CN102646823B - Lithium titanate cathode material and method for preparing same, and battery produced by employing same - Google Patents
Lithium titanate cathode material and method for preparing same, and battery produced by employing same Download PDFInfo
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- CN102646823B CN102646823B CN2012101542732A CN201210154273A CN102646823B CN 102646823 B CN102646823 B CN 102646823B CN 2012101542732 A CN2012101542732 A CN 2012101542732A CN 201210154273 A CN201210154273 A CN 201210154273A CN 102646823 B CN102646823 B CN 102646823B
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract 16
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract 16
- 229910052744 lithium Inorganic materials 0.000 title claims abstract 16
- 239000010406 cathode material Substances 0.000 title abstract 6
- 229910052735 hafnium Inorganic materials 0.000 claims abstract 3
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000126 substance Substances 0.000 claims abstract 2
- 239000010405 anode material Substances 0.000 claims 9
- 239000000463 material Substances 0.000 claims 5
- 239000011575 calcium Substances 0.000 claims 4
- 238000002360 preparation method Methods 0.000 claims 3
- 239000010936 titanium Substances 0.000 claims 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims 2
- 229910052791 calcium Inorganic materials 0.000 claims 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims 1
- 229910000019 calcium carbonate Inorganic materials 0.000 claims 1
- 239000001110 calcium chloride Substances 0.000 claims 1
- 229910001628 calcium chloride Inorganic materials 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 239000000428 dust Substances 0.000 claims 1
- WOEQEDQNDRKHPV-UHFFFAOYSA-N ethanol;hafnium Chemical compound [Hf].CCO WOEQEDQNDRKHPV-UHFFFAOYSA-N 0.000 claims 1
- 229910000449 hafnium oxide Inorganic materials 0.000 claims 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 claims 1
- 239000002184 metal Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 claims 1
- 238000005245 sintering Methods 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 238000005303 weighing Methods 0.000 claims 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract 1
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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Abstract
The invention provides a lithium titanate cathode material and a method for preparing the same, and a battery produced by employing the same. The chemical formula of the lithium titanate cathode material is as follows: Li4-xCaxTi5-yHfyO12, wherein x is greater than or equal to 0.01 and less than or equal to 0.05, and y is greater than or equal to 0.001 and less than or equal to 0.01. The lithium titanate cathode material is added with calcium element so that the electric conductivity of the battery is improved; besides, hafnium is added to inhibit grain growth; therefore, the rate capability of the lithium titanate cathode material is improved; and the problems of poor electric conductivity and unsatisfactory electrochemical properties of the lithium titanate cathode material are solved.
Description
Technical field
The present invention relates to lithium ion battery, ultracapacitor field, especially, relate to a kind of lithium titanate anode material and preparation method.In addition, the invention still further relates to a kind of battery that adopts above-mentioned negative material to make.
Background technology
Along with the exhaustion day by day of fossil energy and increasingly sharpening of environmental pollution, the source problem that comes of automobile power receives unprecedented concern.The power supply of mobile electronic device adopts lithium ion battery usually at present, and it is the electric automobile energy supply that this battery can be used as ultracapacitor simultaneously.But it is negative pole for anodal, material with carbon element that existing commercialization lithium ion battery adopts cobalt acid lithium or nickel-cobalt-manganese ternary material usually, if the pairing of this both positive and negative polarity is applied on the electrokinetic cell, will produce very big safety problem.In the continuous charge and discharge process of electrokinetic cell, lithium ion probably forms Li dendrite at carbon material surface, causes battery short circuit thereby pierce through barrier film.A kind of novel lithium ionic cell cathode material lithium titanate becomes the focus of research gradually at present, it has plurality of advantages: (1) embeds at lithium ion that crystal structure can keep the stability of height in the process of deviating from, and makes it have good cycle performance and discharge voltage stably; (2) have higher relatively electrode voltage (1.55V), this makes this electrode material to use in the electrolytical burning voltage of most liquid interval, thereby has avoided the generation of electrolyte decomposition phenomenon or protective layer; (3) Li
4Ti
5O
12Platform appears in voltage when being charged to spinel structure and rock salt structure two-phase section, utilizes this point, can be used as the indication that charging finishes; (4) Li
4Ti
5O
12Chemical diffusion coefficient at normal temperatures is 2 * 10
-8Cm
2S
-1, than big 1 order of magnitude of carbon negative pole material, charge-discharge velocity is very fast.
