CN107768633A - A kind of fluorophosphate cladding lithium titanate composite material, preparation method and the usage - Google Patents
A kind of fluorophosphate cladding lithium titanate composite material, preparation method and the usage Download PDFInfo
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- CN107768633A CN107768633A CN201710963278.2A CN201710963278A CN107768633A CN 107768633 A CN107768633 A CN 107768633A CN 201710963278 A CN201710963278 A CN 201710963278A CN 107768633 A CN107768633 A CN 107768633A
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Abstract
The present invention relates to a kind of fluorophosphate cladding lithium titanate composite material, preparation method and the usage, the composite includes lithium titanate and is coated on the fluorophosphate clad on the lithium titanate surface.Methods described includes：Lithium titanate is dissolved in solvent, is stirring evenly and then adding into fluorophosphate, fluorophosphate coating is formed on lithium titanate particle surface through low temperature spray drying；Then fluorophosphate is obtained by microwave method high temperature sintering and coats lithium titanate composite material.The present invention fluorophosphate cladding lithium titanate composite material discharge capacity, cycle performance and high rate performance be improved significantly, not only good conductivity, rate capability are high for the lithium ion battery being prepared using the composite as negative material, have extended cycle life, the advantages of also with aerogenesis less, there is good prospects for commercial application.
Description
Technical field
The invention belongs to lithium ion battery negative material field, be related to a kind of fluorophosphate cladding lithium titanate composite material,
Preparation method and the usage, and in particular to a kind of fluorophosphate cladding lithium titanate composite material, its preparation method and the composite wood
Expect the purposes in lithium ion battery as negative material.
Background technology
Lithium titanate (Li4Ti5O12) it is 1.55V to the current potential of lithium, theoretical specific capacity 175mAh/g, actual specific capacity is
160-170mAh/.Lithium titanate has face-centered cubic spinel structure, space group Fd3m, cell parameter a=0.836nm, current potential
It is higher than graphite, it is not likely to produce lithium dendrite arm；And 3 lithium ions can be accommodated in discharge and recharge, embedded and deintercalation is several to crystalline structure
Do not influence, be kind of " a zero strain material ", show preferable cycle performance.
At present lithium ion battery to fast charge and it is macrocyclic require more and more higher, be the advantages of lithium titanate fast charge, long circulating,
High magnification and high temperature performance are excellent.However, lithium titanate is a kind of very poor material of electric conductivity, the capacity attenuation under high magnification
It hurry up.Although the electric conductivity of lithium titanate can be improved by reducing particle size and adding conductive agent, lithium titanate and electrolyte are caused
Aerogenesis is easier in long circulating (1500-2000 times), so as to reduce battery performance and cycle life, this just needs to take some to arrange
Apply and avoid above mentioned problem.
The B of CN 104600280 disclose a kind of method for preparing carbon coating lithium titanate, comprise the following steps：(1) lithium will be contained
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 emulsifying agent SDS are added afterwards, nitrogen is led to after vacuumizing and is stirred, and 60-70 DEG C are heated to after system emulsification, in this temperature
Lower addition initiator, stop heating after reacting 3-5h, and continue stirring until cooling, then adds methanol demulsification, then use alcohol precipitation
Form sediment, be filtrated to get polymer/lithium titanate compound particle precursor B；(3) it is calcined under nitrogen environment, obtains the lithium titanate of carbon coating
Material.Carbon source is coated on lithium titanate surface even compact in the composite obtained using this method, and product particle is small, and size is equal
It is even, good dispersion, high-rate charge-discharge capability and cycle performance can be improved.But this method is cumbersome, unfavorable industry
Production, and can not solve the problems, such as that aerogenesis is more.
The content of the invention
For the above-mentioned problems in the prior art, it is an object of the invention to provide a kind of fluorophosphate to coat metatitanic acid
Lithium composite material, preparation method and the usage.The discharge capacity of the fluorophosphate cladding lithium titanate composite material of the present invention, circulation
Performance and high rate performance be improved significantly, the lithium ion battery being prepared using the composite as negative material is not only
Good conductivity, rate capability are high, have extended cycle life, and the advantages of also lacking with aerogenesis, have good prospects for commercial application.
For the above-mentioned purpose, the present invention uses following technical scheme：
In a first aspect, the present invention provides a kind of fluorophosphate cladding lithium titanate composite material, the composite includes titanium
Sour lithium and the fluorophosphate clad for being coated on the lithium titanate surface.
