CN102633300A - Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof - Google Patents
Carbon-coated lithium titanate cathode material as well as preparation method and applications thereof Download PDFInfo
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Abstract
The invention relates to a carbon-coated lithium titanate cathode material as well as a preparation method and applications thereof, wherein the carbon-coated lithium titanate cathode material has uniform particle sizes ( the particle size distribution range is 0.5-1.5mu m), high purity, favorable electricity conductivity performance and high-multiplying-power electricity discharge capacity, and the primary electricity discharge capacity under 0.2C multiplying power reaches 170.1mAh/g, and approaches to the theory capacity, and the capacity can still maintain 100mAh/g above under 5C high-multiplying-power electricity discharge, moreover the capacity maintaining rate after electricity charge and discharge for 25 times can be greater than 93%, and the capacity maintaining rate after electricity charge and discharge for 50 times is greater than 90%, and the carbon-coated lithium titanate cathode material has a stable and favorable cycle performance.
Description
Technical field
The invention belongs to the lithium ion battery material field, be specifically related to a kind of carbon and coat lithium titanate anode material and preparation method thereof and its application.
Background technology
Lithium ion battery is a kind of novel rechargeable cell, has high-voltage, high-energy-density, advantage such as environment friendly and pollution-free, is described as by " the most promising chemical power source ", just receives much concern once coming out.In recent years, lithium ion battery has been widely used in various portable type electronic products and the communication tool.Under the deficient day by day situation of world today's energy, national governments are stepping up exploitation with each big automobile enterprise does not have discharging, free of contamination electromobile, how to improve that the high rate performance of battery becomes new research focus in the electromobile.
Lithium ion battery mainly comprises parts such as positive pole, negative pole, barrier film, electrolytic solution and shell, and its security and high rate performance largely depend on the composition and the character of negative material.The successful commercialization of lithium ion battery is used and is mainly given the credit to the technical progress that replaces lithium anode to obtain with lithium intercalation compound.
At present, business-like lithium ion battery negative material adopts embedding lithium carbon material mostly.Carbon material have wide material sources, cheap, the charging/discharging voltage platform is low, the theoretical capacity advantages of higher, but exist first charge-discharge efficiency low, have an effect with electrolytic solution, the poor safety performance of battery, defectives such as high rate during charging-discharging is poor, cycle life is short.Therefore, searching security negative material better, that the high rate charge-discharge performance is more excellent is imperative.
1996, Canadian Studies person K.zaghib proposed first, adopted lithium titanate material to make negative pole and high-voltage anode material composition lithium ion battery, formed electrochemical capacitor with carbon electrode.Afterwards, the lot of domestic and international investigator has carried out research with it as lithium ion battery negative material.2007, Toshiba Corp announced the lithium ion battery " SCiB " of exploitation based on lithium titanate material, is intended to be applied to the hybrid power field.U.S. Enerdel company has showed hybrid vehicle lithium titanate power cell in the AABC-07 meeting.
But lithium titanate is a kind of high performance lithium ionic cell cathode material with long lifetime high current charge-discharge, safety, environmental protection, equilibrium potential height, good cycle performance, very smooth characteristics such as voltage platform; And its platform capacity surpasses 85% of total volume; Replace carbon negative pole material can fundamentally eliminate the potential safety hazard of lithium ion battery with it, make the cycle performance of lithium ion battery and fast charging and discharging performance be able to improve significantly, and the Li dendrite of having avoided the metallic lithium deposition to produce; Lithium ion is in the process that embeds and deviate from; Volume change is called " zero strain " material less than 1%, and possesses that raw material is easy to get, advantage such as preparation easily.But the specific conductivity of lithium titanate is low, and electrical capacity can not be brought into play well when high power charging-discharging, therefore, need improve its electroconductibility to its modification.