But lithium ion battery must possess macroion conductivity and electron conduction simultaneously if possess good electrochemical.The spinel structure of lithium titanate provides good three-dimensional channel for lithium ion, and lithium ion conductivity is quite high; But the electronic conductivity of lithium titanate material is then very poor.Prior art is being improved on the lithium titanate conductivity, adopts two kinds of methods substantially: (1) is other element that mixes in lithium titanate anode material, as; Sodium (Na), magnesium (Mg), zinc (Zn), tantalum (Ta), niobium (Nb), zirconium (Zr), copper (Cu), chromium (Cr), nickel (Ni), manganese (Mn), yttrium (Y) and some thuliums (group of the lanthanides); (2) surface carbon coats.Though above method can solve the problem of lithium titanate material electronic conductance rate variance to a certain extent, its chemical property is still undesirable.
Summary of the invention
The battery that the object of the present invention is to provide this negative material of a kind of lithium titanate anode material and preparation method and employing to make is to solve lithium titanate material electronic conductance rate variance, the problem that chemical property is undesirable.
For achieving the above object, an aspect of of the present present invention provides a kind of lithium titanate anode material, and the chemical formula of above-mentioned lithium titanate anode material is: Li
4-xCa
xTi
5-yHf
yO
12, wherein, 0.01≤x≤0.05,0.001≤y≤0.01.
Further, scope 0.015≤x≤0.03 of X, scope 0.0015≤y≤0.005 of Y.
Further, X=0.02, Y=0.002.
Further, the particle diameter of lithium titanate anode material is 1～5 μ m.
Another aspect of the present invention also provides a kind of preparation method of lithium titanate anode material, may further comprise the steps: with the titanium source, and the lithium source, calcium source and hafnium source obtain first material after mixing; First material is carried out sintering obtain second material; Second material is pulverized, disperseed, obtain lithium titanate anode material.
Further, the calcium source is one or more in calcium carbonate, calcium hydroxide, the calcium chloride.
Further, the hafnium source is one or more of Hf metal dust, hafnium oxide or ethanol hafnium.
Another aspect of the present invention also provides a kind of battery, and this battery adopts above-mentioned lithium titanate anode material as negative material.
The present invention has following beneficial effect:
The present invention makes lithium titanate anode material have excellent high rate performance, excellent conducting performance by doping calcium, two kinds of elements of hafnium, has the cycle performance excellence, high repeatability and other advantages, and cost of material is cheap, and preparation technology is simple, is fit to industrial-scale production.
Except purpose described above, feature and advantage, the present invention also has other purpose, feature and advantage.With reference to figure, the present invention is further detailed explanation below.
Description of drawings
The accompanying drawing that constitutes the application's a part is used to provide further understanding of the present invention, and illustrative examples of the present invention and explanation thereof are used for explaining the present invention, do not constitute improper restriction of the present invention.In the accompanying drawings:
Fig. 1 is 50 circulation volume resolution charts of preferred embodiment of the present invention product;
Fig. 2 is the high rate performance curve chart of preferred embodiment of the present invention product;
Fig. 3 is the X-ray diffracting spectrum of preferred embodiment of the present invention product;
Fig. 4 is the stereoscan photograph of preferred embodiment of the present invention product;
Fig. 5 is the particle diameter distribution map of preferred embodiment of the present invention product.
Embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated, but the multitude of different ways that the present invention can be defined by the claims and cover is implemented.
One aspect of the present invention provides a kind of lithium titanate anode material, adopts calcium constituent (Ca
2+) and hafnium element (Hf) be entrained in simultaneously in the lithium titanate, obtaining chemical formula is Li
4-xCa
xTi
5-yHf
yO
12Chemicals, wherein, 0.01≤x≤0.05,0.001≤y≤0.01.Ca
2+Replace the lithium ion (Li that is positioned at tetrahedron or octahedral voids
+), generate excess electron, make free electron concentration raise, thereby improve the electronic conductivity of lithium titanate.
Hf and titanium (Ti) are positioned at same subgroup, and electron configuration is arranged similar to Ti, and therefore, chemical property is comparatively similar, can occupy the octahedral voids of Ti atom.The purpose that Hf partly replaces Ti mainly is to form defective, suppresses the further growth of crystal grain, obtains monodispersed particle, thereby reduces Li
+With the migration path of electronics, make electrolyte soak into electrode material fully, improve high rate performance.