In the fluorophosphate cladding lithium titanate composite material of the present invention, fluorophosphate clad can effectively suppress lithium titanate
Occur side reaction with electrolyte or moisture, chemistry occurs for the metal ions M in F ion and lithium titanate in fluorophosphate clad
Effect, formed combine can be stronger M-F ionic bonds, therefore can prevent the dissolving in the electrolytic solution of lithium titanate metallic atom and
Its structure change.
Preferably, the particle diameter of the lithium titanate is 200-500nm, for example, 200nm, 220nm, 240nm, 280nm, 300nm,
350nm, 375nm, 400nm, 450nm or 500nm etc..
Preferably, the fluorophosphate is LiMPO4F, wherein, any one in M=Al, Ni, Mn, Co, Fe, V or Mo
Or at least two combination.
Preferably, the fluorophosphate clad is three-dimensional structure.Fluorophosphate clad has stable three-dimensional structure,
Characteristic with lithium ion conductor and electronic conductor, so the electric conductivity of material can be improved.
Preferably, the thickness of the fluorophosphate clad is 2-5nm, such as 2nm, 3nm, 4nm or 5nm etc., is preferably
3nm。
Preferably, the mass ratio of fluorophosphate clad and lithium titanate is (0.01-0.1):1, such as 0.01:1、0.03:
1、0.04:1、0.05:1、0.06:1、0.08:1、0.09:1 or 0.1:1 etc..If mass ratio is less than 0.01:1, the bag to be formed can be made
Coating is too thin to cause coating function failure and lithium titanate circulation and rate capability not to improve；If mass ratio is more than 0.1:1, meeting
Make the clad to be formed is blocked up to cause lithium ion mobility resistance excessive so that lithium titanate rate capability declines.
Second aspect, the present invention provide the preparation side of fluorophosphate cladding lithium titanate composite material as described in relation to the first aspect
Method, it the described method comprises the following steps：
(1) lithium titanate is dissolved in solvent, is stirring evenly and then adding into fluorophosphate, done in 150 DEG C of -160 DEG C of cold nebulizations
It is dry, form fluorophosphate coating on lithium titanate particle surface；
(2) Spray dried products thing is sintered by microwave method, obtains fluorophosphate cladding lithium titanate composite material.
In the method for the present invention, be spray-dried as low temperature spray drying, temperature at 150 DEG C -160 DEG C, such as 150 DEG C, 152
DEG C, 153 DEG C, 155 DEG C, 157 DEG C, 158 DEG C or 160 DEG C etc..
In the method for the present invention, microwave method is sintered to microwave method high temperature sintering.
In the method for the present invention, spray drying and microwave method have programming rate fast, and heat treatment time is short, is existed by elder generation
150 DEG C -160 DEG C of low temperature spray drying, then heated by microwave and carry out high temperature sintering, matrix material and cladding material can be made
Material zero gradient uniformly heats, therefore can realize that fluorophosphate is uniformly coated on lithium titanate particle surface.
In the method for the present invention, by low temperature spray drying again after first mixing lithium titanate and fluorophosphate, then microwave
High temperature sintering, synthesis fluorophosphate cladding lithium titanate composite material.In the composite prepared using this method, fluorophosphate bag
Layer evenness is good, and with stable three-dimensional structure, can not only suppress lithium titanate and side reaction occurs with electrolyte or moisture, also
Significantly improve the electric conductivity of material.
As the optimal technical scheme of the method for the invention, the chemical composition of the lithium titanate is Li4Ti5O12。
Preferably, the preparation method of the lithium titanate includes：The compound of compound containing lithium and titanium is well mixed
Afterwards, in reducibility gas or inert gas, 700 DEG C -900 DEG C is warming up to and is incubated, obtains lithium titanate.
Wherein, 700 DEG C -900 DEG C, such as 700 DEG C, 725 DEG C, 750 DEG C, 770 DEG C, 800 DEG C, 825 DEG C, 850 DEG C are warming up to
Or 900 DEG C etc..