The existing preparation method of lithium titanate mainly comprises solid phase method and sol-gel method, and wherein, the product of solid phase method is relatively poor micron or a submicron powder of high-rate performance; Sol-gel method is the effective ways of preparation high-performance lithium titanate with spinel structure, and its product granularity is little, centralized particle diameter; Cycle life and high rate during charging-discharging obviously are superior to the solid state reaction product, but most employing of this method costs an arm and a leg easy and uniform dispersive titanium, lithium organic cpds; And the material system that contains organic solvent or organic crosslinking agent; So exist raw materials cost high, operational path is tediously long, is unfavorable for defectives such as industriallization conversion.CN101847717A discloses the method that solid phase method prepares lithium ion battery lithium titanate composite negative pole material, and this method is Li
2CO
3Powder and TiO
2After the powder ingredients, add alcohol furnishing pasty state, after the ball milling drying, carry out bakes to burn the article; Obtain lithium titanate material, add metallic compound again, carry out re-baking behind the ball milling; Obtain the lithium titanate composite negative pole material, the specific discharge capacity of lithium titanate composite negative pole material under the 0.5C discharge-rate that makes is 227mAh/g, reaches 161mAh/g during 5C; Showed good ground high rate charge-discharge performance, still, this method adopts twice ball milling to increase reaction mechanism; And need to add metallic compound, increased manufacturing cost.CN101172646A discloses a kind of preparation method of lithium titanate with spinel structure; This method is a raw material with the mineral compound of titanium, lithium; Organic acid or ammonium salt are coordination agent, adopt aqueous solution sol-gel method synthesized gel rubber precursor, and the gel precursor is through roasting; Making loose porous, size range is the lithium titanate with spinel structure of 0.5-10 μ m, and performance such as high-rate performance of the lithium titanate with spinel structure of gained, ohmic internal resistance all is superior to the solid state reaction product.But there is complex process in this method, and cost is high, is not suitable for defectives such as scale operation.For this reason, seek low cost of manufacture, be fit to industriallization, the method that makes the good lithium titanate of chemical property becomes the focus of present research.
Summary of the invention
The object of the present invention is to provide a kind of carbon to coat lithium titanate anode material, described lithium titanate anode material adopts a step semi-liquid phase method for mixing to prepare, and a described step semi-liquid phase batch mixing preparation method comprises the steps:
(1) lithium source, titanium source and carbon source are ground into fine powder, sieve is got particle diameter and is not higher than 300 purpose parts, takes by weighing lithium source, titanium source and the carbon source of aequum; Be placed in the shaker mixer; Vibration makes uniform raw mix, wherein to mixing; Mol ratio between titanium ion and the lithium ion is 1: 0.5-1.5, and the amount of carbon source accounts for the 1-30wt% of three kinds of raw material total amounts;
(2) raw mix that step (1) is made joins in the flocculant solution that concentration is 0.01-0.04g/ml, stirs, and makes the slurry precursor, and wherein, raw mix: the mass volume ratio between the flocculant solution is 1: 0.5-4.0;
(3) under the protection of rare gas element, the slurry precursor that step (2) is made carries out bakes to burn the article, and wherein, the temperature-rise period of bakes to burn the article does; Be warmed up to 100 ℃ with 1 ℃/min speed, constant temperature 2-6h is warming up to 500 ℃-800 ℃ again; Constant temperature 8-20h, reduce to room temperature after, pulverize; Grind, compacting is made into closely knit right cylinder;
(4) under the protection of rare gas element, the closely knit right cylinder that step (3) is made carries out re-baking, and wherein, the temperature-rise period of re-baking does, is warming up to 600-950 ℃, constant temperature 10-24h, reduce to room temperature after, pulverize, grind, promptly get.
In the optimal technical scheme of the present invention, said lithium source is selected from any or its combination of Quilonum Retard, Lithium Hydroxide MonoHydrate, Lithium Oxide 98min, Lithium Acetate, lithium iodide, lithium fluoride, is preferably any or its combination of Quilonum Retard, Lithium Hydroxide MonoHydrate.
In the optimal technical scheme of the present invention, said titanium source is selected from Detitanium-ore-type TiO
2, rutile TiO
2, amorphous TiO
2In any or its combination, be preferably Detitanium-ore-type TiO
2
In the optimal technical scheme of the present invention, said carbon source is selected from any or its combination of glucose, sucrose, lactose, Hydrocerol A, acetylene black, active carbon powder, is preferably any or its combination of Hydrocerol A, glucose.
In the optimal technical scheme of the present invention, the mol ratio between titanium ion and the lithium ion is 1: 0.7-1.2 is preferably 1: 0.8-1.0.
In the optimal technical scheme of the present invention, the amount of carbon source accounts for the 5-25% of three kinds of raw material total amounts, is preferably 10-20%.
