CN100530780C - Composite lithium titanate electrode material and preparation method thereof - Google Patents
Composite lithium titanate electrode material and preparation method thereof Download PDFInfo
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- CN100530780C CN100530780C CNB2006100636120A CN200610063612A CN100530780C CN 100530780 C CN100530780 C CN 100530780C CN B2006100636120 A CNB2006100636120 A CN B2006100636120A CN 200610063612 A CN200610063612 A CN 200610063612A CN 100530780 C CN100530780 C CN 100530780C
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Abstract
The invention discloses an electrode material of composite lithium titanate and its preparation method, which is secondary particles with spherical or similar spherical shape and porous nanometer channels, which is made from lithium titanate particles, nano-carbon coated materials and doped modifier. The preparation method includes: milling the inorganic lithium salt, titanium dioxide, nano-carbon coated material or doped modifier, scattering them into the organic solvent for further drying, processing heat treatment, and cooling. Comparing with the existing technologies, this electrode material has the high-rate performance, highly reversible electrochemical capacity, and smaller surface area to enhance its first Coulomb efficiency and cycle stability, applying to rechargeable and once-use lithium-ion battery.
Description
Technical field
The present invention relates to a kind of battery electrode material and preparation method thereof, particularly a kind of composite titanic acid lithium material that is used for lithium battery and preparation method thereof.
Background technology
In recent years, spinel type lithium titanate Li
4Ti
5O
12Electrode material as novel energy storage cell comes into one's own day by day, this is because spinel type lithium titanate crystal structure in lithium ion embedding-Tuo embedding process can keep the stability of height, lithium ion all is a spinel structure before and after embedding, and lattice constant changes very little, change in volume is very little simultaneously, less than 1%, so Li
4Ti
5O
12Be called as " zero strain " electrode material.This can be avoided in the charge and discharge cycles owing to the flexible back and forth of electrode material causes structural damage, thereby the cycle performance and the useful life of improving electrode has reduced the decay that brings the specific capacity amplitude with the increase of cycle-index, makes Li
4Ti
5O
12Has excellent cycle performance.Compare Li with carbon negative pole material
4Ti
5O
12Equilibrium potential is higher, has avoided the deposition of lithium metal, and its platform capacity surpasses 85% of total capacity, and current potential rose rapidly when charging finished, and this phenomenon can be used for indication and stops charging, avoided overcharging, so Li
4Ti
5O
12The fail safe of negative pole is than carbon negative pole material height; Li
4Ti
5O
12The big order of magnitude of chemical diffusion coefficient ratio carbon negative pole material, the speed that discharges and recharges is very fast.Li
4Ti
5O
12Though specific capacity is littler than carbon negative pole material, by other parts of battery are improved, both respectively with LiCoO
2Specific energy was suitable when positive pole was formed battery.Li
4Ti
5O
12Electrode also has high rate during charging-discharging.Li
4Ti
5O
12As negative material and LiCoO
2, LiMn
2O
4, LiNiO
2Can form lithium ion battery, all-solid-state battery and hybrid super capacitor with active carbon etc., show the excellent application performance energy.Simultaneously, advantage such as lithium titanate also has the anti-over-charging performance and thermal stability is good, safe, reliability is high, the life-span is long and specific capacity is big is widely used in fields such as electric automobile, energy-storage batteries.
Lithium titanate is lower with respect to the electromotive force of lithium metal, is about 1.5V, when with the positive electrode LiCoO of 4V
2, LiMn
2O
4Operating voltage is 2 times of nickel metal hydride near 2.5V when forming battery; Form the lithium ion battery of 3V level with the positive electrode of 4.5V level, can be used for substituting the existing occasion of using by two joint dry cells series connection.Lithium titanate can also be applied to the electrode material of ultracapacitor, and ultracapacitor provides the important energy storage device of high power density, has broad application prospects in fields such as electric automobile and hybrid vehicles.
