CN109698339A - A kind of lithium titanate composite material and its preparation method and application - Google Patents
A kind of lithium titanate composite material and its preparation method and application Download PDFInfo
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- CN109698339A CN109698339A CN201811616687.6A CN201811616687A CN109698339A CN 109698339 A CN109698339 A CN 109698339A CN 201811616687 A CN201811616687 A CN 201811616687A CN 109698339 A CN109698339 A CN 109698339A
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- H—ELECTRICITY
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- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- H—ELECTRICITY
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
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Abstract
The invention belongs to electrochemical energy storage fields, it is related to a kind of lithium titanate composite material and its preparation method and application, lithium titanate composite material is coated more particularly to a kind of aluminum phosphate titanium lithium salts, preparation method and the composite material as negative electrode material lithium ion battery purposes, the discharge capacity of phosphate base class solid electrolyte material/lithium titanate composite material provided by the invention, cycle performance and high rate performance be improved significantly, the lithium ion battery being prepared using the composite material as negative electrode material not only good conductivity, rate capability is high, it has extended cycle life, also have the advantages that production gas is few, with good prospects for commercial application.
Description
Technical field
The invention belongs to electrochemical energy storage field, it is related to a kind of lithium titanate composite material and its preparation method and application, tool
Body is related to a kind of aluminum phosphate titanium lithium salts cladding lithium titanate composite material, preparation method and the composite material and exists as negative electrode material
The purposes of lithium ion battery.
Background technique
Lithium titanate (Li4Ti5O12) it is 1.55V to the current potential of lithium, theoretical specific capacity 175mAh/g, actual specific capacity is
160-170mAh/g.Lithium titanate has face-centered cubic spinel structure, space group Fd3m, cell parameter a=0.836nm, electricity
Position is higher than graphite, is not likely to produce lithium dendrite arm；And 3 lithium ions can be accommodated in charge and discharge, insertion and deintercalation are to crystalline structure
It has little effect, is kind of " a zero strain material ", shows preferable cycle performance.
At present lithium ion battery to fast charge and it is macrocyclic require it is higher and higher, the advantages of lithium titanate be fast charge, long circulating,
High magnification and high temperature performance are excellent.However, lithium titanate is a kind of material that electric conductivity is very poor, the capacity attenuation under high magnification
Fastly.Although the electric conductivity of lithium titanate can be improved by reducing particle size and adding conductive agent, lithium titanate and electrolyte are caused
It is easier to produce gas at long circulating (3000 times or more), to reduce battery performance and cycle life, this just needs to take some arrange
It applies and avoids the above problem.
104600280 B of CN discloses a kind of method for preparing carbon coating lithium titanate, comprising the following steps: (1) will contain lithium
Compound and titanium-containing oxide ball milling, sintering obtain precursor A；(2) precursor A and deionized water are added in a kettle, so
Monomer and emulsifier SDS are added afterwards, nitrogen is led to after vacuumizing and stirs, 60-70 DEG C is heated to after system emulsification, in this temperature
Lower addition initiator stops heating after reacting 3-5h, and continues stirring up to cooling, methanol demulsification is then added, then use alcohol precipitation
It forms sediment, polymer/lithium titanate compound particle precursor B is obtained by filtration；(3) it is roasted under nitrogen environment, obtains carbon-coated lithium titanate
Material.Carbon source is coated on lithium titanate surface even compact in the composite material obtained using this method, and product particle is small, and size is equal
Even, good dispersion can improve high-rate charge-discharge capability and cycle performance.But this method is cumbersome, unfavorable industry
Production, and can not solve the problems, such as that production gas is more.
Phosphate base class solid electrolyte series material clad provided by the invention is able to suppress metallic atom and is being electrolysed
Dissolution in liquid and lithium titanate structural damage is prevented, while promoting the electric conductivity and ion of material as a kind of solid electrolyte
Diffusion coefficient, so as to keep the stabilization of lithium titanate surface texture and internal structure, thus it is shown that higher cycle performance
With the ability for inhibiting production gas.