In the optimal technical scheme of the present invention; Said flocculation agent is the macromolecular material material that its aqueous solution has certain viscosity in this area; The preferred material of forming flocculation agent is selected from any or its combination in polyoxyethylene glycol, starch, CMC 99.5, HPMC, methylcellulose gum, modified starch, the branching starch, more preferably any or its combination of polyoxyethylene glycol, starch.
In the optimal technical scheme of the present invention, raw mix: the mass volume ratio between the flocculant solution is 1: 1.0-3.5 is preferably 1: 1.5-2.0.
In the optimal technical scheme of the present invention, said rare gas element is any or its combination of nitrogen, argon gas, hydrogen, helium.
In the optimal technical scheme of the present invention, the said compaction pressure of step (3) is 50-500Mpa, is preferably 100-200Mpa.
The preparation raw material sources of carbon coating lithium titanate anode material of the present invention are extensive, cheap, environment friendly and pollution-free, carry out batch mixing No. one time through titanium source, lithium source, carbon source uniform mixing are placed on flocculant solution; Make reaction raw materials uniform mixing under the semi-liquid phase condition, the particle contact is more abundant, reacts more abundant; Significantly improve its reaction efficiency, and the particle diameter of prepared carbon coating lithium titanate anode material is even; Purity is high, and conductivity is good, and big multiplying power discharging capacity is high; Loading capacity reaches 170.1mAh/g first, and near theoretical capacity, and its capability retention after discharging and recharging through 25 times is greater than 93%; Capability retention after discharging and recharging for 50 times is greater than 90%, and capacity still can keep having stable excellent cycle performance more than the 100mAh/g under the big multiplying power discharging of 5C.A step mixing method of the present invention prepares the method that carbon coats lithium titanate anode material, has not only simplified reinforced operation, and; It is simple to have technology, easy and simple to handle, low for equipment requirements; Be fit to advantages such as industrialization, and overcome solid phase method and the existing defective of sol-gel method.
Another object of the present invention is to provide a kind of carbon to coat the lithium titanate anode preparation methods, comprise the steps:
(1) lithium source, titanium source and carbon source are ground into fine powder, sieve is got particle diameter and is not higher than 300 purpose parts, takes by weighing lithium source, titanium source and the carbon source of aequum; Be placed in the shaker mixer; Vibration makes uniform raw mix, wherein to mixing; Mol ratio between titanium ion and the lithium ion is 1: 0.5-1.5, and the amount of carbon source accounts for the 1-30wt% of three kinds of raw material total amounts;
(2) raw mix that step (1) is made joins in the flocculant solution that concentration is 0.01-0.04g/ml, stirs, and makes the slurry precursor, and wherein, raw mix: the mass volume ratio between the flocculant solution is 1: 0.5-4.0;
(3) under the protection of rare gas element, the slurry precursor that step (2) is made carries out bakes to burn the article, and wherein, the temperature-rise period of bakes to burn the article does; Be warmed up to 100 ℃ with 1 ℃/min speed, constant temperature 2-6h is warming up to 500 ℃-800 ℃ again; Constant temperature 8-20h, reduce to room temperature after, pulverize; Grind, compacting is made into closely knit right cylinder;
(4) under the protection of rare gas element, the closely knit right cylinder that step (3) is made carries out re-baking, and wherein, the temperature-rise period of re-baking does, is warming up to 600-950 ℃, constant temperature 10-24h, reduce to room temperature after, pulverize, grind, promptly get.
In the optimal technical scheme of the present invention, said lithium source is selected from any or its combination of Quilonum Retard, Lithium Hydroxide MonoHydrate, Lithium Oxide 98min, Lithium Acetate, lithium iodide, lithium fluoride, is preferably any or its combination of Quilonum Retard, Lithium Hydroxide MonoHydrate.
In the optimal technical scheme of the present invention, said titanium source is selected from Detitanium-ore-type TiO
2, rutile TiO
2, amorphous TiO
2In any or its combination, be preferably Detitanium-ore-type TiO
2
In the optimal technical scheme of the present invention, said carbon source is selected from any or its combination of glucose, sucrose, lactose, Hydrocerol A, acetylene black, active carbon powder, is preferably any or its combination of Hydrocerol A, glucose.
In the optimal technical scheme of the present invention, the mol ratio between titanium ion and the lithium ion is 1: 0.7-1.2 is preferably 1: 0.8-1.0.