The synthetic method of lithium titanate is many, and solid reaction process, high-energy ball milling method and sol-gel process are arranged usually.
Solid reaction process: at the process engineering journal, 2003 the 5th the 2nd phases of volume, " amorphous TiO
2Synthetic spinel Li
4Ti
5O
12Performance " in, human solid reaction processes such as Yang Jianwen have synthesized lithium titanate.Press n
Li: n
Ti=0.84 mol ratio accurately takes by weighing Li
2CO
3With amorphous TiO
2And be scattered in the ethanol, with three-head grinding machine continuously grinding 2h, remove ethanol, contain in the corundum boat, place in the tube furnace, in air, the control programming rate is 5 ℃/min, and temperature is kept 24h after reaching 950 ℃, slowly be cooled to below 100 ℃, use continuously grinding 2h in the three-head grinding machine air again, 250 ℃ of oven dry are stored in the drier standby.Product cycle performance with this prepared is relatively poor.
High-energy ball milling method: at battery, 2004 the 34th volumes, the 5th phase, " synthesis temperature is to Li4Ti
5O
12The influence of chemical property " in, people such as Gao Ling are with LiOHH
2O, anatase TiO
2Press amount of substance and mixed than 4: 5, absolute ethyl alcohol is as dispersant, and ball milling 6h, the slurry that obtains after the air dry, are warming up to 700 ℃ or 800 ℃ with 5 ℃/min under air atmosphere, behind the insulation 12h, cools to room temperature with the furnace.After pulverizing, sieving, further calcining: be warming up to 700 ℃ or 800 ℃ respectively with 5 ℃ of min, insulation 8h obtains lithium titanate after the cooling, and the specific capacity after its 30 times circulations is more than 155mAh/g.But this kind technology is complicated, is difficult to realize industrial production.
Sol-gel process: at J Power Sources, 2003,119-121:637-643, " Thermodynamic and kinetic approaches to lithium intercalation intoLi[Ti
5/3Li
1/3] O
4Film electrode " in, people such as K.N.Jung are dissolved in acetylacetonate lithium and acetylacetone,2,4-pentanedione titanium oxide in n-butanol and the acetic acid solution, and lithium, titanium amount of substance ratio are 4: 5.Mixed solution is stirred 24h, then at room temperature, in being full of the glove box of argon gas, use ultrasonic waves for cleaning 5min, be that the polytetrafluoroethylene PTFE membrane filtration of 0.2 μ m obtains colloidal sol with average pore size again, adopt the method for " rotation plating " to be deposited on the thick platinum electrode of 200nm.Dry a few minutes under 350 ℃, desolvate and organic matter to remove, in air, calcine 1h at last under 750 ℃, promptly obtain Li
4Ti
5O
12Product.The lithium titanate charging/discharging voltage platform of this method preparation is 1.56V, 1mol Li
4Ti
5O
12In can embed the lithium of 3mol.Sol-gel process has the following advantages: 1. chemical uniformity is good, by the colloidal sol that slaine is made, can reach atom level and evenly distribute; 2. chemical purity height, stoichiometric proportion can accurately be controlled; 3. heat treatment temperature reduction, time shorten; 4. can prepare nano-powder and film; 5. by control sol gel process parameter, might realize material structure is accurately controlled.Its shortcoming also is conspicuous: be added with organic compounds and caused the cost rising; In the process of sintering, it is the violent process that expands of a volume that gel becomes powder, so the utilance of reacting furnace is lower; Organic substance produces a large amount of CO in the process of sintering
2Gas; Complex process is difficult to realize that large-scale industrial production satisfies the wilderness demand of energy field.
Because the conductivity of lithium titanate itself is very poor, capacity can not well be brought into play when high power charging-discharging, therefore need be by its modification be improved its conductivity, thereby improve the high rate capability of lithium titanate, also to keep its high reversible electrochemical capacity and good cyclical stability simultaneously, and need with low cost.
