CN103280568B - Lithium titanate composite material and preparation method thereof and its application - Google Patents
Lithium titanate composite material and preparation method thereof and its application Download PDFInfo
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Abstract
The invention provides a kind of lithium titanate composite material and preparation method thereof and its application.Described lithium titanate composite material comprises: lithium titanate particle; And lithium phosphate glass, be coated on lithium titanate particle surface.Described preparation method comprises: in liquid system solvent, mix, the mixture in lithium titanate particle and lithium source and phosphorus source to obtain mixing liquid; Mixing liquid is carried out ball milling to form slurry, afterwards slurry taken out and dry, obtaining the precursor powder of this composite material; Calcined by the precursor powder of this composite material, after cooling, fragmentation obtains the lithium titanate composite material of the coated lithium phosphate glass of surperficial lithium titanate.Lithium titanate composite material is applied as the electrode material of lithium ion battery active material or capacitor.Lithium titanate composite material can suppress the flatulence of lithium ion battery when being applied to lithium ion battery, improve high temperature storage and the cycle performance of lithium ion battery, improve the diffusion coefficient of lithium ion in active material, contributes to the high rate performance improving lithium titanate.
Description
Technical field
The present invention relates to field of lithium ion battery, particularly relate to a kind of lithium titanate composite material and preparation method thereof and its application.
Background technology
Lithium titanate is as a kind of zero strain material, and when its negative active core-shell material as lithium ion battery, lithium ion battery has the feature such as good cycle performance and longer useful life.When research finds to use lithium titanate as negative active core-shell material, lithium ion battery cycle life at normal temperatures can reach more than 20000 times, and this makes lithium titanate in lithium ion battery, have good application prospect.In addition, lithium titanate is used also to have discharging voltage balance and the high feature of voltage platform as the lithium ion battery (hereinafter referred to as " lithium titanate battery ") of negative material, can not produce and analyse lithium phenomenon, therefore there is very high fail safe, there is very large application advantage in electric automobile.But lithium titanate battery high temperature cyclic performance is poor, and more gas can be produced, cause greatly reduce its useful life.
For the problems referred to above, a kind of method that solution take lithium titanate as the power lithium-ion battery flatulence problem of negative pole is disclosed in the Chinese patent application publication number CN102055020A announced on May 11st, 2011, it by keeping the regular hour by the lithium titanate battery after precharge at certain state-of-charge, certain temperature, strengthen the stability of the passivating film that lithium titanate anode is formed in pre-charging stage, suppress lithium titanate and electrolyte solution to react, thus reduce the gas production of battery.The Chinese patent application publication number CN102280661A announced on December 14th, 2011 discloses a kind of lithium titanate battery and electrolyte thereof, it adopts additive at lithium titanate surface filming to realize the isolation of electrolyte and lithium titanate, reduces the gas production of lithium titanate battery simultaneously.These two kinds of methods all can solve the flatulence problem of lithium titanate to a certain extent, but form passivating film on the surface of lithium titanate particle often fine and close not, there is no effective coated lithium titanate, thus electrolyte can cannot be kept apart preferably, when discharge and recharge, passivating film may be eliminated and regrowth, greatly can lose electrolyte, and grow new passivating film, this passivating film easily increases the internal resistance of battery.Also there is researcher to use the metal oxide such as aluminium oxide, magnesium oxide to be coated on the surface of lithium titanate, form layer protecting film on its surface, thus change lithium titanate active material Surface Physical Chemistry characteristic.But, because oxide is difficult to coated densification, limited to the suppression of its aerogenesis, and the lithium ion conductivity of oxide is smaller, can affect the high rate performance of lithium titanate after coated.
Summary of the invention
In view of background technology Problems existing, the object of the present invention is to provide a kind of lithium titanate composite material and preparation method thereof and its application, it can reduce the flatulence of lithium ion battery when being applied to lithium ion battery, and then improves high temperature storage and the cycle performance of lithium ion battery.
Another object of the present invention is to provide a kind of lithium titanate composite material and preparation method thereof and its application, it can improve the diffusion coefficient of lithium ion in active material, contributes to the high rate performance improving lithium titanate.