Preferably, during preparing lithium titanate, the compound containing lithium be lithium acetate, lithium carbonate, lithium hydroxide,
Any one in lithium nitrate, lithium sulfate or lithium chloride or at least two mixtures mixed in any proportion, the mixture
Typical but non-limiting examples have：The mixture of the mixture of lithium acetate and lithium carbonate, lithium acetate and lithium hydroxide, lithium acetate and
The mixture of the mixture of lithium nitrate, lithium carbonate and lithium sulfate, the mixture of lithium carbonate, lithium hydroxide and lithium chloride etc..
Preferably, during preparing lithium titanate, the compound of the titanium is tetraethyl titanate, butyl titanate, metatitanic acid first
Any one in ester, titanium chloride or titanium dioxide or at least two mixtures mixed in any proportion, the mixture allusion quotation
Type but non-limiting examples have：The mixture of the mixture of tetraethyl titanate and butyl titanate, tetraethyl titanate and titanium chloride, metatitanic acid
The mixture of ethyl ester, butyl titanate and metatitanic acid methyl esters, the mixing of butyl titanate, metatitanic acid methyl esters, titanium chloride and titanium dioxide
Thing etc..
Preferably, during preparing lithium titanate, the compound of mixture and titanium containing lithium is according to mole Li:Ti=
1:1.25 mixed.
Preferably, during preparing lithium titanate, the reducibility gas or inert gas are nitrogen, argon gas, titanium dioxide
In carbon or hydrogen any one or at least two mixed gas.
Preferably, during preparing lithium titanate, heating rate is 1 DEG C/min-3 DEG C/min, such as 1 DEG C/min, 1.2
DEG C/min, 1.5 DEG C/min, 1.8 DEG C/min, 2 DEG C/min, 2.5 DEG C/min or 3 DEG C/min etc..
Preferably, during preparing lithium titanate, time of insulation is 8h-12h, for example, 8h, 8.5h, 9h, 9.5h, 10h,
11h, 11.5h or 12h etc..
Preferably, during preparing lithium titanate, after insulation, it is quickly cooled to 5 DEG C/min-10 DEG C/min speed
Room temperature.
As the optimal technical scheme of the method for the invention, step (1) described fluorophosphate is LiMPO4F, wherein, M
In=Al, Ni, Mn, Co, Fe, V or Mo any one or at least two combination, such as can be fluorophosphoric acid aluminium lithium, fluorine phosphorus
Sour nickel lithium, manganese fluorophosphate lithium, fluorophosphoric acid cobalt lithium, fluorophosphoric acid iron lithium, fluorine phosphorofluoric acid vanadium lithium and fluorophosphoric acid molybdenum lithium etc..
Preferably, step (1) described solvent is other solvents, preferably deionized water or ethanol such as water or alcohol.
Preferably, the mass ratio of step (1) solvent and lithium titanate is 1:1, the ratio can make lithium titanate and fluorine phosphorus
Hydrochlorate coating is dispersed.
Preferably, the mass ratio of step (1) lithium fluophosphate and lithium titanate is 0.01-0.1.
Preferably, the time of step (1) low temperature spray drying is 1min-2min.
Preferably, step (2) detailed process that is sintered by microwave method is：Spray dried products are put into instead
Container is answered, microwave is heated and is incubated, and is realized sintering, is removed reaction vessel after cooling, takes out the fluorophosphate cladding titanium of the inside
Sour lithium composite material.
As the optimal technical scheme of the method for the invention, it is described be sintered by microwave method during, microwave
Be heated to 400 DEG C -600 DEG C and be incubated 20min-30min, such as 400 DEG C of the temperature that microwave is heated to, 420 DEG C, 440 DEG C, 450
DEG C, 465 DEG C, 480 DEG C, 500 DEG C, 550 DEG C, 575 DEG C or 600 DEG C etc.；The soaking time of sintering such as 20min, 22min,
24min, 26min, 28minh or 30min etc..
Preferably, methods described is additionally included in after the completion of step (2) sintering, quick with 5 DEG C/min-10 DEG C/min speed
Room temperature is cooled to, the speed of cooling is such as 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min or 10 DEG C/min.