Summary of the invention
The purpose of this invention is to provide a kind of composite lithium titanate electrode material and preparation method thereof, the technical problem that solve is to improve the electric conductivity of lithium titanate, reduces its cost, adapts to suitability for industrialized production.
The present invention is by the following technical solutions: a kind of composite lithium titanate electrode material, the second particle that described composite lithium titanate electrode material is mixed and formed by lithium titanate particle, the coating of nano-sized carbon clad material or doping vario-property agent, this second particle has the microscopic feature of sphere or class sphere, comprises the porous nano passage in the particle.
Lithium titanate particle of the present invention is the nano lithium titanate particle; The nano-sized carbon clad material is the cracking carbon or the Nano graphite powder of carbohydrate; The doping vario-property agent is sucrose, lactose, glucose, Nano graphite powder, conductive black, aluminium oxide, magnesium oxide, tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide or tungsten oxide.
Carbohydrate of the present invention is glucose, sucrose or lactose.
Nano-sized carbon clad material of the present invention shared ratio in composite lithium titanate electrode material is 1wt%～10wt%.
Doping vario-property agent of the present invention proportion in composite lithium titanate electrode material is to 10wt% greater than 0.
The particle diameter of combination electrode material of the present invention is 5～50 μ m, specific area 0.5～10.0m
2/ g, tap density 0.7～1.5g/cm
3
A kind of preparation method of composite lithium titanate electrode material, may further comprise the steps:, grind dispersion with high-speed stirred or ball grinding method and made the composite lithium titanate precursor mixture in 2 to 40 hours one, in proportion with the nano-sized carbon clad material of 27.5～24.75wt% inorganic lithium salt, 72.5～65.25wt% titanium dioxide, 1wt%～10wt% or greater than 0 to 10wt% doping vario-property agent; Two, said mixture is scattered in organic solvent ethanol or the acetone, adopts the transient state drying means to make the dispersion powder; Three, will disperse powder heat treatment 4 to 40 hours in 500 to 950 ℃ temperature range; Four, naturally cool to below 150 ℃, pulverize and sieve.
Ball grinding method of the present invention is solid phase high-energy ball milling method or liquid phase high-energy ball milling method.
The present invention adopts the liquid phase high-energy ball milling method, adds the hot water of absolute ethyl alcohol or 60～100 ℃ during ball milling, and ball milling finishes 80～150 ℃ of oven dry.
Method of the present invention will disperse powder to charge into protective gas in the heat treatment process in 500 to 950 ℃ temperature range, and described protective gas is nitrogen, argon gas, helium, neon, CO or CO
2Gas.
Inorganic lithium salt is lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide or lithium iodide in the method for the present invention, and described titanium dioxide is technical grade titanium dioxide.
The nano-sized carbon clad material is cracking carbon, the Nano graphite powder of carbohydrate in the method for the present invention, and carbohydrate is glucose, sucrose or lactose; The doping vario-property agent is sucrose, lactose, glucose, Nano graphite powder, conductive black, aluminium oxide, magnesium oxide, tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide or tungsten oxide.
The present invention compared with prior art, form composite lithium titanate electrode material by coating or doping and high-energy ball milling with good conductivity, thereby improve the high rate capability of lithium titanate, the powder granule that the transient state drying and granulating method makes has the nanochannel of some, the effecting reaction area of electrode and the passage of lithium ion turnover have been increased, make electrode material that very high reversible electrochemical capacity be arranged, the less specific area of spheric granules has improved its coulombic efficiency and cyclical stability first, and improved the processing characteristics of pole piece, low cost product of the present invention, excellent performance, satisfy the requirement of lithium-ion-power cell to the electrode material heavy-current discharge, its preparation method is simple, satisfies the demand of suitability for industrialized production, is applicable to chargeable lithium ion battery, lithium primary battery.
Description of drawings
Fig. 1 is the SEM figure of the granular precursor of embodiment of the invention composite lithium titanate.