To achieve these goals, in a first aspect of the present invention, the invention provides a kind of lithium titanate composite material, it comprises: lithium titanate particle; And lithium phosphate glass, be coated on lithium titanate particle surface.
In a second aspect of the present invention, the invention provides a kind of preparation method of lithium titanate composite material, it is for the preparation of lithium titanate composite material described according to a first aspect of the present invention, comprise step: in liquid system solvent, mix, the mixture in lithium titanate particle and lithium source and phosphorus source to obtain mixing liquid; Mixing liquid is carried out ball milling to form slurry, afterwards slurry taken out and dry, obtaining the precursor powder of this composite material; Calcined by the precursor powder of this composite material, after cooling, fragmentation obtains the lithium titanate composite material of the coated lithium phosphate glass of surperficial lithium titanate.
In a third aspect of the present invention, the lithium titanate composite material that the invention provides described first aspect is as the application of the electrode material of lithium ion battery active material or capacitor.
Beneficial effect of the present invention is as follows:
In the present invention, due to directly at the coated lithium phosphate glass of lithium titanate intimate surface, due to closely coated, therefore lithium titanate and electrolyte can be kept apart, prevent lithium titanate directly to contact with electrolyte, inhibit the solvent in electrolyte in the reaction of anode surface, greatly reduce the probability of its aerogenesis, reduce gas production, its aerogenesis problem can be solved preferably, reduce the thickness of the expansion of battery core when high temperature storage, and then improve high temperature storage and the cycle performance of lithium ion battery.
Coated lithium phosphate glass can not introduce side reaction when lithium ion battery discharge and recharge, therefore can not affect the chemical property of lithium titanate active material; Coated lithium phosphate glass has comparatively high ionic conductivity, can increase the diffusion admittance of lithium ion, therefore improves lithium ion diffusion coefficient in the material, contributes to the high rate performance improving lithium titanate.
Preparation method's technique of lithium titanate composite material of the present invention is simple, easily operates, reproducible, with low cost, and little to the pollution of environment, is suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is the charge and discharge cycles curve chart of the button cell adopting the lithium titanate composite material in the embodiment of the present invention 1 to be assembled into;
Fig. 2 is the button cell that adopts the lithium titanate composite material of the embodiment of the present invention 1, embodiment 10, comparative example 1 and comparative example 2 the to be assembled into charge/discharge capacity conservation rate figure at 10C/10C.
Embodiment
The following detailed description of lithium titanate composite material according to the present invention and preparation method thereof and its application and embodiment.
First lithium titanate composite material is according to a first aspect of the present invention described.
Lithium titanate composite material according to a first aspect of the present invention comprises: lithium titanate particle; And lithium phosphate glass, be coated on lithium titanate particle surface.
In lithium titanate composite material according to a first aspect of the present invention, preferably, the chemical formula of lithium phosphate glass is xLi
2o (1-x) P
2o
5, wherein 0<x<1, is preferably 0.2≤x≤0.7.
In lithium titanate composite material according to a first aspect of the present invention, preferably, the mass ratio of described lithium phosphate glass and lithium titanate particle is (0.001 ~ 0.1): 1, is preferably (0.005 ~ 0.03): 1.If the amount of lithium phosphate glass may cause lithium titanate coated imperfect very little, and if the amount of lithium phosphate glass is too many, the energy density of lithium titanate can be reduced.
In lithium titanate composite material according to a first aspect of the present invention, preferably, described lithium titanate is pure lithium titanate or the lithium titanate of doping.Preferably, the lithium titanate of described doping is one or more of adulterating in Nb, Mg, Zn, La, Zr, N, Al, V, Cr, Fe, Co, Ni, Cu, Ag, Ta, Mo and Y element in pure lithium titanate.
In lithium titanate composite material according to a first aspect of the present invention, preferably, the particle diameter of described lithium titanate particle is 10nm ~ 500 μm, is more preferably 100nm ~ 1000nm.
Secondly the preparation method of lithium titanate composite material is according to a second aspect of the present invention described.