In the optimal technical scheme of the present invention, the amount of carbon source accounts for the 5-25% of three kinds of raw material total amounts, is preferably 10-20%.
In the optimal technical scheme of the present invention; Said flocculation agent is the macromolecular material material that its aqueous solution has certain viscosity in this area; The preferred material of forming flocculation agent is selected from any or its combination in polyoxyethylene glycol, starch, CMC 99.5, HPMC, methylcellulose gum, modified starch, the branching starch, more preferably any or its combination of polyoxyethylene glycol, starch.
In the optimal technical scheme of the present invention, raw mix: the mass volume ratio between the flocculant solution is 1: 1.0-3.5 is preferably 1: 1.5-2.0.
In the optimal technical scheme of the present invention, said rare gas element is any or its combination of nitrogen, argon gas, hydrogen, helium.
In the optimal technical scheme of the present invention, the said compaction pressure of step (3) is 50-500Mpa, is preferably 100-200Mpa.
Another object of the present invention is to provide a kind of carbon to coat the application that lithium titanate anode material is used for preparing lithium ion battery.
The particle diameter of lithium titanate according to the invention detects and adopts the MASTERSIZER 2000 type laser particle analyzers of Britain Ma Erwen company to test, and refractive index is 2.6, and distilled water medium wet method is disperseed, ultrasonic-wave assisted dispersion.
Aspects such as the surface topography of the Japanese JSM-6700F scanning electron microscope observation sample of science of the electronic scanning of lithium titanate according to the invention micro-(SEM) test employing, particle size, emission voltage is 5KV, and powder surface is carried out vacuum metal spraying 2min.Wherein, Sem scans the high-power electron beam that gathering obtains on sample; Inspire various physical signallings; Comprise secondary electron, times scattered electrons, transmitted electron, absorption electronics, visible light and X ray etc., and the reception through these signals, amplify and be shown as picture and analytical sample, obtain the various information of sample topography.
The purity of lithium titanate according to the invention and crystalline structure detect the X-ray diffraction analysis method that adopts, and the Cu-Ka source of radiation is used in this XRD test, and Guan Liuwei 40mA, pipe press and be 40KV, 12 °/min of sweep velocity, and sweep limit 10-90 °, step-length is 0.020 °.
The charge-discharge performance test of lithium titanate according to the invention adopts LAND CT2001A battery test system that simulated battery is carried out the constant current charge-discharge test, and the voltage tester scope is 1-2.5V.The making of simulated battery comprises the steps: to coat lithium titanate, conductive carbon black, pvdf (PVDF) by certain mass than taking by weighing the carbon that makes; Active material and conductive carbon black ground in mortar it is mixed; Join in N-Methyl pyrrolidone (NMP) solution of PVDF, stir, make slurry; Again it is coated on the Copper Foil, processes pole piece through oven dry, roll extrusion.Make counter electrode with metal lithium sheet; Celgard2400 is a barrier film; 1mol/L LiPF6/EC (NSC 11801)+DMC (dimethyl carbonate)+EMC (methyl ethyl carbonate fat) (volume ratio 1: 1: 1) is an electrolytic solution, in the glove box of logical argon gas, is assembled into simulated battery, tests after leaving standstill 12h.
In order clearly to explain protection scope of the present invention, the present invention defines term as follows:
Li dendrite of the present invention is meant the lithium cell that adopts liquid electrolyte when charging, the dendritic metal lithium simple substance that the lithium ion reduction forms.
" a step semi-liquid phase hybrid system " of the present invention; Claim " a step semi-liquid phase blending means " or " a step semi-liquid phase hybrid mode " again; Be meant in the disposable flocculant solution that is distributed to certain viscosity of raw material uniform mixture of the present invention, form pasty state semi-liquid phase reaction precursor.
Flocculant solution of the present invention is meant flocculant aqueous solution; Be the aqueous solution that has the macromolecular material material of certain viscosity in this area; Wherein, the material of composition flocculation agent comprises polyoxyethylene glycol, starch, CMC 99.5, HPMC, methylcellulose gum, modified starch, branching starch etc.
Except as otherwise noted; When per-cent of the present invention is the per-cent between liquid and the liquid volume per-cent; When per-cent is the per-cent between liquid and the solid volume/weight per-cent; Be weight/volume percent when per-cent is the per-cent between solid and the liquid, all the other are weight/weight percent.