As the further preferred technical scheme of the method for the invention, the described method comprises the following steps：
(1) compound containing lithium and the compound of titanium are pressed into mole Li:Ti=1:After 1.25 is well mixed, reducing
Property gas or inert gas in, be raised to 700 DEG C -900 DEG C with 1 DEG C/min-3 DEG C/min speed, be incubated 8h-12h, then with 5
DEG C/min-10 DEG C/min quickly cools down, obtain lithium titanate；
(2) lithium titanate that step (1) obtains is dissolved in deionized water or ethanol, is stirring evenly and then adding into fluorophosphate,
Through 150 DEG C of -160 DEG C of low temperature spray dryings, fluorophosphate coating is formed on lithium titanate particle surface；
(3) by Spray dried products, microwave is heated to 400 DEG C -600 DEG C and is incubated 20min-30min in microwave agglomerating furnace
Afterwards, quickly cooled down with 5 DEG C/min-10 DEG C/min, obtain fluorophosphate cladding lithium titanate composite material；
Wherein it is preferred to the mass ratio of step (1) solvent and lithium titanate is 1:1, the matter of lithium fluophosphate and lithium titanate
It is (0.01-0.1) to measure ratio:1.
The third aspect, the present invention provide a kind of negative pole, and the negative pole includes the fluorophosphate cladding titanium described in first aspect
Sour lithium composite material.
Fourth aspect, the present invention provide a kind of lithium ion battery, and the lithium ion battery includes the fluorine described in first aspect
Phosphate coating lithium titanate composite material is as negative material.
Compared with the prior art, the present invention has the advantages that：
(1) present invention is by 150 DEG C of -160 DEG C of low temperature spray dryings, and further prepares fluorophosphate using microwave sintering
Coat lithium titanate composite material.This method has yield height, coating thickness is controllable, method is simple and easy, is easy to industrial metaplasia
The advantages of production, huge economic benefit can be produced to lithium titanate anode material commercial application.
(2) in fluorophosphate of the invention cladding lithium titanate composite material, fluorophosphate clad is uniform, can suppress titanium
The side reaction that sour lithium occurs with electrolyte or moisture, fluorine, which is bonded with metal ion and (forms M-F ionic bonds), can also prevent metal raw
The dissolving of son and the structure change of lithium titanate.In addition, fluorophosphate clad has stable three-dimensional structure, there is lithium ion
The characteristic of conductor and electronic conductor, the electric conductivity of material can be significantly improved.
(3) discharge capacity, cycle performance and the high rate performance of fluorophosphate of the invention cladding lithium titanate composite material obtain
To being obviously improved, the lithium ion battery being prepared using the composite as negative material not only hold by good conductivity, multiplying power
Amount is high, has extended cycle life, and the advantages of also lacking with aerogenesis, has good prospects for commercial application.
Brief description of the drawings
Fig. 1 (a) and Fig. 1 (b) is respectively the uncoated lithium titanate of comparative example 1 and the fluorophosphoric acid aluminium lithium of embodiment 1 cladding metatitanic acid
The SEM figures of lithium composite material；
Fig. 2 is to coat lithium titanate composite material system using the uncoated lithium titanate of comparative example 1 and the fluorophosphoric acid aluminium lithium of embodiment 1
Into battery high rate performance comparison diagram, wherein, " uncoated " corresponding comparative example 1, " fluorophosphoric acid aluminium lithium cladding " correspondence embodiment
1；
Fig. 3 is to coat lithium titanate composite material system using the uncoated lithium titanate of comparative example 1 and the fluorophosphoric acid aluminium lithium of embodiment 1
Into battery 1C cycle life comparison diagram, wherein, " uncoated " corresponding comparative example 1, " fluorophosphoric acid aluminium lithium cladding " corresponding reality
Apply example 1.
Embodiment
Further illustrate technical scheme below in conjunction with the accompanying drawings and by embodiment.
Embodiment 1：
(1) lithium acetate and tetraethyl titanate are pressed into mole Li:Ti=1:After 1.25 is well mixed, in nitrogen with 1 DEG C/
Min is raised to 700 DEG C from room temperature, is incubated 12h, is then quickly cooled to room temperature with 5 DEG C/min and obtains lithium titanate.
(2) lithium titanate is dissolved in deionized water, be stirring evenly and then adding into 0.01wt% (using lithium titanate quality as
100wt% count) fluorophosphoric acid aluminium lithium, on spray dryer after 150 DEG C of drys 2min formation fluorophosphoric acid aluminium lithium be coated on metatitanic acid
Lithium particle surface, it is then placed in reaction vessel after 400 DEG C of insulation 30min are heated in microwave agglomerating furnace, it is cold with 5 DEG C/min
But to reaction vessel is removed after room temperature, the fluorophosphoric acid aluminium lithium cladding lithium titanate composite material of the inside is taken out.