Summary of the invention
For the above-mentioned problems in the prior art, the purpose of the present invention is to provide a kind of phosphate base class solid-state electricity
Solve material/lithium titanate composite material and its preparation method and application.Phosphate base class solid electrolyte material/titanium of the invention
Discharge capacity, cycle performance and the high rate performance of sour lithium composite material be improved significantly, using the composite material as cathode
Not only good conductivity, rate capability are high for the lithium ion battery that material is prepared, have extended cycle life, and also have and produce few excellent of gas
Point has good prospects for commercial application.
Specifically, in a first aspect, the present invention provides the composite woods of a kind of phosphate base class solid electrolyte and lithium titanate
Material, the composite material include lithium titanate and are coated on the lithium titanate surface or intergranular phosphate base class solid state electrolysis
Material.
Preferably, the phosphate base class solid electrolyte material includes metal lithium salts, M compound, aluminium compound, titanizing
Close object, template, dihydric phosphate.It is furthermore preferred that the phosphate base class solid electrolyte material is by metal lithium salts, M chemical combination
Object, aluminium compound, titanium compound, template, dihydric phosphate mix according to molar ratio, disperse, is dry, then in inert gas
Under the conditions of high-temperature process obtain.
It is further preferred that the metal lithium salts is selected from lithium acetate, lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate, chlorine
Any one in change lithium, lithium dihydrogen phosphate or at least two combinations.The mixture is typical but non-limiting example has: lithium acetate
With the mixture of lithium carbonate, the mixture of lithium acetate and lithium hydroxide, the mixture of lithium acetate and lithium nitrate, lithium carbonate and sulfuric acid
The mixture of lithium, lithium carbonate, lithium hydroxide and mixture of lithium chloride etc..Lithium hydroxide is chosen as lithium hydroxide, a hydronium(ion)
Lithia.
Preferably, the M compound any one or at least two combined gold in Ca, Mg, Ge, La, Si or Sr
Belong to oxide, hydroxide, phosphate or phosphoric acid lithium salts.Phosphoric acid lithium salts is selected from aluminum phosphate lithium, titanium phosphate lithium, phosphoric acid aluminum magnesium titanate
Lithium, aluminum phosphate titanium lanthanum lithium；Metal oxide is typical but non-limiting example has: SiO2、LaO3；Hydroxide is typical but unrestricted
Property example has magnesium hydroxide.
Preferably, the aluminium compound in aluminum nitrate, aluminium citrate, aluminium oxide, aluminum phosphate any one or at least
Two kinds of combinations.
Preferably, the titanium compound is selected from tetraethyl titanate, butyl titanate, metatitanic acid methyl esters, titanium chloride or titanium dioxide
In any one or at least two combination.The mixture is typical but non-limiting example has: tetraethyl titanate and butyl titanate
Mixture, the mixture of tetraethyl titanate and titanium chloride, the mixture of tetraethyl titanate, butyl titanate and metatitanic acid methyl esters, metatitanic acid
Four butyl esters, metatitanic acid methyl esters, titanium chloride and mixture of titanium dioxide etc..
Preferably, the template is selected from glucose, sucrose, citric acid, polyethylene glycol, polyvinylpyrrolidone, carbon and receives
Any one in mitron or at least two combinations.
Preferably, the dihydric phosphate any one or two kinds in lithium dihydrogen phosphate, ammonium dihydrogen phosphate.
It is further preferred that Li:M in the metal lithium salts, M compound, aluminium compound, titanium compound, dihydric phosphate:
Al:Ti:PO4Molar ratio is (1+x+y): y:x:(2-x): (3+y), wherein 0≤x≤2.0,0≤y≤0.1.
Preferably, the usage amount of the template be gross mass 1~10%, such as 3%, 4%, 5%, 6%, 8%,
10% etc..