Fig. 2 is the dried SEM figure of embodiment of the invention composite lithium titanate transient state.
Fig. 3 is the SEM figure (500 times) of embodiment of the invention composite lithium titanate final products.
Fig. 4 is the SEM figure (3000 times) of embodiment of the invention composite lithium titanate final products.
Fig. 5 (a) is the standard powder diffraction XRD figure of lithium titanate.
Fig. 5 (b) is the powder diffraction XRD figure of composite lithium titanate electrode material of the present invention.
Fig. 6 is the charging and discharging curve figure of composite lithium titanate electrode material of the present invention.
Fig. 7 is the charge-discharge performance figure of composite lithium titanate electrode material of the present invention.
Embodiment
Below in conjunction with embodiment the present invention is described in further detail.Composite lithium titanate electrode material of the present invention is by the nano lithium titanate particle, the second particle that the nano-sized carbon clad material coats or the doping vario-property agent is mixed and formed, nano-sized carbon clad material shared ratio in composite lithium titanate electrode material is 1wt%～10wt%, and doping vario-property agent proportion in composite lithium titanate electrode material is to 10wt% greater than 0.Composite lithium titanate electrode material has the microscopic feature of sphere or class sphere, contain a large amount of in the composite lithium titanate particle by the micro chink or the microchannel that mutually combine between nano lithium titanate particle and the nano-carbon material and form, form the nanochannel that lithium ion can pass in and out, its particle diameter is 5～50 μ m, specific area 0.5～10.0m
2/ g, tap density 0.7～1.5g/cm
3
The nano-sized carbon clad material is cracking carbon, the Nano graphite powder of carbohydrate, and carbohydrate is glucose, sucrose or lactose.The doping vario-property agent is sucrose, lactose, glucose, Nano graphite powder, conductive black, aluminium oxide, magnesium oxide, tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide or tungsten oxide.
The preparation method of composite lithium titanate electrode material of the present invention, may further comprise the steps:, made the composite lithium titanate precursor mixture in 2 to 40 hours with high-speed stirred, solid phase high-energy ball milling method or liquid phase high-energy ball milling method mill one, in proportion with the nano-sized carbon clad material of 27.5～24.75wt% inorganic lithium salt, 72.5～65.25wt% technical grade titanium dioxide, 1wt%～10wt% or greater than 0 to 10wt% doping vario-property agent; Two, said mixture is scattered in organic solvent ethanol or the acetone, adopts the transient state drying means to make the dispersion powder; Three, will disperse powder heat treatment 4 to 40 hours in 500 to 950 ℃ temperature range, and charge into protective gas in the heat treatment process, described protective gas is nitrogen, argon gas, helium, neon, CO or CO
2Gas; Four, naturally cool to below 150 ℃, pulverize and sieve.
Solid phase high-energy ball milling method that method of the present invention adopts or liquid phase high-energy ball milling method are at battery, and 2004 the 34th roll up, and the 5th phase, " synthesis temperature is to Li4Ti
5O
12The influence of chemical property " in address, the transient state drying means is addressed in patent application 200610062255.6.
Among the preparation method of composite lithium titanate electrode material of the present invention, inorganic lithium salt is lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide or lithium iodide.Titanium dioxide is technical grade titanium dioxide.The nano-sized carbon clad material is cracking carbon, the Nano graphite powder of carbohydrate, and carbohydrate is glucose, sucrose or lactose.The doping vario-property agent is sucrose, lactose, glucose, Nano graphite powder, conductive black, aluminium oxide, magnesium oxide, tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide or tungsten oxide.
It is the feedstock production lithium titanate that the present invention adopts the titanium dioxide of technical grade and lithium salts.In preparation process, utilize high energy ball mill that raw material ball is milled to nanometer materials; fully increase the contact area of titanium dioxide and lithium salts; improve its homogeneity; mix simultaneously, improved its electric conductivity, it is little that the spheric granules electrode material of preparation has specific area; the tap density height; the characteristics that irreversible capacity is little through the operation process of high-energy ball milling, doping, transient state drying and granulating and roasting under the non-oxidizing gas protection, have been made the composite titanic acid lithium material of excellent combination property.