Test：
Lithium ion battery is made as negative material in the lithium titanate composite material coated using the present embodiment fluorophosphoric acid aluminium lithium
Assembling process it is as follows：
By the negative material that the lithium titanate composite material that fluorophosphoric acid aluminium lithium coats is used as and conductive black, binding agent PVDF
(Kynoar) presses 80:10:After 10 mass ratio mixing, add NMP (1-METHYLPYRROLIDONE) and be tuned into uniform sizing material coating
On copper foil, after drying in an oven, the pressure rolling through 10Mpa is cut into a diameter of 14mm circular pole piece.By in industry
CR2025 types button cell assembles lithium ion battery, and barrier film is Cellgard barrier films, and electrolyte is that solvent is EC/PC/DEC
1mol/L LiPF6Solution, to extremely lithium piece.Whole assembling process is assembled in the glove box full of argon gas, in glove box
Oxygen content and moisture are controlled in below 0.5ppm.
Lithium ion battery test condition is：Temperature is 25 DEG C ± 2 DEG C, and the voltage range of charge and discharge cycles is 1.2V-2.5V,
Size of current is 0.1C (15mAh/g).
Fig. 1 (a) and Fig. 1 (b) is respectively the uncoated lithium titanate of comparative example 1 and the fluorophosphoric acid aluminium lithium of embodiment 1 cladding metatitanic acid
The SEM comparison diagrams of lithium composite material, as seen from the figure, the fluorophosphoric acid aluminium lithium cladding lithium titanate composite material that embodiment 1 obtains
In, it is 3nm in the surface coated fluorophosphoric acid aluminium lithium thickness of lithium titanate, and thickness is more uniform, illustrates microwave method covered effect
Preferably.
Fig. 2 is to coat lithium titanate composite material system using the uncoated lithium titanate of comparative example 1 and the fluorophosphoric acid aluminium lithium of embodiment 1
Into battery high rate performance comparison diagram, as seen from the figure, coat fluorophosphoric acid aluminium lithium after lithium titanate different multiplying times
Rate capacity is all higher than uncoated lithium titanate capacity.Because there is fluorophosphoric acid aluminium lithium three-dimensional structure and ion and electronics to lead
Electrically, lithium ion and electronics can quickly be transmitted.
Fig. 3 is to coat lithium titanate composite material system using the uncoated lithium titanate of comparative example 1 and the fluorophosphoric acid aluminium lithium of embodiment 1
Into battery 1C cycle life comparison diagram, as seen from the figure, coat fluorophosphoric acid aluminium lithium 500 circulation volumes of lithium titanate
Conservation rate is 95.8%, higher than the 93.1% of uncoated fluorophosphoric acid aluminium lithium lithium titanate.Because fluorophosphoric acid aluminium lithium clad can press down
Metallic atom processed dissolving in the electrolytic solution and prevent lithium titanate structural damage, so as to keep lithium titanate surface texture and
The stabilization of internal structure, thus it is shown that higher cycle performance.
Embodiment 2：
(1) lithium carbonate and titanium dioxide are pressed into mole Li:Ti=1:After 1.25 is well mixed, in hydrogen with 3 DEG C/
Min is raised to 800 DEG C from room temperature, is incubated 10h, is then quickly cooled to room temperature with 10 DEG C/min and obtains lithium titanate.
(2) lithium titanate is dissolved in ethanol, is stirring evenly and then adding into 0.05wt% (being counted using lithium titanate quality as 100wt%)
Fluorophosphoric acid nickel lithium, on spray dryer after 150 DEG C of dry 1min formed fluorophosphoric acid nickel lithium be coated on lithium titanate particle surface,
It is then placed in reaction vessel after 600 DEG C of insulation 20min are heated in microwave agglomerating furnace, after being cooled to room temperature with 10 DEG C/min
Reaction vessel is removed, takes out the fluorophosphoric acid nickel lithium cladding lithium titanate composite material of the inside.