Preferably, the chemical composition of the lithium titanate is Li4Ti5O12。
It is furthermore preferred that the mass ratio of the phosphate base class solid electrolyte material and lithium titanate is 0.01:1~0.1:1,
Such as 0.01:1,0.02:1,0.03:1,0.04:1,0.05:1,0.06:1,0.07:1,0.08:1,0.09:1 or 0.1:1 etc..
If mass ratio is less than 0.01:1, it can make the clad to be formed is too thin coating function failure and lithium titanate circulation and multiplying power is caused to be held
Amount does not improve；If mass ratio is greater than 0.1:1, it can make the clad to be formed is blocked up to cause lithium ion mobility resistance excessive to make
The decline of lithium titanate rate capability.
Second aspect, the present invention also provides a kind of preparation methods of above-mentioned composite material, comprising the following steps:
(1) preparation of phosphate base class solid electrolyte material: metal lithium salts, M compound, aluminium compound, titanizing are closed
Object, template, dihydric phosphate mix according to molar ratio, disperse, is dry, and then high-temperature process obtains under inert gas conditions
Phosphate base class solid electrolyte material；
(2) composite material nanometerization handle: lithium salts, titanium compound are distributed in aqueous solvent according to molar ratio, then to
Phosphoric acid is added for 0.01~0.1:1 according to the mass ratio of phosphate base class solid electrolyte material and lithium titanate in above-mentioned dispersion liquid
Salt base class material obtains nanosizing slurry by nanosizing high power treatment；
(3) composite material spray-drying process: by the nanosizing slurry spray-drying process of step (2), phosphate is obtained
Base class/titanium-containing oxide powder composite precursor；
(4) composite material high temperature sintering: the powder composite precursor that step (3) is obtained high temperature under inert gas protection
Processing, natural cooling cool down to obtain the composite material of phosphate base class solid electrolyte and lithium titanate.
Preferably, high-temperature process temperature is 750-850 DEG C under step (1) inert gas conditions, and the time is 2~10h.Such as
Temperature is 750 DEG C, 770 DEG C, 800 DEG C, 825 DEG C or 850 DEG C etc.；Reaction time be 2h, 3h, 4h, 5h, 6h, 7h, 8h, 8.5h,
9h, 9.5h or 10h etc..
Preferably, lithium salts, titanium compound molar ratio are weighed according to 0.8~0.88:1 in step (2)；Then phosphate base is pressed
The mass ratio of class solid electrolyte material and lithium titanate is that phosphate base class material is added in 0.01~0.1:1, after above-mentioned weighing
Raw material addition appropriate amount of deionized water is added to progress nanosizing in high-energy ball milling mixing apparatus and handles to obtain mixture nanometer slurrying
Material, the nanosizing processing time are 2~12h, and dispersion grinding rate is 400~800r/min.For example, phosphate base class solid-state
The mass ratio of electrolyte and lithium titanate is 0.01:1,0.02:1,0.04:1,0.06:1,0.08:1,0.1:1；At nanosizing
Managing the time is 2h, 4h, 6h, 8h, 10h, 12h；Dispersing grinding rate is 400r/min, 500r/min, 600r/min, 700r/
min、800r/min。
Preferably, step (3) spray-drying process feed rate is 1~10kg/h, and drying temperature is set as 200~280
DEG C, such as feed rate is 1kg/h, 2kg/h, 4kg/h, 6kg/h, 8kg/h, 10kg/h；Drying temperature be 200 DEG C, 220 DEG C,
230 DEG C, 235 DEG C, 245 DEG C, 250 DEG C, 260 DEG C, 270 DEG C or 280 DEG C etc..
Preferably, step (4) high-temperature process temperature is 650~850 DEG C, and the time is 2~15 hours.Such as temperature is 650
DEG C, 675 DEG C, 700 DEG C, 725 DEG C, 750 DEG C, 770 DEG C, 800 DEG C, 825 DEG C or 850 DEG C etc.；Reaction time be 2h, 3h, 4h, 5h,
6h, 7h, 8h, 8.5h, 9h, 9.5h, 10h, 11h, 11.5h, 12h, 13h, 14h or 15h etc..