Embodiment 1: take by weighing industrial titanium dioxide of 500g and 189.6g lithium carbonate in ball grinder; add the 36.3g Nano graphite powder again; obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 10 hours; granular precursor as shown in Figure 1; mixture is scattered in the ethanol; adopt the transient state drying means to make the dispersion powder; disperse powder as shown in Figure 2; gained disperses powder to put into crucible; place nitrogen atmosphere protection high temperature furnace; be warming up to 600 ℃; be incubated after 15 hours; naturally cool to below 150 ℃; take out; through pulverizing; promptly get the composite titanic acid lithium material after the screening; as shown in Figure 3 and Figure 4; the second particle that the composite lithium titanate particle that makes is made up of nano lithium titanate and nano-carbon material; the composite lithium titanate particle has the microscopic feature of sphere or class sphere; comprise the porous nano passage in the lithium titanate second particle; promptly contain a large amount of by the micro chink or the microchannel that mutually combine between nano lithium titanate particle and the nano-carbon material and forms, the nanochannel that the formation lithium ion can pass in and out.
Embodiment 2: take by weighing industrial titanium dioxide of 500g and 189.6g lithium carbonate in ball grinder; add 76.6g glucose again as carbon encapsulated material; obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 40 hours; mixture is scattered in the alcohol solvent; adopt the transient state drying means to make the dispersion powder; gained disperses powder to put into crucible; place nitrogen atmosphere protection high temperature furnace; be warming up to 950 ℃; be incubated after 4 hours; naturally cool to below 150 ℃, take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Embodiment 3: take by weighing industrial titanium dioxide of 500g and 189.6g lithium carbonate in ball grinder; add the 6.97g Nano graphite powder again; and then add the absolute ethyl alcohol of 700mL; on the planetary ball mill with the rotating speed ball milling of 350rpm after 2 hours; obtain precursor mixture at drying box with 80～150 ℃ of oven dry; mixture is scattered in the acetone solvent; adopt the transient state drying means to make the dispersion powder; gained disperses powder to put into crucible, places argon atmospher protection high temperature furnace, is warming up to 500 ℃; be incubated after 40 hours; naturally cool to below 150 ℃, take out, through pulverizing; promptly get the composite titanic acid lithium material after the screening.
Embodiment 4: take by weighing industrial titanium dioxide of 500g and 222.8g lithium hydroxide in ball grinder; add the 28.7g Nano graphite powder again; obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 30 hours; mixture is scattered in the alcohol solvent; adopt the transient state drying means to make the dispersion powder; gained disperses powder to put into crucible; place CO atmosphere protection high temperature stove; be warming up to 750 ℃; be incubated after 16 hours; naturally cool to below 150 ℃, take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Embodiment 5: take by weighing the 222.8g lithium hydroxide and be dissolved in 60～100 ℃ the hot water; add industrial titanium dioxide of 500g and 28.7g Nano graphite powder again; after being stirred to pasty state with the rotating speed of 2000rpm; obtain precursor mixture at drying box with 80～150 ℃ of oven dry; mixture is scattered in the acetone solvent; adopt the transient state drying means to make the dispersion powder; gained disperses powder to put into crucible; place neon atmosphere protection high temperature furnace; be warming up to 700 ℃, be incubated after 12 hours, naturally cool to below 150 ℃; take out, through pulverizing; promptly get the composite titanic acid lithium material after the screening.