The preparation method of lithium titanate composite material according to a second aspect of the present invention, it is for the preparation of lithium titanate composite material described according to a first aspect of the present invention, comprise step: in liquid system solvent, mix, the mixture in lithium titanate particle and lithium source and phosphorus source to obtain mixing liquid; Mixing liquid is carried out ball milling to form slurry, afterwards slurry taken out and dry, obtaining the precursor powder of this composite material; Calcined by the precursor powder of this composite material, after cooling, fragmentation obtains the lithium titanate composite material of the coated lithium phosphate glass of surperficial lithium titanate.
Adopt Surface coating to have the lithium titanate particle of lithium phosphate glass to realize the isolation of lithium titanate and electrolyte, wherein lithium phosphate glass is a kind of by Li
2o and P
2o
5admittedly the eutectic after melting in varing proportions, meeting melting under the state of heating, molten state more completely can be coated on the surface of lithium titanate, therefore effectively can suppress the aerogenesis of lithium titanate battery.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, Ball-milling Time is 2 ~ 24h; Calcining heat is 500 DEG C ~ 1500 DEG C, and calcination time is 2 ~ 48h.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium citrate, lithium dihydrogen phosphate.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, lithium dihydrogen phosphate.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, in the mixture in described lithium source and phosphorus source, the mol ratio of elemental lithium and P elements is x/ (1-x), wherein 0<x<1, is preferably 0.2≤x≤0.7.When lower than 0.2 and higher than 0.7 time, make the content of another component too low, cause it to be difficult to effectively form vitreum.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, the Li that in described lithium source and phosphorus source, elemental lithium is corresponding respectively with P elements
2o and P
2o
5quality sum and the mass ratio of lithium titanate be (0.001 ~ 0.01): 1.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, described liquid system solvent is selected from least one in absolute ethyl alcohol, deionized water.
In the preparation method of lithium titanate composite material according to a second aspect of the present invention, preferably, the particle diameter of described lithium titanate particle is 10nm ~ 500 μm, is preferably 100nm ~ 1000nm.When the particle diameter of particle is less than 100nm, when mixing in liquid system solvent, be difficult to dispersion; When grain diameter is greater than 1000nm, the reduction of its high rate performance can be caused more greatly due to granularity.
The application of following explanation lithium titanate composite material according to a third aspect of the present invention, that is, according to the application as lithium ion battery active material or capacitor electrode material of the lithium titanate composite material of described first aspect present invention.
Finally illustrate according to lithium titanate composite material of the present invention and preparation method thereof and its embodiment applied, comparative example and test result.
Embodiment 1
Be 300nm lithium titanate particle by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.5:0.5, the Li that wherein in lithium carbonate and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 2.150g lithium carbonate and 7.627g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.01:1 with the mass ratio of lithium titanate particle) mix in deionized water; After mixing, on ball mill, ball milling 6h obtains slurry; Afterwards slurry is dried the precursor powder obtaining lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 24h 1000 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.5Li
2o0.5P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.01:1) of lithium phosphate glass.
Embodiment 2
Be 100nm lithium titanate particle by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.67:0.33, the Li that wherein in lithium hydroxide and ammonium dihydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 1.200g lithium hydroxide and 2.839g ammonium dihydrogen phosphate
2o and P
2o
5quality sum be 0.005:1 with the mass ratio of lithium titanate particle) mix in absolute ethyl alcohol; After mixing, on ball mill, ball milling 8h obtains slurry, afterwards slurry is dried the precursor powder obtaining lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 2h 1500 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.67Li
2o0.33P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.005:1) of lithium phosphate glass.
Embodiment 3
Be 500nm lithium titanate particle by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.63:0.37, the Li that wherein in lithium hydroxide and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 2.115g lithium hydroxide and 6.849g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.01:1 with the mass ratio of lithium titanate particle) mix in absolute ethyl alcohol, after mixing, on ball mill, ball milling 10h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 6h 1000 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.63Li
2o0.37P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.01:1) of lithium phosphate glass.