Wherein, step (1), the inert gas in (4) are nitrogen, argon gas, carbon dioxide or hydrogen.In step (1), (4)
Heating rate is preferably 1~15 DEG C/min, such as 1 DEG C/min, 5 DEG C/min, 10 DEG C/min or 15 DEG C/min etc..
Further, the solid electrolyte material of phosphate base class described in composite material and preparation method thereof；The lithium metal
Salt, M compound, aluminium compound, titanium compound, template, dihydric phosphate, lithium titanate；The metal lithium salts, M compound, aluminium
Compound, titanium compound, template, Li:M:Al:Ti:PO in dihydric phosphate4Molar ratio；The usage amount of the template；Institute
State the preferred embodiments such as the mass ratio of phosphate base class solid electrolyte material and lithium titanate with phosphate base described in first aspect
Class solid electrolyte is identical with the composite material of lithium titanate.
The third aspect, negative electrode material and/or capacitor the invention further relates to the composite material as lithium ion battery
Electrode material preparation method.
That is, the cathode includes phosphate base class solid-state described in first aspect the present invention relates to a kind of negative electrode material
Electrolyte/lithium titanate composite material.The invention further relates to a kind of lithium ion battery, the lithium ion battery includes first party
Phosphate base class solid electrolyte material/lithium titanate composite material is as negative electrode material described in face.
In phosphate base class solid electrolyte material/lithium titanate composite material of the invention, phosphate base class solid state electrolysis
Material clad can effectively inhibit lithium titanate and electrolyte or moisture that side reaction, phosphate base class solid electrolyte material occurs
Material has preferable compatibility with electrolyte, provides the inhibition point that lithium titanate surface is reacted with electrolyte interface, prevents electrolyte
Middle solvent is reacted with the catalysis of metal ion in lithium titanate material, is reduced and is prevented lithium titanate metallic atom in the electrolytic solution molten
Solution and its structure change.
It is mentioned in phosphate base class solid electrolyte material/lithium titanate composite material due to the introducing of solid electrolyte simultaneously
The electronic conductivity and ionic conductivity for rising material, reach while being promoted the synthesis conductivity of material, solve single promotion electronics
Conductivity causes the problem of lithium ion relaxation time in charge and discharge process, effectively supplements local lithium ion vacancy, reduces in electrification
It learns during being slipped into reaction process due to lithium ion, Ti caused by diffusive migration problem4+-Ti3+Variation of valence reduces Ti3+'s
In the presence of and by it cause catalytic pyrolysis electrolyte solvent production gas side reaction, so that it is bigger than normal to lower battery polarization caused by material
The problem of.
Also, more preferably, the phosphate base class solid electrolyte material clad is three-dimensional structure.Phosphate base
Class solid electrolyte material clad has stable three-dimensional structure, the characteristic with lithium ion conductor and electronic conductor, so
It can be improved the electric conductivity of material.
The composite material that the present invention obtains is that nanoscale phosphate base class is formed between lithium titanate particle surface and particle
Material cladding or compound.
In method of the invention, high-energy ball milling is nanosizing dispersion step, and raw material is promoted to be sufficiently mixed；It is spraying dry
Dry to have heating rate fast, heat treatment time is short, and the low temperature spray drying by elder generation at 200 DEG C -280 DEG C can make matrix material
Material and covering material zero gradient are evenly heated, therefore be can be realized nanoscale phosphate base class material and equably coated or adhere to
On lithium titanate particle surface.