Embodiment 6: take by weighing industrial titanium dioxide of 500g and 189.6g lithium carbonate in ball grinder, add 36.3g conductive black Super-P powder again, obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 20 hours, mixture is scattered in the alcohol solvent, adopt the transient state drying means to make the dispersion powder, gained disperses powder to put into crucible, places CO
2In the atmosphere protection high temperature stove, be warming up to 600 ℃, be incubated after 10 hours, naturally cool to below 150 ℃, take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Embodiment 7: take by weighing industrial titanium dioxide of 500g and 183.0g lithium carbonate in ball grinder; add the 13.9g alumina powder again; obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 3 hours; mixture is scattered in the acetone solvent; adopt the transient state drying means to make the dispersion powder; gained disperses powder to put into crucible; place the nitrogen atmosphere protection high temperature furnace; be warming up to 800 ℃; be incubated after 5 hours; naturally cool to below 150 ℃, take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Embodiment 8: take by weighing industrial titanium dioxide of 500g and 183.0g lithium carbonate in ball grinder; add the 76.6g cupric oxide powder again; obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 10 hours; mixture is scattered in the acetone solvent; adopt the transient state drying means to make the dispersion powder; gained disperses powder to put into crucible; place the nitrogen atmosphere protection high temperature furnace; be warming up to 600 ℃; be incubated after 8 hours; naturally cool to below 150 ℃, take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Comparative Examples 1: take by weighing industrial titanium dioxide of 500g and 189.6g lithium carbonate in ball grinder; on the planetary ball mill with the rotating speed ball milling of 350rpm after 3 hours; mixture is scattered in the acetone solvent, adopts the transient state drying means to make the dispersion powder, gained disperses powder to put into crucible; place the nitrogen atmosphere protection high temperature furnace; be warming up to 700 ℃, be incubated after 8 hours, naturally cool to below 150 ℃; take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Comparative Examples 2: take by weighing industrial titanium dioxide of 500g and 189.6g lithium carbonate in ball grinder; add the 36.3g Nano graphite powder again; obtain precursor mixture at the rotating speed ball milling with 350rpm on the planetary ball mill after 10 hours; the gained powder is put into crucible, places nitrogen atmosphere protection high temperature furnace, is warming up to 600 ℃; be incubated after 15 hours; naturally cool to below 150 ℃, take out, after pulverizing, sieving, promptly get the composite titanic acid lithium material.
Electrochemical property test: respectively with the composite titanic acid lithium material that is prepared among the embodiment 1 to 8 and in the Comparative Examples 1, (PVDF mixes by 82: 10: 8 weight ratios conductive carbon black with the polyvinylidene fluoride that is dissolved in N-methyl pyrrolidone NMP, be applied on the Copper Foil collector electrode, standby through vacuum drying chamber oven dry 8 hours, simulated battery is assemblied in the glove box of applying argon gas and carries out, electrolyte is 1mol/L LiPF6/DMC+EMC+EC, 1: 1: 1, metal lithium sheet is to electrode, electrochemical property test carries out on new prestige battery performance test instrument, the charging/discharging voltage scope is 1.0V to 2.5V, charge-discharge magnification is 0.5C, and test result is listed in table 1.
Making the employed positive electrode of lithium ion battery by composite lithium titanate electrode material of the present invention, can be the various composite oxides that contain lithium ion, as: LiCoO
2, LiNiO
2Or LiMn
2O
4, used electrolyte can adopt general various electrolyte and solvent, and electrolyte can be inorganic electrolyte and organic bath, as LiClO
4, LiPF
6, LiAsF
6, LiBF
4Or Li (CF
3SO
2)
2N, solvent generally are made up of the carbonic acid cyclenes ester and the mixing of low viscous chain hydrocarbon carbonic ester of high-k, as ethylene carbonate EC, and propene carbonate PC, dimethyl carbonate DMC, diethyl carbonate DEC or methyl ethyl carbonate EMC etc.Using negative material of the present invention to make the used barrier film of lithium ion battery does not have clear and definite restriction, can adopt commercially available polythene PE, polypropylene PP or poly-second propylene PEP barrier film.Make cathode pole piece and use Copper Foil to make collector electrode, used stick can be with binding agents such as the Kynoar PVDF that is dissolved in the N-methyl pyrrolidone, water miscible styrene-butadiene latex SBR or LA-133.