Embodiment 4
Be 800nm lithium titanate particle by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.2:0.8, the Li that wherein in lithium acetate and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 2.208g lithium acetate and 17.677g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.02:1 with the mass ratio of lithium titanate particle) mix in deionized water, after mixing, on ball mill, ball milling 12h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 8h 1400 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.20Li
2o0.80P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.02:1) of lithium phosphate glass.
Embodiment 5
Be 1 μm of lithium titanate particle by 500g particle diameter, with the mixture of 31.086g lithium citrate and 13.889g phosphoric acid (be wherein 0.7:0.3 by the mol ratio of elemental lithium and P elements, the Li that wherein in lithium citrate and phosphoric acid, elemental lithium is corresponding respectively with P elements
2o and P
2o
5quality sum be 0.03:1 with the mass ratio of lithium titanate particle) mix in absolute ethyl alcohol, after mixing, on ball mill, ball milling 16h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 12h 1300 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.70Li
2o0.30P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.03:1) of lithium phosphate glass.
Embodiment 6
Be 5 μm of lithium titanate particle by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.45:0.55, the Li that wherein in lithium dihydrogen phosphate and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 25.552g lithium dihydrogen phosphate and 7.215g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.05:1 with the mass ratio of lithium titanate particle) mix in absolute ethyl alcohol, after mixing, on ball mill, ball milling 18h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 16h 1200 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.45Li
2o0.55P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.05:1) of lithium phosphate glass.
Embodiment 7
Be 500 μm of lithium titanate particle by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.55:0.45, the Li that wherein in lithium carbonate and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 25.303g lithium carbonate and 73.998g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.1:1 with the mass ratio of lithium titanate particle) mix in deionized water, after mixing, on ball mill, ball milling 24h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 20h 1000 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.55Li
2o0.45P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.1:1) of lithium phosphate glass.
Embodiment 8
Be the lithium titanate particle of 10nm by 500g particle diameter, (wherein the mol ratio of elemental lithium and P elements is 0.65:0.35, the Li that wherein in lithium nitrate and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 0.649g lithium nitrate and 0.664g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.001:1 with the mass ratio of lithium titanate particle) mix in deionized water, after mixing, on ball mill, ball milling 8h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 24h 900 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.65Li
2o0.35P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.001:1) of lithium phosphate glass.
Embodiment 9
Be the lithium titanate particle Li of 500nm doping Nb element by 500g particle diameter
4ti
4.95nb
0.05o
12, (wherein the mol ratio of elemental lithium and P elements is 0.67:0.33, the Li that wherein in lithium carbonate and lithium dihydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 3.758g lithium carbonate and 10.259g lithium dihydrogen phosphate
2o and P
2o
5quality sum be 0.02:1 with the mass ratio of lithium titanate particle) mix in deionized water, after mixing, on ball mill, ball milling 10h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 36h 800 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.67Li
2o0.33P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.02:1) of lithium phosphate glass.
Embodiment 10
Be the lithium titanate particle Li of 300nm doping La rare earth element by 500g particle diameter
4ti
4.9la
0.1o
12, (wherein the mol ratio of elemental lithium and P elements is 0.5:0.5, the Li that wherein in lithium citrate and diammonium hydrogen phosphate, elemental lithium is corresponding respectively with P elements with the mixture of 10.941g lithium citrate and 15.371g diammonium hydrogen phosphate
2o and P
2o
5quality sum be 0.02:1 with the mass ratio of lithium titanate particle) mix in deionized water, after mixing, on ball mill, ball milling 12h obtains slurry, is dried by slurry afterwards and obtains the precursor powder of lithium titanate composite material;
The precursor powder of lithium titanate composite material is placed in crucible, is then placed in tube furnace calcining at constant temperature 48h 600 DEG C time, pulverized after cooling and obtain lithium titanate particle Surface coating and have 0.50Li
2o0.50P
2o
5the lithium titanate composite material (wherein the mass ratio of lithium phosphate glass and lithium titanate particle is 0.02:1) of lithium phosphate glass.
Comparative example 1
Only 500g particle diameter is adopted to be 300nm lithium titanate particle (namely not carrying out Surface coating process).
Comparative example 2
Only 500g particle diameter is adopted to be that 500nm is coated with 1% magnesian lithium titanate particle.