The scope of X: 0.01≤x≤0.05 wherein; The scope of Y: 0.001≤y≤0.01.If X or Y's is too small, then the concentration of calcium or hafnium is low excessively, the uniformity of calcium and hafnium in the very difficult assurance doping process, and concentration is low excessively simultaneously, can obviously not improve chemical property; X or Y's is excessive, then can influence Li
4Ti
5O
12Original cubic spinel structure, thus Li influenced
4Ti
5O
12Stability of structure in discharge process, and reduce its specific discharge capacity.
When the scope of X is 0.015≤x≤0.03, the scope of Y is 0.0015≤y≤0.005 o'clock, the battery performance excellence of resulting lithium titanate anode material assembling, good cycle, specific discharge capacity height.
When X is that 0.02, Y is 0.002 o'clock, lithium titanate anode material is Li
3.98Ca
0.02Ti
4.998Hf
0.002O
12The battery of this negative material assembling, specific discharge capacity is the highest, and 500 times circulation back 1C discharge capacity still can reach 150mAh/g, cycle performance the best.
The particle diameter of lithium titanate anode material is 1～5 μ m.The particle diameter of lithium titanate anode material is too high or too low, all can influence the chemical property of lithium titanate anode material.
According to molecular formula Li
4-xCa
xTi
5-yHf
yO
12, can calculate the titanium source by this formula of quality=molal weight * molecular weight, lithium source, calcium source, the weight that feeds intake in hafnium source.
Another aspect of the present invention also provides a kind of preparation method of lithium titanate anode material, may further comprise the steps:
Mix: with the titanium source, the lithium source, calcium source and hafnium source obtain first material after mixing.
Sintering: first material is carried out sintering obtain second material.
Pulverize: second material is pulverized, disperseed, obtain lithium titanate anode material.
Detitanium-ore-type (TiO is adopted in the titanium source
2), metatitanic acid (H
2TiO
3), rutile-type (TiO
2), isopropyl titanate Ti{OCH (CH
3)
2}
4In one or more.
Lithium carbonate (Li is adopted in the lithium source
2CO
3), lithium hydroxide (LiOH), lithium hydroxide (LiOHH
2O), lithium acetate (CH
3COOLi) one or more in.
Calcium carbonate (CaCO is adopted in the calcium source
3), calcium hydroxide (Ca (OH)
2), in the calcium chloride (CaCl) one or more.
Hf metal dust, hafnium oxide (HfO are adopted in the hafnium source
2), ethanol hafnium Hf (OC
2H
5)
4One or more.
Synthetic lithium titanate Li
4-xCa
xTi
5-yHf
yO
12Adopt the operation of conventional high temperature solid-state method or sol-gal process.
Blend step adopts conventional doing to mix or the mode of wet mixing is operated, and charging sequence is: add the titanium source compound earlier, add Li source compound again, add calcium source and hafnium source at last.
Sintering step adopts full-automatic air electricity pushed bat kiln to carry out sintering, and push pedal speed is 10～50min/ push pedal.Bubbling air in the burner hearth, each warm area throughput is 4～20L/min.Sintering temperature is 650～900 ℃.Burner hearth has 10 warm areas, and temperature rises gradually.Main warm area temperature is sintering temperature.
Material disperseed after pulverising step adopted conventional crushing operation to sintering.
Another aspect of the present invention also provides a kind of battery, and this battery adopts above-mentioned lithium titanate anode material as negative material.Above-mentioned lithium titanate anode material and metal lithium sheet are formed half-cell, lithium titanate activating agent, binding agent, conductive black are 91: 5: 4 inputs according to mass ratio, drip N-methyl pyrrolidone (NMP) solvent, evenly be coated on slurry on the aluminium foil after fully grinding, 120 ℃ of following vacuumize 12 hours, stamp out the electrode slice of required area then, with electrolyte lithium hexafluoro phosphate (LiPF
6) to be dissolved in volume ratio be to form electrolyte in 1: 1 the mixed solution of ethylene carbonate (EC) and dimethyl carbonate (DMC), concentration is 1mol/L, finishes the assembling of CR2032 button cell in glove box.Binding agent is Kynoar (PVDF).
Embodiment
Following examples specimen in use and instrument are commercially available.
The detection of conductivity: respectively with the lithium titanate anode material of embodiment 1～5.