The present invention is compound by lithium titanate and carbon, after roasting, make the lithium titanate particle with satisfactory electrical conductivity, this particle has very high reversible electrochemical capacity, coulombic efficiency and good high rate capability, stable circulation performance as lithium ion battery negative material.Composite lithium titanate electrode material particle diameter of the present invention is 5～50 μ m, specific area 0.5～10.0m
2/ g, tap density 0.7～1.5g/cm
3Wherein particle diameter adopts the Malvern2000 laser particle analyzer, and specific area adopts the BET method of nitrogen replacement to measure, and tap density adopts QuantachromeAutoTap tap density instrument to record.Its crystal structure characterizes as Fig. 5 (b) shown in, contrasts with the standard powder diagram of lithium titanate shown in Fig. 5 (a) and finds out, extremely the be near the mark crystal structure of spinel lithium titanate of composite lithium titanate material crystals structure of the present invention.As shown in Figure 6 and Figure 7, through electrochemical property test, composite lithium titanate electrode material charge/discharge capacity height of the present invention, potential curve is smooth, and cycle performance is superior.
Because the conductivity of lithium titanate itself is very poor, capacity can not well be brought into play when high power charging-discharging, greatly limited the application of this material on lithium-ion-power cell, it is little to adopt preparation method of the present invention to adopt the spheric granules of distinctive transient state dry technology preparation to make electrode material have specific area, the tap density height, characteristics such as irreversible capacity is little, also has very high reversible electrochemical capacity simultaneously, improved its coulombic efficiency and cyclical stability first, and the process industrial art performance of material is good, and preparation cost is cheap.Be applicable to chargeable lithium ion battery, lithium primary battery.
Adopt Nano graphite powder, glucose, conductive black, aluminium oxide, cupric oxide in the embodiments of the invention respectively, other doping vario-property agent such as sucrose, lactose, magnesium oxide, tin oxide, vanadium oxide, nickel protoxide, chromium oxide or the tungsten oxide do not enumerated, has identical chemical property with the doping vario-property agent among the embodiment, can improve the conductivity of lithium titanate material, thereby reach technique effect of the present invention.Inorganic lithium salt adopts lithium hydroxide, lithium carbonate, other inorganic lithium salt, can produce identical or similar chemical reaction with titanium dioxide as lithia, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide or lithium iodide and generate spinel lithium titanate, can reach the same technique effect of the present invention as the donor of lithium.
The The performance test results of table 1 composite titanic acid lithium material and the contrast of unadulterated lithium titanate
| Embodiment | Lithium salts | The coating-doping material | Prilling process | Specific discharge capacity (mAh/g) | Coulombic efficiency (%) first | 50 circulation volume conservation rates (%) | |
| 1 | Lithium carbonate | Nano graphite powder 5% | The transient state drying | 172.0 | 95.9 | 97.5 | |
| 2 | | Glucose | 10% | The transient state drying | 165.6 | 95.6 | 91.2 |
| 3 | Lithium carbonate | Nano graphite powder 1% | The transient state drying | 158.0 | 94.8 | 93.4 | |
| 4 | Lithium hydroxide | Nano graphite powder 4% | The transient state drying | 154.2 | 96.1 | 92.9 | |
| 5 | Lithium hydroxide | Nano graphite powder 4% | The transient state drying | 166.4 | 94.4 | 98.0 | |
| 6 | Lithium carbonate | Super-P5％ | The transient state drying | 166.2 | 96.1 | 95.5 | |
| 7 | Lithium carbonate | Aluminium oxide 2% | The transient state drying | 156.1 | 94.5 | 93.7 | |
| 8 | Lithium carbonate | |
The transient state drying | 156.0 | 96.8 | 94.9 | |
| Comparative Examples 1 | Lithium carbonate | Do not mix | The transient state drying | 149.6 | 92.6 | 87.8 | |
| Comparative Examples 2 | Lithium carbonate | Nano graphite powder 5% | No transient state drying | 145.1 | 91.6 | 82.7 |
Claims (12)
1. composite lithium titanate electrode material, it is characterized in that: the second particle that described composite lithium titanate electrode material is mixed and formed by lithium titanate particle, the coating of nano-sized carbon clad material or doping vario-property agent, this second particle has the microscopic feature of sphere or class sphere, comprises the porous nano passage in the particle.