Test：
Lithium ion battery is carried out as negative material using the fluorophosphoric acid nickel lithium cladding lithium titanate composite material of the present embodiment
Assembling and test, assembly method, method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Embodiment 3：
(1) lithium hydroxide and butyl titanate are pressed into mole Li:Ti=1:After 1.25 is well mixed, in carbon dioxide
700 DEG C are raised to from room temperature with 2 DEG C/min, 8h is incubated, room temperature is then quickly cooled to 5 DEG C/min and obtains lithium titanate.
(2) lithium titanate is dissolved in ethanol, is stirring evenly and then adding into 0.10wt% (being counted using lithium titanate quality as 100wt%)
Manganese fluorophosphate lithium, on spray dryer after 160 DEG C of dry 1min formed manganese fluorophosphate lithium be coated on lithium titanate particle surface,
It is then placed in reaction vessel after 500 DEG C of insulation 30min are heated in microwave agglomerating furnace, after being cooled to room temperature with 10 DEG C/min
Reaction vessel is removed, takes out the manganese fluorophosphate lithium cladding lithium titanate composite material of the inside.
Lithium ion battery is carried out as negative material using the manganese fluorophosphate lithium cladding lithium titanate composite material of the present embodiment
Assembling and test, assembly method, method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Embodiment 4：
(1) lithium nitrate and metatitanic acid methyl esters are pressed into mole Li:Ti=1:After 1.25 is well mixed, in carbon dioxide and nitrogen
700 DEG C are raised to from room temperature with 1 DEG C/min in gaseous mixture, 12h is incubated, room temperature is then quickly cooled to 10 DEG C/min and obtains metatitanic acid
Lithium.
(2) lithium titanate is dissolved in deionized water, be stirring evenly and then adding into 0.08wt% (using lithium titanate quality as
100wt% count) fluorophosphoric acid cobalt lithium, on spray dryer after 150 DEG C of drys 2min formation fluorophosphoric acid cobalt lithium be coated on metatitanic acid
Lithium particle surface, it is then placed in reaction vessel after 550 DEG C of insulation 25min are heated in microwave agglomerating furnace, with 10 DEG C/min
Reaction vessel is removed after being cooled to room temperature, takes out the fluorophosphoric acid cobalt lithium cladding lithium titanate composite material of the inside.
Lithium ion battery is carried out as negative material using the fluorophosphoric acid cobalt lithium cladding lithium titanate composite material of the present embodiment
Assembling and test, assembly method, method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Embodiment 5：
(1) lithium sulfate and titanium chloride are pressed into mole Li:Ti=1:After 1.25 is well mixed, in hydrogen and nitrogen mixture
In with 3 DEG C/min be raised to 900 DEG C from room temperature, be incubated 10h, room temperature be then quickly cooled to 6 DEG C/min and obtains lithium titanate.
(2) lithium titanate is dissolved in deionized water, be stirring evenly and then adding into 0.04wt% (using lithium titanate quality as
100wt% count) fluorophosphoric acid iron lithium, on spray dryer after 155 DEG C of drys 2min formation fluorophosphoric acid iron lithium be coated on metatitanic acid
Lithium particle surface, it is then placed in reaction vessel after 400 DEG C of insulation 20min are heated in microwave agglomerating furnace, it is cold with 5 DEG C/min
But to reaction vessel is removed after room temperature, the fluorophosphoric acid iron lithium cladding lithium titanate composite material of the inside is taken out.
Lithium ion battery is carried out as negative material using the fluorophosphoric acid iron lithium cladding lithium titanate composite material of the present embodiment
Assembling and test, assembly method, method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Embodiment 6：
(1) lithium chloride and titanium dioxide are pressed into mole Li:Ti=1:After 1.25 is well mixed, mixed in argon gas and nitrogen
800 DEG C are raised to from room temperature with 3 DEG C/min in gas, 12h is incubated, room temperature is then quickly cooled to 10 DEG C/min and obtains lithium titanate.
(2) lithium titanate is dissolved in ethanol, is stirring evenly and then adding into 0.04wt% (being counted using lithium titanate quality as 100wt%)
Fluorophosphoric acid vanadium lithium, on spray dryer after 155 DEG C of dry 1min formed fluorophosphoric acid vanadium lithium be coated on lithium titanate particle surface,
It is then placed in reaction vessel after 450 DEG C of insulation 25min are heated in microwave agglomerating furnace, after being cooled to room temperature with 10 DEG C/min
Reaction vessel is removed, takes out the fluorophosphoric acid vanadium lithium cladding lithium titanate composite material of the inside.