In method of the invention, by the way that first lithium titanate raw material lithium salts, titanium dioxide and metal salt and phosphate are mixed
Low temperature spray drying again after nanosizing, then high temperature sintering, synthesizes phosphate base class solid electrolyte material/metatitanic acid lithium composite
Material.In composite material using this method preparation, phosphate base class solid electrolyte material fabricated in situ, clad uniformity
It is good, there is stable three-dimensional structure after ball-typeization processing, lithium titanate and electrolyte or moisture can not only be inhibited to occur secondary anti-
It answers, also significantly improves the electric conductivity of material.
Specific embodiment
The present invention will be further described with reference to the examples below.Described embodiment and its result are merely to illustrate
The present invention, without the present invention described in detail in claims should will not be limited.
Embodiment 1
(1) prepared by phosphate base class solid electrolyte material: being n according to nonstoichiometric molar ratio(LiOH·H2O):n(SiO2):
n(Al2O3):n(TiO2):n(NH4H2PO4)=1.32:0.02:0.3:1.7:3.02 weighs each substance, carries out mixing dispersion, adds simultaneously
The glucose that total weight is 3% is uniformly mixed, and dry, then at 800 DEG C, high-temperature process 9h under inert gas conditions obtains phosphorus
Hydrochlorate base class solid electrolyte material；
(2) preparation of composite material: aqueous solvent is distributed to after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.84:1
In, the phosphate base class that above-mentioned synthesis is added in dispersion liquid for 0.02:1 according to phosphate/lithium titanate weight ratio is stated then up
Material, control drum's speed of rotation obtain nanosizing slurry by 5h nanosizing high power treatment for 650rad/min；Mixture paste
Spray-drying process, feed rate 8kg/h, drying temperature set 260 DEG C, obtain phosphate base class/titanium-containing oxide compound precursor
Body；By powder presoma with the heating rate of 8 DEG C/min, N2It is hot within the temperature range of 800 DEG C under the conditions of/Ar protective gas
12h is handled, in N2Cooling obtains phosphate base/lithium titanate composite anode material under the conditions of protective gas.The composite material be
Nanoscale phosphate base class material cladding or compound is formed between lithium titanate particle surface and particle.
Embodiment 2
(1) prepared by phosphate base class solid electrolyte material: being n according to nonstoichiometric molar ratio(LiOH·H2O):n(SiO2):
n(Al2O3):n(TiO2):n(NH4H2PO4)=1.44:0.04:0.4:1.6:3.04 weighs each substance, carries out mixing dispersion, adds simultaneously
The glucose that total weight is 5% is uniformly mixed, and dry, then at 820 DEG C, high-temperature process 10h under inert gas conditions is obtained
Phosphate base class solid electrolyte material；
(2) it the preparation of composite material: is distributed to after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.832:1 water-soluble
In agent, the phosphate base that above-mentioned synthesis is added in dispersion liquid for 0.04:1 according to phosphate/lithium titanate weight ratio is stated then up
Class material, control drum's speed of rotation obtain nanosizing slurry by 5h nanosizing high power treatment for 650rad/min；Mixture slurry
Expect spray-drying process, feed rate 10kg/h, drying temperature sets 260 DEG C, obtain phosphate base class/titanium-containing oxide it is compound before
Drive body；By powder presoma with the heating rate of 5 DEG C/min, N2Under the conditions of/Ar protective gas, within the temperature range of 780 DEG C
It is heat-treated 12h, in N2It is cooled to 100 DEG C under the conditions of protective gas and obtains phosphate base/lithium titanate composite anode material.This is compound
Material is that nanoscale phosphate base class material cladding or compound is formed between lithium titanate particle surface and particle.