2. composite lithium titanate electrode material according to claim 1 is characterized in that: described lithium titanate particle is the nano lithium titanate particle; The nano-sized carbon clad material is the cracking carbon or the Nano graphite powder of carbohydrate; The doping vario-property agent is sucrose, lactose, glucose, Nano graphite powder, conductive black, aluminium oxide, magnesium oxide, tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide or tungsten oxide.
3. composite lithium titanate electrode material according to claim 2 is characterized in that: described carbohydrate is glucose, sucrose or lactose.
4. composite lithium titanate electrode material according to claim 3 is characterized in that: described nano-sized carbon clad material shared ratio in composite lithium titanate electrode material is 1wt%～10wt%.
5. composite lithium titanate electrode material according to claim 2 is characterized in that: described doping vario-property agent proportion in composite lithium titanate electrode material is to 10wt% greater than 0.
6. according to claim 4 or 5 described composite lithium titanate electrode materials, it is characterized in that: the particle diameter of described combination electrode material is 5～50 μ m, specific area 0.5～10.0m
2/ g, tap density 0.7～1.5g/cm
3
7. the preparation method of a composite lithium titanate electrode material, may further comprise the steps:, grind dispersion with high-speed stirred or ball grinding method and made the composite lithium titanate precursor mixture in 2 to 40 hours one, in proportion with the nano-sized carbon clad material of 27.5～24.75wt% inorganic lithium salt, 72.5～65.25wt% titanium dioxide, 1wt%～10wt% or greater than 0 to 10wt% doping vario-property agent; Two, said mixture is scattered in organic solvent ethanol or the acetone, adopts the transient state drying means to make the dispersion powder; Three, will disperse powder heat treatment 4 to 40 hours in 500 to 950 ℃ temperature range; Four, naturally cool to below 150 ℃, pulverize and sieve.
8. the preparation method of composite lithium titanate electrode material according to claim 7, it is characterized in that: described ball grinding method is solid phase high-energy ball milling method or liquid phase high-energy ball milling method.
9. the preparation method of composite lithium titanate electrode material according to claim 8 is characterized in that: described employing liquid phase high-energy ball milling method, add the hot water of absolute ethyl alcohol or 60～100 ℃ during ball milling, and ball milling finishes 80～150 ℃ of oven dry.
10. the preparation method of composite lithium titanate electrode material according to claim 9; it is characterized in that: the described powder that will disperse charges into protective gas in the heat treatment process in 500 to 950 ℃ temperature range, described protective gas is nitrogen, argon gas, helium, neon, CO or CO
2Gas.
11. the preparation method of composite lithium titanate electrode material according to claim 10, it is characterized in that: described inorganic lithium salt is lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide or lithium iodide, and described titanium dioxide is technical grade titanium dioxide.
12. the preparation method of composite lithium titanate electrode material according to claim 11 is characterized in that: cracking carbon, Nano graphite powder that described nano-sized carbon clad material is a carbohydrate, carbohydrate are glucose, sucrose or lactose; The doping vario-property agent is sucrose, lactose, glucose, Nano graphite powder, conductive black, aluminium oxide, magnesium oxide, tin oxide, cupric oxide, vanadium oxide, nickel protoxide, chromium oxide or tungsten oxide.
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