Finally provide the performance of lithium ion battery testing result of embodiment 1-10 and comparative example 1-2.
(1) the surface coated lithium titanate obtained by embodiments of the invention 1, conductive carbon and Kynoar (PVDF) mix rear film according to the ratio of mass ratio 90:5:5 with NMP and make diaphragm on aluminium foils, then with lithium sheet for negative pole, polyethylene film is barrier film, injects 1mol/LLiPF
6ethylene carbonate (EC) and the electrolyte of diethyl carbonate (DMC) (mass ratio is 1:1), button cell is assembled in oxygen and water content are all lower than the glove box of 0.1ppm, after leaving standstill 12h, this button cell is installed on blue electric tester, with the rate charge-discharge of 0.1C, voltage range is 1.0V ~ 2.5V, stops, obtaining charging and discharging curve as shown in Figure 1 after circulating 5 weeks; As shown in Figure 1, the button cell adopting lithium titanate composite material of the present invention to prepare has smooth charge and discharge platform and higher reversible capacity.
(2) lithium titanate of Surface coating process is not carried out as active material using in the surface coated lithium titanate of embodiment of the present invention 1-10 and comparative example 1-2, the ratio being 90:5:5 in mass ratio with conductive carbon and PVDF mixes rear film with NMP and on aluminium foil, is made into diaphragm as anode, using ternary material (NCM111) as cathode active material, the ratio being 92:5:3 in mass ratio with conductive carbon and PVDF mixes rear film with NMP and on aluminium foil, is made into diaphragm as negative electrode, take polyethylene film as barrier film, by colding pressing, itemize, winding, encapsulation, baking obtains the battery core treating fluid injection, inject the ethylene carbonate (EC) of 1mol/LLiPF6 and the electrolyte of diethyl carbonate (DMC) (mass ratio is 1:1), the model of battery core is 383450(thickness is 3.8mm, width is 34mm, length is 50mm).Battery core is completely charged to 2.8V with 0.5C, and then under 2.8V, constant voltage is charged to electric current≤0.05C and obtains the lithium ion battery that in embodiments of the invention 1-10 and comparative example 1-2, lithium titanate is assembled into, and is numbered S1-S10 and D1-D2 respectively.
High temperature cyclic performance test is carried out to the battery being numbered S1-S10 and D1-D2: the first thickness d 1 of the front battery of record circulation, then at 60 DEG C 1.5 ~ 2.8V voltage range in, charge with the multiplying power of 1C, the multiplying power discharging of 1C carries out loop test, circulate and again record the thickness d 2 of battery after 500 times, calculate its thickness swelling (d2-d1)/d1, acquired results is in table 1.
High-temperature storage performance test is carried out to the battery being numbered S1-S10 and D1-D2: first record stores the thickness d 3 of front battery, then at 85 DEG C, 4h is stored, the thickness d 4 of battery after record stores, calculate its thickness swelling (d4-d3)/d3, acquired results is in table 1.
The performance test results of table 1 embodiment 1-10 and comparative example 1-2
Get S1, S10 and D1, D2 group, carry out multiplying power test respectively, first test its capability value Q1 when 1C/1C, and then test its capacity Q2 when 10C/10C, calculate its capability retention Q2/Q1, obtain as shown in Figure 2 S1, S10, D1 and D2 at the capability retention figure of 10C/10C discharge and recharge.
As can be seen from Table 1, adopt the high-temperature storage performance of the lithium ion battery of surface coated lithium titanate and high temperature cyclic performance to be obtained for very large improvement, thickness swelling reduces all greatly.This is because lithium titanate bread of the present invention is covered with lithium phosphate glass, avoid lithium titanate directly to contact with electrolyte, therefore the probability of lithium titanate aerogenesis is greatly reduced, greatly inhibit the flatulence phenomenon in lithium titanate battery, reduce the thickness that battery core expands when high temperature storage and high temperature circulation, and then improve high-temperature storage performance and the high temperature cyclic performance of lithium titanate battery; In addition, as shown in Figure 2, it is lithium phosphate glass because lithium titanate is surface coated, side reaction can not be introduced when lithium ion battery discharge and recharge, and this lithium phosphate glass is a kind of lithium ion conductor, effectively can promote its lithium ion transport speed, be compared to not coated lithium titanate and be coated with magnesian lithium titanate, the coated lithium titanate of this lithium phosphate glass can significantly improve its high rate performance, and then adopts the lithium ion battery of lithium titanate active material to have longer useful life.