Embodiment 3
(1) prepared by phosphate base class solid electrolyte material: being n according to nonstoichiometric molar ratio(LiOH·H2O):n(Mg(OH)2):
n(Al2O3):n(TiO2):n(NH4H2PO4)=1.46:0.06:0.4:1.6:3.06 weighs each substance, carries out mixing dispersion, adds simultaneously
The glucose that total weight is 4% is uniformly mixed, and dry, then at 810 DEG C, high-temperature process 8h under inert gas conditions obtains phosphorus
Hydrochlorate base class solid electrolyte material；
(2) it the preparation of composite material: is distributed to after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.828:1 water-soluble
In agent, the phosphate base that above-mentioned synthesis is added in dispersion liquid for 0.04:1 according to phosphate/lithium titanate weight ratio is stated then up
Class material, control drum's speed of rotation obtain nanosizing slurry by 6h nanosizing high power treatment for 750rad/min；Mixture slurry
Expect spray-drying process, feed rate 10kg/h, drying temperature sets 250 DEG C, obtain phosphate base class/titanium-containing oxide it is compound before
Drive body；By powder presoma with the heating rate of 10 DEG C/min, N2Under the conditions of/Ar protective gas, within the temperature range of 795 DEG C
It is heat-treated 12h, in N2It is cooled to 100 DEG C under the conditions of protective gas and obtains phosphate base class/lithium titanate composite anode material.This is multiple
Condensation material is that nanoscale phosphate base class material cladding or compound is formed between lithium titanate particle surface and particle.
Embodiment 4
(1) prepared by phosphate base class solid electrolyte material: being n according to nonstoichiometric molar ratio(LiOH·H2O):n(Mg(OH)2):
n(Al2O3):n(TiO2):n(NH4H2PO4)=1.4:0.1:0.3:1.7:3.1 weighs each substance, carries out mixing dispersion, while adding gross weight
The glucose that amount is 8% is uniformly mixed, and dry, then at 850 DEG C, high-temperature process 8h under inert gas conditions obtains phosphate
Base class solid electrolyte material；
(2) it the preparation of composite material: is distributed to after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.828:1 water-soluble
In agent, the phosphate base that above-mentioned synthesis is added in dispersion liquid for 0.08:1 according to phosphate/lithium titanate weight ratio is stated then up
Class material, control drum's speed of rotation obtain nanosizing slurry by 6h nanosizing high power treatment for 750rad/min；Mixture slurry
Expect spray-drying process, feed rate 10kg/h, drying temperature sets 250 DEG C, obtain phosphate base class/titanium-containing oxide it is compound before
Drive body；By powder presoma with the heating rate of 15 DEG C/min, N2Under the conditions of/Ar protective gas, within the temperature range of 810 DEG C
It is heat-treated 10h, in N2It is cooled to 100 DEG C under the conditions of protective gas and obtains phosphate base/lithium titanate composite anode material.This is compound
Material is that nanoscale phosphate base class material cladding or compound is formed between lithium titanate particle surface and particle.
Embodiment 5
(1) prepared by phosphate base class solid electrolyte material: being n according to nonstoichiometric molar ratio(LiOH·H2O):n(LaO3):
n(Al2O3):n(TiO2):n(NH4H2PO4)=2.05:0.05:1:1:3.05 weighs each substance, carries out mixing dispersion, while adding gross weight
The glucose that amount is 10% is uniformly mixed, and dry, then at 750 DEG C, high-temperature process 10h under inert gas conditions obtains phosphoric acid
Salt base class solid electrolyte material；
(2) it the preparation of composite material: is distributed to after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.828:1 water-soluble
In agent, the phosphate base class that above-mentioned synthesis is added in dispersion liquid for 0.1:1 according to phosphate/lithium titanate weight ratio is stated then up
Material, control drum's speed of rotation obtain nanosizing slurry by 6h nanosizing high power treatment for 750rad/min；Mixture paste
Spray-drying process, feed rate 10kg/h, drying temperature set 250 DEG C, obtain phosphate base class/titanium-containing oxide compound precursor
Body；By powder presoma with the heating rate of 10 DEG C/min, N2It is hot within the temperature range of 820 DEG C under the conditions of/Ar protective gas
11h is handled, in N2It is cooled to 100 DEG C under the conditions of protective gas and obtains phosphate base/lithium titanate composite anode material.The composite wood
Material is that nanoscale phosphate base class material cladding or compound is formed between lithium titanate particle surface and particle.