Lithium ion battery is carried out as negative material using the fluorophosphoric acid vanadium lithium cladding lithium titanate composite material of the present embodiment
Assembling and test, assembly method, method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Embodiment 7：
(1) lithium chloride and titanium dioxide are pressed into mole Li:Ti=1:After 1.25 is well mixed, mixed in argon gas and nitrogen
800 DEG C are raised to from room temperature with 3 DEG C/min in gas, 12h is incubated, room temperature is then quickly cooled to 10 DEG C/min and obtains lithium titanate.
(2) lithium titanate is dissolved in ethanol, is stirring evenly and then adding into 0.04wt% (being counted using lithium titanate quality as 100wt%)
Fluorophosphoric acid vanadium lithium, on spray dryer after 160 DEG C of dry 1min formed fluorophosphoric acid vanadium lithium be coated on lithium titanate particle surface,
It is then placed in reaction vessel after 550 DEG C of insulation 20min are heated in microwave agglomerating furnace, after being cooled to room temperature with 5 DEG C/min
Reaction vessel is removed, takes out the fluorophosphoric acid vanadium lithium cladding lithium titanate composite material of the inside.
Lithium ion battery is carried out as negative material using the fluorophosphoric acid vanadium lithium cladding lithium titanate composite material of the present embodiment
Assembling and test, assembly method, method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Comparative example 1：
The difference of this comparative example 1 and embodiment 1 is：Fluorophosphoric acid aluminium lithium cladding is not carried out to lithium titanate.
Using this comparative example lithium titanate as negative material carry out lithium ion battery assembling and test, assembly method,
Method of testing and test condition are same as Example 1, and test result is shown in Table 1.
Comparative example 2：
The cladding of fluorophosphoric acid aluminium lithium is carried out to lithium titanate using the agglutinating nature yeast of routine.
In this comparative example, agglutinating nature yeast colloid drying time is longer, generally up to 12h or so, and follow-up sintering temperature
Spend higher (700 DEG C or so) and soaking time it is longer (3-5h), exist clad uneven thickness it is uniform be difficult to control, Yi Jibei
The shortcomings of rate discharge capacity and cycle life improve unobvious.
Contrasted from embodiment 1-7 and comparative example 1-2, the fluorophosphate being prepared using the method for the present invention is coated
Lithium titanate composite material has excellent discharge capacity, high rate performance and cycle performance；And comparative example 1 is without fluorophosphate bag
Cover, comparative example 2 does not use the method cladding fluorophosphate of the present invention, is unable to reach the excellent effect of the present invention.
The embodiment 1-7 of table 1 fluorophosphate cladding lithium titanate contrasts with the uncoated lithium titanate circulation of comparative example 1
Applicant states that the present invention illustrates the method detailed of the present invention, but not office of the invention by above-described embodiment
It is limited to above-mentioned method detailed, that is, does not mean that the present invention has to rely on above-mentioned method detailed and could implemented.Art
Technical staff it will be clearly understood that any improvement in the present invention, equivalence replacement and auxiliary element to each raw material of product of the present invention
Addition, selection of concrete mode etc., within the scope of all falling within protection scope of the present invention and disclosing.
Claims (10)
1. a kind of fluorophosphate coats lithium titanate composite material, it is characterised in that the composite includes lithium titanate and cladding
Fluorophosphate clad on the lithium titanate surface.
2. composite according to claim 1, it is characterised in that the chemical composition of the lithium titanate is Li4Ti5O12；
Preferably, the particle diameter of the lithium titanate is 200-500nm；
Preferably, the fluorophosphate is LiMPO4F, wherein, in M=Al, Ni, Mn, Co, Fe, V or Mo any one or extremely
Few two kinds combination；
Preferably, the fluorophosphate clad is three-dimensional structure；
Preferably, the thickness of the fluorophosphate clad is 2-5nm, preferably 3nm；
Preferably, the mass ratio of fluorophosphate clad and lithium titanate is (0.01-0.1):1.
3. the preparation method of fluorophosphate cladding lithium titanate composite material as claimed in claim 1 or 2, it is characterised in that institute
The method of stating comprises the following steps：
(1) lithium titanate is dissolved in solvent, is stirring evenly and then adding into fluorophosphate, in 150 DEG C of -160 DEG C of low temperature spray dryings,
Lithium titanate particle surface forms fluorophosphate coating；
(2) Spray dried products are sintered by microwave method, obtain fluorophosphate cladding lithium titanate composite material.