Embodiment 1: according to molecular formula Li
3.98Ca
0.02Ti
4.998Hf
0.002O
12Stoichiometric proportion, take by weighing 39.91kg Detitanium-ore-type TiO
2, the Li of 14.70kg
2CO
3, the CaCO of 0.20kg
3, the HfO of 0.042kg
2, in the 100L dry mixer, mix; Enter the fully automatic electric ejection plate kiln after mixing and carry out 750 ℃ of sintering, sintering adopts the staged temperature schedule, temperature value of setting of different warm areas is (250 ℃ of 1 warm areas, 350 ℃ of 2 warm areas, 450 ℃ of 3 warm areas, 550 ℃ of 4 warm areas, 600 ℃ of 5 warm areas, 6 to 10 warm areas are 750 ℃) push pedal speed is the 20min/ push pedal; Utilize airslide disintegrating mill to pulverize after sintering is finished, regulate and pulverize and value parameter, making and pulverizing air pressure is 0.5MPa, and the feeding frequency is 40Hz, and the grading wheel frequency is 90Hz, obtains grain and is the lithium titanate anode material of D50=1.5 μ m.
Negative material and the metal lithium sheet of embodiment 1 are formed half-cell, lithium titanate activating agent, PVDF, conductive black are adding in 91: 5: 4 by mass ratio, drip an amount of nmp solvent, evenly be coated on slurry on the aluminium foil after fully grinding, 120 ℃ of following vacuumize 12h, stamp out the electrode slice of required area then, with electrolyte LiPF
6Be dissolved in volume ratio and be in the mixed solution of 1: 1 EC and DMC and form electrolyte, concentration is 1mol/L, finishes the assembling of CR2032 button cell in glove box.
Make constant current charge-discharge behavior behind the battery by the lithium titanate anode material in the LAND charge-discharge test instrument test implementation example 1, first discharge specific capacity (0.1C) is 170.1mAh/g, the 6C discharge capacity can reach 145mAh/g, the 20C capacity reaches 130mAh/g, and 500 circulation back 1C discharge capacities still can reach 150mAh/g.
Lithium titanate anode material among the embodiment 1 is placed the piston type compression mold, and depressing to diameter at 20Mpa pressure is 1.5cm, and thickness is the disk of 1cm.Adopt four probe method to measure the resistivity of zones of different on the disk, the resistivity on the same disk is averaged, and mean value is got the conductivity that inverse obtains lithium titanate anode material.The conductivity of lithium titanate anode material is 1.48 * 10 among the embodiment 1
-3Scm
-1
Lithium titanate anode material among the embodiment 1 made carries out 50 circulation specific discharge capacities tests behind the battery, the result as shown in Figure 1, among the figure 1, the current density of 2 circulations (cyc) is 0.1C, 3,4cyc is 0.2C, and 5cyc is 0.5C, 6cyc is 0.8C, 7cyc is 1C, and 8cyc is 2C, and 9cyc is 5C, 10cyc is 10C, and 11cyc all is later the 1C discharge.As can be seen from Figure 1, the lithium titanate capacity is almost undamped in cyclic process.Lithium titanate anode material among the embodiment 1 made carries out the high rate performance test behind the battery, the result as shown in Figure 2, it is very good that the lithium titanate voltage platform keeps.Lithium titanate anode material among the embodiment 1 is carried out X-ray diffraction, the result as shown in Figure 3, the lithium titanate anode material of embodiment 1 is pure spinel structure, the visible a small amount of miscellaneous growth that can not influence the lithium titanate crystal.Lithium titanate anode material among the embodiment 1 is carried out electron-microscope scanning, the result as shown in Figure 4, the lithium titanate anode material of the embodiment of the invention 1 is that monodispersed submicron particles is formed.Lithium titanate anode material among the embodiment 1 is carried out particle size distribution test, the result as shown in Figure 5, the lithium titanate anode material particle diameter particle size distribution of the embodiment of the invention 1 is comparatively concentrated, is normal distribution.
Embodiment 2: according to molecular formula Li
3.95Ca
0.05Ti
4.999Hf
0.001O
12Stoichiometric proportion, take by weighing the TiO (OH) of 48.93kg
2, the CH of 13.03kg
3COOLi, the Ca of 3.70kg (OH)
2, the Hf (OC2H of 0.21kg
5)
4, press the solid-liquid volume ratio and add deionized water at 3: 1, and add the 0.62kg polyethylene glycol, in duplicate rows star power mixer, mix; Carrying out drying under reduced pressure after mixing and remove solvent, pressure is-0.08～-0.09MPa; Be dried to and enter the fully automatic electric ejection plate kiln behind the powder and carry out 700 ℃ of sintering, push pedal speed is the 25min/ push pedal.Sintering adopts the staged temperature schedule, temperature value of setting of different warm areas is (250 ℃ of 1 warm areas, 300 ℃ of 2 warm areas, 400 ℃ of 3 warm areas, 500 ℃ of 4 warm areas, 600 ℃ of 5 warm areas, 6 to 10 warm areas are 700 ℃) sintering carries out pulverising step (revolution rotating speed: 200 rev/mins of rotation rotating speeds: 600 rev/mins), obtain the lithium titanate anode material that suitable particle size is D50=1.5 μ m after finishing.