Embodiment 6
(1) prepared by phosphate base class solid electrolyte material: being n according to nonstoichiometric molar ratio(LiOH·H2O):n(LaO3):
n(Al2O3):n(TiO2):n(NH4H2PO4)=1.22:0.02:0.2:1.8:3.02 weighs each substance, carries out mixing dispersion, adds simultaneously
The glucose that total weight is 6% is uniformly mixed, and dry, then at 800 DEG C, high-temperature process 10h under inert gas conditions is obtained
Phosphate base class solid electrolyte material；
(2) it the preparation of composite material: is distributed to after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.824:1 water-soluble
In agent, the phosphate base that above-mentioned synthesis is added in dispersion liquid for 0.02:1 according to phosphate/lithium titanate weight ratio is stated then up
Class material, control drum's speed of rotation obtain nanosizing slurry by 4h nanosizing high power treatment for 700rad/min；Mixture slurry
Expect spray-drying process, feed rate 10kg/h, drying temperature sets 270 DEG C, obtain phosphate base class/titanium-containing oxide it is compound before
Drive body；By powder presoma with the heating rate of 6 DEG C/min, N2Under the conditions of/Ar protective gas, within the temperature range of 790 DEG C
It is heat-treated 11h, in N2It is cooled to 100 DEG C under the conditions of protective gas and obtains phosphate base/lithium titanate composite anode material.This is compound
Material is that nanoscale phosphate base class material cladding or compound is formed between lithium titanate particle surface and particle.
Comparative example
It is distributed in aqueous solvent after lithium carbonate, titanium dioxide are weighed according to molar ratio 0.828:1, controls drum's speed of rotation
Nanosizing slurry is obtained by 6h nanosizing high power treatment for 750rad/min；Mixture paste spray-drying process feed rate
10kg/h, drying temperature set 250 DEG C, obtain titanium-containing oxide presoma；By powder presoma with the heating rate of 10 DEG C/min,
N2Under the conditions of/Ar protective gas, it is heat-treated 11h within the temperature range of 820 DEG C, in N2100 DEG C are cooled under the conditions of protective gas
Obtain lithium titanate anode material.
Embodiment and comparative example (pure lithium titanate) are subjected to electrochemical property test: will be prepared into above-described embodiment respectively
Phosphate base class solid electrolyte material/lithium titanate composite material negative electrode active material, conductive black and the Kynoar arrived
(PVDF) it is uniformly mixed, is applied in copper foil current collector by 80:10:10 weight ratio, it is vacuum dried to be dried for standby；Simulate half-cell
It is assemblied in the glove box of applying argon gas and carries out, electrolyte is 1mol/L LiPF6/ EC+DMC+EMC solution, wherein EC, DMC, EMC
Volume ratio is 1:1:1, and metal lithium sheet is to electrode, and electrochemical property test carries out on land battery performance test instrument, charge and discharge
Piezoelectric voltage range is 1.0V to 2.5V.
Claims (12)
1. a kind of composite material of phosphate base class solid electrolyte and lithium titanate, the composite material include lithium titanate and cladding
In the lithium titanate surface or intergranular phosphate base class solid electrolyte material.
2. composite material as described in claim 1, which is characterized in that the phosphate base class solid electrolyte material includes gold
Belong to lithium salts, M compound, aluminium compound, titanium compound, template, dihydric phosphate.