Compared with prior art, the present invention has following advantage:
1, the preparation raw material sources of carbon coating lithium titanate anode material of the present invention are extensive; Cheap, environment friendly and pollution-free, through being placed on, titanium source, lithium source, carbon source uniform mixing carry out batch mixing in the flocculant solution No. one time; Make reaction raw materials uniform mixing under the semi-liquid phase condition; The particle contact is more abundant, reacts more abundant, significantly improves its reaction efficiency.
2, the carbon that makes of the present invention particle diameter evenly (particle size distribution range is 0.5-1.5 μ m) that coats lithium titanate anode material; Purity high (purity is up to more than 99%), conductivity is good, and big multiplying power discharging capacity is high; 0.2C under the multiplying power first loading capacity reach 170.1mAh/g; Near theoretical capacity, capacity still can keep more than the 100mAh/g under the big multiplying power discharging of 5C, and its capability retention after discharging and recharging through 25 times is greater than 93%; Capability retention after discharging and recharging for 50 times has stable excellent cycle performance greater than 90%.
3, the present invention adopts a step mixing method to prepare carbon and coats lithium titanate anode material, and this method has not only been simplified reinforced operation, and it is simple to have technology; Easy and simple to handle; Low for equipment requirements, be fit to advantages such as industrialization, and overcome solid phase method and the existing defective of sol-gel method.
Description of drawings
The carbon of Fig. 1 embodiment 1 preparation coats the SEM figure (amplifying 10000 times) of lithium titanate material;
The carbon of Fig. 2 embodiment 1 preparation coats the XRD figure of lithium titanate material;
The carbon of Fig. 3 embodiment 1 preparation coats the first charge-discharge performance curve of lithium titanate material under 0.1C;
The carbon of Fig. 4 embodiment 1 preparation coats the cycle performance curve of lithium titanate material under 5C.
Embodiment
Below will combine embodiment to specify the present invention, embodiments of the invention only are used to technical scheme of the present invention is described, and non-limiting essence of the present invention.
Embodiment 1Carbon of the present invention coats the preparation of lithium titanate anode material
Carbon of the present invention coats the lithium titanate anode preparation methods, comprises the steps:
(1) with Detitanium-ore-type TiO
2, Quilonum Retard becomes fine powder with the glucose pulverize separately, cross 300 mesh sieves after, take by weighing 400g Detitanium-ore-type TiO
2, 155.4g Quilonum Retard and 27.8g glucose, be placed in the shaker mixer, vibration makes the raw mix that mixes to mixing;
(2) raw mix that step (1) is obtained joins in the polyoxyethylene glycol aqueous solution that 1000ml concentration is 0.02g/ml, is stirred to mix, and makes the slurry precursor;
(3) under protection of nitrogen gas, the slurry precursor that step (2) is made carries out bakes to burn the article, wherein; The temperature-rise period of bakes to burn the article is to be warmed up to 100 ℃ with 1 ℃/min speed, constant temperature 4h; Be warming up to 600 ℃ of constant temperature 12h again, reduce to room temperature after, pulverize, grind; Under 100Mpa pressure, it is pressed into closely knit right cylinder;
(4) under protection of nitrogen gas, the closely knit right cylinder that step (3) is made carries out re-baking, and wherein, the temperature-rise period of re-baking does, is warming up to 900 ℃ of constant temperature 16h, reduce to room temperature after, pulverize, grind, cross 300 mesh sieves, promptly get carbon coating lithium titanate anode material.
According to detection method of the present invention; The carbon of test implementation example 1 preparation coats the SEM, XRD of lithium titanate material, at the first charge-discharge performance curve under 0.1C and the 0.2C, the cycle performance curve under 5C, particle diameter, purity, 25 times and 50 circulation volume conservation rates, the result sees Fig. 1-Fig. 4 and table 1.And, can find out that by XRD figure the peak shape of each diffraction peak is sharp-pointed, corresponding one by one with each diffraction peak of standard card (PDF49-0207), and do not have impurity peaks.