Claims (12)
1. a lithium titanate composite material, is characterized in that, comprising:
Lithium titanate particle; And
Lithium phosphate glass, is completely closely coated on lithium titanate particle surface;
The particle diameter of described lithium titanate particle is 10nm ~ 500 μm;
The mass ratio of described lithium phosphate glass and lithium titanate particle is (0.001 ~ 0.1): 1;
Wherein, the preparation method of lithium titanate composite material comprises step:
The mixture in lithium titanate particle and lithium source and phosphorus source is mixed, to obtain mixing liquid in liquid system solvent;
Mixing liquid is carried out ball milling to form slurry, afterwards slurry taken out and dry, obtaining the precursor powder of this composite material;
Calcined by the precursor powder of this composite material, after cooling, fragmentation obtains the lithium titanate composite material of lithium titanate Surface coating lithium phosphate glass.
2. lithium titanate composite material according to claim 1, is characterized in that, the chemical formula of lithium phosphate glass is xLi
2o (1-x) P
2o
5, wherein 0<x<1.
3. lithium titanate composite material according to claim 2, is characterized in that, 0.2≤x≤0.7.
4. lithium titanate composite material according to claim 1, is characterized in that, the mass ratio of described lithium phosphate glass and lithium titanate particle is (0.005 ~ 0.03): 1.
5. lithium titanate composite material according to claim 1, is characterized in that, described lithium titanate is pure lithium titanate or the lithium titanate of doping.
6. lithium titanate composite material according to claim 5, it is characterized in that, the lithium titanate of described doping is one or more of adulterating in Nb, Mg, Zn, La, Zr, N, Al, V, Cr, Fe, Co, Ni, Cu, Ag, Ta, Mo and Y element in pure lithium titanate.
7. lithium titanate composite material according to claim 1, is characterized in that, the particle diameter of described lithium titanate particle is 100nm ~ 1000nm.
8. lithium titanate composite material according to claim 1, is characterized in that, Ball-milling Time is 2 ~ 24h; Calcining heat is 500 DEG C ~ 1500 DEG C, and calcination time is 2 ~ 48h.
9. lithium titanate composite material according to claim 1, is characterized in that,
Described lithium source is one or more in lithium carbonate, lithium hydroxide, lithium nitrate, lithium acetate, lithium citrate, lithium dihydrogen phosphate;
Described phosphorus source is one or more in ammonium dihydrogen phosphate, diammonium hydrogen phosphate, phosphoric acid, lithium dihydrogen phosphate.
10. lithium titanate composite material according to claim 1, is characterized in that, the Li that in described lithium source and phosphorus source, elemental lithium is corresponding respectively with P elements
2o and P
2o
5quality sum and the mass ratio of lithium titanate particle be (0.001 ~ 0.1): 1.
11. lithium titanate composite materials according to claim 1, is characterized in that, described liquid system solvent is selected from least one in absolute ethyl alcohol, deionized water.
12. 1 kinds of lithium titanate composite materials according to any one of claim 1-11 are as the application of the active material of lithium ion battery or the electrode material of capacitor.
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| CN201310202923.0A CN103280568B (en) | 2013-05-28 | 2013-05-28 | Lithium titanate composite material and preparation method thereof and its application |
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| CN201310202923.0A CN103280568B (en) | 2013-05-28 | 2013-05-28 | Lithium titanate composite material and preparation method thereof and its application |
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| CN105280910A (en) * | 2014-07-11 | 2016-01-27 | 北京当升材料科技股份有限公司 | Phosphorus-contained lithium ion battery positive electrode material and preparation method therefor |
| CN109698339A (en) * | 2018-12-28 | 2019-04-30 | 安徽科达铂锐能源材料有限公司 | A kind of lithium titanate composite material and its preparation method and application |
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