3. composite material as claimed in claim 2, which is characterized in that the metal lithium salts is selected from lithium acetate, lithium carbonate, hydrogen-oxygen
Change lithium, lithium nitrate, lithium sulfate, lithium chloride, any one in lithium dihydrogen phosphate or at least two combinations；The M compound is selected from
Any one in Ca, Mg, Ge, La, Si or Sr or at least two combined metal oxides, hydroxide, phosphate or phosphoric acid
Lithium salts；The aluminium compound in aluminum nitrate, aluminium citrate, aluminium oxide, aluminum phosphate any one or at least two combination；Institute
State titanium compound in tetraethyl titanate, butyl titanate, metatitanic acid methyl esters, titanium chloride or titanium dioxide any one or at least two
Kind combination；The template is appointed in glucose, sucrose, citric acid, polyethylene glycol, polyvinylpyrrolidone, carbon nanotube
Anticipating, a kind of or at least two combine；The dihydric phosphate in lithium dihydrogen phosphate, ammonium dihydrogen phosphate any one or two
Kind.
4. according to the described in any item composite materials of claim 2, which is characterized in that the metal lithium salts, M compound, calorize
Close object, titanium compound, Li:M:Al:Ti:PO in dihydric phosphate4Molar ratio is (1+x+y): y:x:(2-x): (3+y), wherein
0≤x≤2.0,0≤y≤0.1；The usage amount of template is the 1~10% of gross mass.
5. composite material as described in claim 1, which is characterized in that the chemical composition of the lithium titanate is Li4Ti5O12。
6. composite material as described in claim 1, which is characterized in that the phosphate base class solid electrolyte material and metatitanic acid
The mass ratio of lithium is 0.01:1~0.1:1.
7. a kind of preparation method of composite material described in claim 1, comprising the following steps:
(1) preparation of phosphate base class solid electrolyte material: by metal lithium salts, M compound, aluminium compound, titanium compound, mould
Plate agent, dihydric phosphate mix according to molar ratio, disperse, is dry, and then high-temperature process obtains phosphoric acid under inert gas conditions
Salt base class solid electrolyte material；
(2) composite material nanometerization is handled: lithium salts, titanium compound being distributed in aqueous solvent according to molar ratio, stated then up
Phosphate base is added for 0.01~0.1:1 according to the mass ratio of phosphate base class solid electrolyte material and lithium titanate in dispersion liquid
Class material obtains nanosizing slurry by nanosizing high power treatment；
(3) composite material spray-drying process: by the nanosizing slurry spray-drying process of step (2), obtain phosphate base class/
Titanium-containing oxide powder composite precursor；
(4) composite material high temperature sintering: the powder composite precursor that step (3) is obtained is under inert gas protection at high temperature
Reason, natural cooling cool down to obtain the composite material of phosphate base class solid electrolyte and lithium titanate.
8. preparation method as claimed in claim 7, which is characterized in that high-temperature process temperature under step (1) inert gas conditions
It is 750-850 DEG C, the time is 2~10h.
9. preparation method as claimed in claim 7, which is characterized in that lithium salts in step (2), titanium compound molar ratio according to
0.8~0.88:1 weighing；It then is that 0.01~0.1:1 adds by the mass ratio of phosphate base class solid electrolyte material and lithium titanate
Enter phosphate base class material, raw material addition appropriate amount of deionized water after above-mentioned weighing is added in high-energy ball milling mixing apparatus and is carried out
Nanosizing handles to obtain mixture nanosizing slurry, and the nanosizing processing time is 2~12h, and dispersion grinding rate is 400~
800r/min。
10. preparation method as claimed in claim 7, which is characterized in that step (3) spray-drying process feed rate be 1~
10kg/h, drying temperature are set as 200~280 DEG C.
11. preparation method as claimed in claim 7, which is characterized in that step (4) high-temperature process temperature is 650~850 DEG C,
Time is 2~15 hours.
12. such as negative electrode material and/or capacitor of the described in any item composite materials of claim 1-11 as lithium ion battery
Electrode material preparation method.
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| CN111848151A (en) * | 2020-08-10 | 2020-10-30 | 西安航空学院 | Titanium magnesium aluminum lithium phosphate LAMTP single-phase ceramic wave-absorbing material and preparation method and application thereof |
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