Embodiment 2Carbon of the present invention coats the preparation of lithium titanate anode material
Carbon of the present invention coats the lithium titanate anode preparation methods, comprises the steps:
(1) with amorphous TiO
2, Quilonum Retard becomes fine powder with the glucose pulverize separately, cross 300 mesh sieves after, take by weighing the amorphous TiO of 400g
2, 155.4g Quilonum Retard and 55.5g glucose are placed in the shaker mixer, and vibration makes the raw mix that mixes to mixing;
(2) mixture that step (1) is obtained joins in the polyoxyethylene glycol aqueous solution that 1000ml concentration is 0.02g/ml, is stirred to mix, and makes the slurry precursor;
(3) under nitrogen protection, the slurry precursor that step (2) is made carries out bakes to burn the article, is warmed up to 100 ℃ with 1 ℃/min speed; Constant temperature 4h is warming up to 600 ℃ of constant temperature 12h again, reduce to room temperature with stove after; Take out to pulverize and grind, under 100Mpa pressure, it is pressed into closely knit right cylinder;
(4) under nitrogen protection, the closely knit right cylinder that step (3) is obtained carries out re-baking, 900 ℃ of constant temperature 16h, reduce to room temperature after, pulverize, grind, product is crossed 300 mesh sieves, promptly get carbon coating lithium titanate anode material.
According to detection method of the present invention, the carbon of test implementation example 2 preparations coats particle diameter, purity, 0.2C first discharge specific capacity (mAh/g), 25 times and 50 circulation volume conservation rates of lithium titanate material, and the result sees table 1.
Embodiment 3Carbon of the present invention coats the preparation of lithium titanate anode material
Carbon of the present invention coats the lithium titanate anode preparation methods, comprises the steps:
(1) with rutile TiO
2, Quilonum Retard becomes fine powder with the Hydrocerol A pulverize separately, cross 300 mesh sieves after, take by weighing the 400g rutile TiO
2, 155.4g Quilonum Retard and 27.8g Hydrocerol A, be placed in the shaker mixer, vibration 2h mixes, and makes the raw mix that mixes;
(2) raw mix that step (1) is obtained joins in the polyoxyethylene glycol aqueous solution that 1000ml concentration is 0.02g/ml, is stirred to the mixing mixing, forms the slurry precursor;
(3) under nitrogen protection, the slurry precursor that step (2) is made carries out bakes to burn the article, is warmed up to 100 ℃ with 1 ℃/min speed; Constant temperature 4h is warming up to 600 ℃ of constant temperature 12h again, reduce to room temperature with stove after; Take out to pulverize and grind, under 100Mpa pressure, it is pressed into closely knit right cylinder;
(4) under nitrogen protection, the closely knit right cylinder that step (3) is obtained carries out re-baking, 900 ℃ of constant temperature 16h, reduce to room temperature after, pulverize, grind, product is crossed 300 mesh sieves, promptly get carbon coating lithium titanate anode material.
According to detection method of the present invention, the carbon of test implementation example 3 preparations coats particle diameter, purity, 0.2C first discharge specific capacity (mAh/g), 25 times and 50 circulation volume conservation rates of lithium titanate material, and the result sees table 1.
Embodiment 4Carbon of the present invention coats the preparation of lithium titanate anode material
Carbon of the present invention coats the lithium titanate anode preparation methods, comprises the steps:
(1) with Detitanium-ore-type TiO
2, Quilonum Retard becomes fine powder with the Hydrocerol A pulverize separately, cross 300 mesh sieves after, take by weighing 400g Detitanium-ore-type TiO
2, 155.4g Quilonum Retard and 55.5g Hydrocerol A are placed in the shaker mixer, and vibration 2h mixes, and makes the raw mix that mixes;
(2) raw mix that step (1) is obtained joins in the amidin that 1000ml concentration is 0.02g/ml, is stirred to mix, and makes the slurry precursor;
(3) under nitrogen protection, the slurry precursor that step (2) is made carries out bakes to burn the article, is warmed up to 100 ℃ with 1 ℃/min speed, constant temperature 4h; Be warming up to 600 ℃ of constant temperature 12h again, reduce to room temperature after, pulverize; Grind, under 100Mpa pressure, it is pressed into closely knit right cylinder;
(4) under nitrogen protection, the closely knit right cylinder that step (3) is obtained carries out re-baking, 900 ℃ of constant temperature 16h, reduce to room temperature after, pulverize, grind, cross 300 mesh sieves, promptly get carbon coating lithium titanate anode material.
According to detection method of the present invention, the carbon of test implementation example 4 preparations coats the circulation volume conservation rate of the particle diameter of lithium titanate material, purity, 0.2C first discharge specific capacity (mAh/g), 25 times and 50 times, and the result sees table 1.