4. according to the method for claim 3, it is characterised in that the chemical composition of the lithium titanate is Li4Ti5O12；
Preferably, the preparation method of the lithium titanate includes：After compound containing lithium and the compound of titanium are well mixed,
In reducibility gas or inert gas, it is warming up to 700 DEG C -900 DEG C and is incubated, obtain lithium titanate.
5. according to the method for claim 4, it is characterised in that during preparing lithium titanate, the chemical combination containing lithium
Thing is any one in lithium acetate, lithium carbonate, lithium hydroxide, lithium nitrate, lithium sulfate or lithium chloride or at least two by any
The mixture of ratio mixing；
Preferably, during preparing lithium titanate, the compound of the titanium is tetraethyl titanate, butyl titanate, metatitanic acid methyl esters, chlorine
Any one in change titanium or titanium dioxide or at least two mixtures mixed in any proportion；
Preferably, during preparing lithium titanate, the compound of mixture and titanium containing lithium is according to mole Li:Ti=1:
1.25 mixed；
Preferably, during preparing lithium titanate, the reducibility gas or inert gas be nitrogen, argon gas, carbon dioxide or
In hydrogen any one or at least two mixed gas；
Preferably, during preparing lithium titanate, heating rate is 1 DEG C/min-3 DEG C/min；
Preferably, during preparing lithium titanate, the time of insulation is 8h-12h；
Preferably, during preparing lithium titanate, after insulation, quickly cooled down with 5 DEG C/min-10 DEG C/min speed.
6. according to the method described in claim any one of 3-5, it is characterised in that step (1) described fluorophosphate is LiMPO4F,
Wherein, any one in M=Al, Ni, Mn, Co, Fe, V or Mo or at least two combination；
Preferably, step (1) described solvent is water or alcohol, preferably deionized water or ethanol；
Preferably, the mass ratio of step (1) solvent and lithium titanate is 1:1；
Preferably, the mass ratio of step (1) lithium fluophosphate and lithium titanate is 0.01-0.1:1；
Preferably, the time of step (1) described low temperature spray drying is 1min-2min.
7. according to the method described in claim any one of 3-6, it is characterised in that step (2) is described to be burnt by microwave method
The detailed process of knot is：Spray dried products are put into reaction vessel, microwave is heated and is incubated, and is realized sintering, is moved after cooling
Go out reaction vessel, take out the fluorophosphate cladding lithium titanate composite material of the inside；
Preferably, it is described be sintered by microwave method during, microwave is heated to 400 DEG C -600 DEG C and is incubated 20min-
30min。
8. according to the method described in claim any one of 3-7, it is characterised in that methods described is additionally included in step (2) sintering
After the completion of, cooled down with 5 DEG C/min-10 DEG C/min speed.
9. according to the method described in claim any one of 3-8, it is characterised in that the described method comprises the following steps：
(1) compound containing lithium and the compound of titanium are pressed into mole Li:Ti=1:After 1.25 is well mixed, in reproducibility gas
In body or inert gas, be raised to 700 DEG C -900 DEG C with 1 DEG C/min-3 DEG C/min speed, be incubated 8h-12h, then with 5 DEG C/
Min-10 DEG C/min is quickly cooled down, and obtains lithium titanate；
(2) lithium titanate that step (1) obtains is dissolved in deionized water or ethanol, fluorophosphate is stirring evenly and then adding into, through 150
DEG C -160 DEG C of low temperature spray dryings, fluorophosphate coating is formed on lithium titanate particle surface；
(3) Spray dried products are heated to 400 DEG C -600 DEG C by microwave in microwave agglomerating furnace and are incubated 20min-30min
Afterwards, cooled down with 5 DEG C/min-10 DEG C/min, obtain fluorophosphate cladding lithium titanate composite material；
Wherein it is preferred to the mass ratio of step (1) solvent and lithium titanate is 1:1, the mass ratio of lithium fluophosphate and lithium titanate
For (0.01-0.1):1.
10. a kind of lithium ion battery, it is characterised in that the lithium ion battery includes the fluorophosphate described in claim 1 or 2
Lithium titanate composite material is coated as negative material.
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