This sample and metal lithium sheet are formed half-cell, finish the battery assembling according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery by the lithium titanate anode material in the LAND charge-discharge test instrument test implementation example 2 assembling, first discharge specific capacity (0.1C) be 168mAh/g, 500 circulations afterwards capability retention are 89.8%.
Lithium titanate anode material among the embodiment 2 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 5.32 * 10
-3Scm
-1
Embodiment 3: according to molecular formula Li
3.97Ca
0.03Ti
4.9985Hf
0.0015O
12Stoichiometric proportion, take by weighing the TiO (OH) of 48.92kg
2, the CH of 13.10kg
3COOLi, the Ca of 0.22kg (OH)
2, the Hf (OC of 0.54kg
2H
5)
4Press the solid-liquid volume ratio and add deionized water at 3: 1, and add the 0.62kg polyethylene glycol, in duplicate rows star power mixer, mix; Carrying out drying under reduced pressure after mixing and remove solvent, pressure is-0.08～-0.09MPa; Be dried to and enter the fully automatic electric ejection plate kiln behind the powder and carry out 800 ℃ of sintering, push pedal speed is the 15min/ push pedal.Sintering adopts the staged temperature schedule, temperature value of setting of different warm areas is (300 ℃ of 1 warm areas, 400 ℃ of 2 warm areas, 500 ℃ of 3 warm areas, 600 ℃ of 4 warm areas, 700 ℃ of 5 warm areas, 6 to 10 warm areas are 800 ℃) sintering carries out pulverising step (revolution rotating speed: 200 rev/mins of rotation rotating speeds: 600 rev/mins), obtain the lithium titanate anode material that suitable particle size is D50=1.5 μ m after finishing.
This sample and metal lithium sheet are formed half-cell, finish the battery assembling according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery by the lithium titanate anode material in the LAND charge-discharge test instrument test implementation example 3 assembling, first discharge specific capacity (0.1C) be 169.3mAh/g, 500 circulations afterwards capability retention are 90.2%.
Lithium titanate anode material among the embodiment 3 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 3.65 * 10
-5Scm
-1
Embodiment 4: according to molecular formula Li
3.985Ca
0.015Ti
4.995Hf
0.005O
12Stoichiometric proportion, take by weighing the Ti{OCH (CH of 141.97kg
3)
2}
4, the LiNO of 13.74kg
3, the CaCl of 0.17kg
2, the Hf (OC of 0.18kg
2H
5)
4Press the solid-liquid volume ratio and add deionized water at 3: 1, and add the 0.62kg polyethylene glycol, in duplicate rows star power mixer, mix; Carrying out drying under reduced pressure after mixing and remove solvent, pressure is-0.08～-0.09MPa; Be dried to and enter the fully automatic electric ejection plate kiln behind the powder and carry out 900 ℃ of sintering, push pedal speed is the 10min/ push pedal.Sintering adopts the staged temperature schedule, temperature value of setting of different warm areas is (250 ℃ of 1 warm areas, 300 ℃ of 2 warm areas, 400 ℃ of 3 warm areas, 500 ℃ of 4 warm areas, 600 ℃ of 5 warm areas, 6 to 10 warm areas are 700 ℃) sintering carries out pulverising step (revolution rotating speed: 200 rev/mins of rotation rotating speeds: 600 rev/mins), obtain the lithium titanate anode material that suitable particle size is D50=1.5 μ m after finishing.
This sample and metal lithium sheet are formed half-cell, finish the battery assembling according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery by the lithium titanate anode material in the LAND charge-discharge test instrument test implementation example 4 assembling.First discharge specific capacity (0.1C) is 171.6mAh/g, and 500 times circulation back capability retention is 89.0%.