Comparative Examples 1
Carbon coats the lithium titanate anode preparation methods, comprises the steps:
(1) took by weighing respectively the 400g Detitanium-ore-type TiO that crosses behind 300 mesh sieves
2, 155.4g Quilonum Retard and 27.8g Hydrocerol A are placed in the shaker mixer, and vibration 2h mixes;
(2) under nitrogen protection, the mixture that step (1) is obtained carries out bakes to burn the article, is warmed up to 100 ℃ with 1 ℃/min speed; Constant temperature 4h is warming up to 600 ℃ of constant temperature 12h again, reduce to room temperature with stove after; Take out to pulverize and grind, depress to closely knit right cylinder at 100Mpa pressure;
(3) under nitrogen protection, the right cylinder that step (2) is obtained carries out re-baking, 900 ℃ of constant temperature 16h, reduce to room temperature with stove after, pulverize and grind, product is crossed 300 mesh sieves, promptly get carbon coating lithium titanate anode material.
According to detection method of the present invention, the carbon of test comparison example 1 preparation coats the circulation volume conservation rate of the particle diameter of lithium titanate material, purity, 0.2C first discharge specific capacity (mAh/g), 25 times and 50 times, and the result sees table 1.
Comparative Examples 2
The preparation method of lithium titanate anode material comprises the steps:
(1) took by weighing respectively the 400g Detitanium-ore-type TiO that crosses behind 300 mesh sieves
2, the 155.4g Quilonum Retard is placed in the shaker mixer, and vibration 2h mixes;
(2) mixture that step (1) is obtained joins in the flocculation agent polyoxyethylene glycol aqueous solution that concentration is 0.02g/ml, and mechanical stirring forms the slurry precursor;
(3) under nitrogen protection, the slurry precursor that step (2) is made carries out bakes to burn the article, is warmed up to 100 ℃ with 1 ℃/min speed; Constant temperature 4h is warming up to 600 ℃ of constant temperature 12h again, reduce to room temperature with stove after; Take out to pulverize and grind, depress to closely knit right cylinder at 100Mpa pressure;
(4) under nitrogen protection, the right cylinder that step (3) is obtained carries out re-baking, 900 ℃ of constant temperature 16h, reduce to room temperature with stove after, pulverize and grind, product is crossed 300 mesh sieves and promptly get carbon coating lithium titanate anode material.
According to detection method of the present invention, the carbon of test comparison example 2 preparations coats the circulation volume conservation rate of the particle diameter of lithium titanate material, purity, 0.2C first discharge specific capacity (mAh/g), 25 times and 50 times, and the result sees table 1.
Embodiment 5Electro-chemical test
The material that embodiment 1-4 and Comparative Examples 1-2 are made is assembled into battery, carries out electro-chemical test.Wherein, Take by weighing the carbon that makes at 82: 10: 8 by mass ratio and coat lithium titanate, conductive carbon black, PVDF, active material (lithium titanate that embodiment 1-4 and Comparative Examples 1-2 make) and conductive carbon black are ground in mortar it is mixed, join in the nmp solution of PVDF; Stir; Make slurry, again it is coated on the Copper Foil, process pole piece through oven dry, roll extrusion.Make counter electrode with metal lithium sheet, Celgard2400 is a barrier film, 1mol/L LiPF
6/ EC+DMC+EMC (volume ratio 1: 1: 1) is an electrolytic solution, in the glove box of logical argon gas, is assembled into simulated battery, leaves standstill 12h.
At ambient temperature, under 0.2C, 5C discharge-rate, carry out the constant current charge-discharge test, voltage range is 1.0-2.5V, and the result sees table 1.
Make the test result contrast that carbon coats lithium titanate material under table 1 different condition
Visible by table 1, the particle diameter of the carbon coating lithium titanate anode material that the present invention's one step method for mixing makes is even, and its particle size distribution range is 0.5-1.5 μ m, has improved the chemical property of material; Purity high (purity is up to more than 99%); Conductivity is good, and big multiplying power discharging capacity is high, under the 0.2C multiplying power first loading capacity reach 170.1mAh/g; Near theoretical capacity; And the capability retention after the capability retention after it discharges and recharges through 25 times discharges and recharges greater than 93%, 50 time has stable excellent cycle performance greater than 90%.The present invention adopts a step mixing method to prepare the method that carbon coats lithium titanate anode material, not only simplified reinforced operation, and it is simple to have technology, and is easy and simple to handle, low for equipment requirements, is fit to advantages such as industrialization.
