulky grain of the partial size at 100 μm -500 μm.
By embodiment 1-6 it is found that in a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material provided by the invention,
Indium bismuth liquid metal is inserted into the lithium titanate of three-dimension-framework in liquid form, forms the bulky grain connected by indium bismuth liquid metal, close
Real lithium titanate.Indium bismuth liquid metal in the lithium titanate-indium bismuth liquid metal material is thoroughly prevented in 90-120 DEG C of phase transformation
The flatulence problem of lithium titanate, so that operation of the lithium titanate battery under more than 100 DEG C hot environments be made to become stable.The present invention mentions
The lithium titanate of confession-indium bismuth Binary liquid metals material preparation method, is ground to nanoscale for the lithium titanate of sintering, is then added
Indium bismuth liquid metal adjusts temperature to 120-180 DEG C, indium bismuth liquid metal is made to be inserted into the metatitanic acid of three-dimension-framework in liquid form
Lithium, and reduce temperature by pneumatic spray drying device, air-flow dispersion form the bulky grain connected by indium bismuth liquid metal, close
Real lithium titanate, this method is simple, easy, is suitble to low cost large-scale production.
Claims (6)
1. a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material, it is characterised in that: the lithium titanate-indium bismuth liquid gold
Category material is bulky grain, and the partial size of the bulky grain is 50 μm -500 μm, and in the bulky grain, indium bismuth alloy receives lithium titanate
Rice grain cladding, phosphide element, bismuth element mass ratio be (0.55-0.8): 1, the mass ratio of the indium bismuth alloy and lithium titanate is
(5-20): (95-80)；
Preparation method includes the following steps:
Step 1: being ground to nanoscale for lithium titanate, forms the nano lithium titanate that partial size is 50nm-500nm；
Step 2: indium bismuth alloy is heated to 120 DEG C -180 DEG C, forms liquid alloy；
Step 3: being (5-20) by the liquid alloy in mass ratio: (95-80) is mixed with the nano lithium titanate, is then set
Air-flow dispersion is carried out in pneumatic spray drying device, obtains lithium titanate-indium bismuth Binary liquid metals material；The air-flowing type spray
The chamber temp of mist drier is 90-120 DEG C.
2. a kind of cathode of lithium battery lithium titanate-indium bismuth liquid metal material according to claim 1, it is characterised in that: described
The pattern of lithium titanate includes the combination of one or more of stratiform, microspheroidal, petal-shaped and sheet.
3. a kind of any one of claim 1-2 preparation method of cathode of lithium battery lithium titanate-indium bismuth liquid metal material,
The following steps are included:
Step 1: being ground to nanoscale for lithium titanate, forms the nano lithium titanate that partial size is 50nm-500nm；
Step 2: bismuth alloy is heated to 120 DEG C -180 DEG C, forms liquid alloy；
Step 3: being (5-20) by the liquid alloy in mass ratio: (95-80) is mixed with the nano lithium titanate, is then set
Air-flow dispersion is carried out in pneumatic spray drying device, obtains lithium titanate-indium bismuth Binary liquid metals material；The air-flowing type spray
The chamber temp of mist drier is 90-120 DEG C.
4. preparation method according to claim 3, it is characterised in that: the step 2 and step 3 in protection gas into
Row, the protection gas bag include nitrogen or inert gas.
5. preparation method according to claim 3, it is characterised in that: the air velocity of the pneumatic spray drying device is
4-6m/s。
6. preparation method according to claim 3, it is characterised in that: the charging rate of the pneumatic spray drying device is
100-200g/min。
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