Lithium titanate anode material among the embodiment 4 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 5.85 * 10
-4Scm
-1
Embodiment 5: according to molecular formula Li
3.99Ca
0.01Ti
4.99Hf
0.01O
12Stoichiometric proportion, take by weighing 141.8kg isopropyl titanate Ti{OCH (CH
3)
2}
4, the LiNO of 13.8kg
3, the CaCl of 0.11kg
2, the Hf (OC of 0.359kg
2H
5)
4, add a certain amount of deionized water, form gel, aging 3h.After this in baking oven, carry out 120 ℃ of oven dry, ball milling.After this drop into the fully automatic electric ejection plate kiln and carry out sintering for 650 ℃, push pedal speed is the 24min/ push pedal; Sintering adopts the staged temperature schedule, and temperature value of setting of different warm areas is (150 ℃ of 1 warm areas, 200 ℃ of 2 warm areas, 350 ℃ of 3 warm areas, 450 ℃ of 4 warm areas, 550 ℃ of 5 warm areas, 6 to 10 warm areas are 650 ℃), after finishing, sintering obtains the lithium titanate anode material of granularity D50=1.8 μ m.
This sample and metal lithium sheet are formed half-cell, finish the assembling of CR2032 button cell according to the method for embodiment 1.The constant current charge-discharge behavior of the lithium battery by the lithium titanate anode material in the LAND charge-discharge test instrument test implementation example 5 assembling, first discharge specific capacity (0.1C) be 170mAh/g, 500 circulations afterwards capability retention are 88.2%.
Lithium titanate anode material among the embodiment 5 is carried out conductivity according to the method for embodiment 1 detect, its conductivity is 2.17 * 10
-4Scm
-1
The above is the preferred embodiments of the present invention only, is not limited to the present invention, and for a person skilled in the art, the present invention can have various changes and variation.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (8)
1. a lithium titanate anode material is characterized in that, the chemical formula of described lithium titanate anode material is: Li
4-xCa
xTi
5-yHf
yO
12, wherein, 0.01≤x≤0.05,0.001≤y≤0.01.
2. lithium titanate anode material according to claim 1 is characterized in that, scope 0.015≤x≤0.03 of described X, scope 0.0015≤y≤0.005 of described Y.
3. lithium titanate anode material according to claim 2 is characterized in that, described X=0.02, described Y=0.002.
4. according to each described lithium titanate anode material among the claim 1-3, it is characterized in that the particle diameter of described lithium titanate anode material is 1～5 μ m.
5. the preparation method of a lithium titanate anode material is characterized in that, may further comprise the steps:
According to molecular formula Li
4-xCa
xTi
5-yHf
yO
12Weighing titanium source, the lithium source, the weight that feeds intake in calcium source and hafnium source obtains first material after the mixing, wherein, 0.01≤x≤0.05,0.001≤y≤0.01;
First material is carried out sintering obtain second material;
Second material is pulverized, disperseed, obtain each described lithium titanate anode material in the claim 1～4.
6. preparation method according to claim 5 is characterized in that, described calcium source is one or more in calcium carbonate, calcium hydroxide, the calcium chloride.
7. preparation method according to claim 5 is characterized in that, described hafnium source is one or more of Hf metal dust, hafnium oxide or ethanol hafnium.
8. a battery is characterized in that, each described lithium titanate anode material is as negative material in the described battery employing claim 1～4.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012101542732A CN102646823B (en) | 2012-05-17 | 2012-05-17 | Lithium titanate cathode material and method for preparing same, and battery produced by employing same |
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|---|---|---|---|
| CN2012101542732A CN102646823B (en) | 2012-05-17 | 2012-05-17 | Lithium titanate cathode material and method for preparing same, and battery produced by employing same |
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| Publication Number | Publication Date |
|---|---|
| CN102646823A CN102646823A (en) | 2012-08-22 |
| CN102646823B true CN102646823B (en) | 2013-08-14 |
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| CN101960655A (en) * | 2008-03-04 | 2011-01-26 | 埃纳德尔公司 | Anode for lithium-ion cell and method of making the same |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
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| CN101960655A (en) * | 2008-03-04 | 2011-01-26 | 埃纳德尔公司 | Anode for lithium-ion cell and method of making the same |
| CN101877407A (en) * | 2009-04-30 | 2010-11-03 | 比亚迪股份有限公司 | Cathode active material, preparation method thereof and battery |
| CN102376945A (en) * | 2010-08-20 | 2012-03-14 | 三星Sdi株式会社 | Negative active material, method of preparing same, and rechargeable lithium battery including same |
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