Claims (12)
1. a carbon coats the lithium titanate anode preparation methods, comprises the steps:
(1) lithium source, titanium source and carbon source are ground into fine powder, sieve is got particle diameter and is not higher than 300 purpose parts, takes by weighing lithium source, titanium source and the carbon source of aequum; Be placed in the shaker mixer; Vibration makes uniform raw mix, wherein to mixing; Mol ratio between titanium ion and the lithium ion is 1: 0.5-1.5, and the amount of carbon source accounts for the 1-30wt% of three kinds of raw material total amounts;
(2) raw mix that step (1) is made joins in the flocculant solution that concentration is 0.01-0.04g/ml, stirs, and makes the slurry precursor, and wherein, raw mix: the mass volume ratio between the flocculant solution is 1: 0.5-4.0;
(3) under the protection of rare gas element, the slurry precursor that step (2) is made carries out bakes to burn the article, and wherein, the temperature-rise period of bakes to burn the article does; Be warmed up to 100 ℃ with 1 ℃/min speed, constant temperature 2-6h is warming up to 500 ℃-800 ℃ again; Constant temperature 8-20h, reduce to room temperature after, pulverize; Grind, compacting is made into closely knit right cylinder;
(4) under the protection of rare gas element, the closely knit right cylinder that step (3) is made carries out re-baking, and wherein, the temperature-rise period of re-baking does, is warming up to 600-950 ℃, constant temperature 10-24h, reduce to room temperature after, pulverize, grind, promptly get.
2. preparation method according to claim 1; Wherein, Said lithium source described in the step (1) is selected from any or its combination of Quilonum Retard, Lithium Hydroxide MonoHydrate, Lithium Oxide 98min, Lithium Acetate, lithium iodide, lithium fluoride, is preferably any or its combination of Quilonum Retard, Lithium Hydroxide MonoHydrate.
3. according to each described preparation method of claim 1-2, wherein, the said titanium source described in the step (1) is selected from Detitanium-ore-type TiO
2, rutile TiO
2, amorphous TiO
2In any or its combination, be preferably Detitanium-ore-type TiO
2
4. according to each described preparation method of claim 1-3; Wherein, Said carbon source described in the step (1) is selected from any or its combination of glucose, sucrose, lactose, Hydrocerol A, acetylene black, active carbon powder, is preferably any or its combination of Hydrocerol A, glucose.
5. according to each described preparation method of claim 1-4, wherein, titanium ion described in the step (1) and the mol ratio between the lithium ion are 1: 0.7-1.2 is preferably 1: 0.8-1.0.
6. according to each described preparation method of claim 1-5, wherein, the amount of the carbon source described in the step (1) accounts for the 5-25% of three kinds of raw material total amounts, is preferably 10-20%.
7. according to each described preparation method of claim 1-6; Wherein, Said flocculation agent described in the step (2) is the macromolecular material material that its aqueous solution has certain viscosity in this area; The preferred material of forming flocculation agent is selected from any or its combination in polyoxyethylene glycol, starch, CMC 99.5, HPMC, methylcellulose gum, modified starch, the branching starch, more preferably any or its combination of polyoxyethylene glycol, starch.
8. according to each described preparation method of claim 1-7, wherein, the raw mix described in the step (2): the mass volume ratio between the flocculant solution is 1: 1.0-3.5 is preferably 1: 1.5-2.0.
9. according to each described preparation method of claim 1-8, wherein, the said rare gas element described in step (3) or the step (4) is appointing of nitrogen, argon gas, hydrogen, helium
1A kind of or its combination.
10. according to each described preparation method of claim 1-9, wherein, the said compaction pressure described in the step (3) is 50-500Mpa, is preferably 100-200Mpa.
11. a carbon coats lithium titanate anode material, is prepared by each described preparation method of claim 1-10.
12. the carbon that each described preparation method of claim 1-10 prepares coats the application that lithium titanate anode material is used for preparing lithium ion battery.
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| CN102916170A (en) * | 2012-11-01 | 2013-02-06 | 多氟多化工股份有限公司 | Method for preparing carbon-coated nano-particle lithium titanate electrode material |
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