CN105118978B - Preparation method of freeze-dried doped modified lithium titanate - Google Patents

Preparation method of freeze-dried doped modified lithium titanate Download PDF

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CN105118978B
CN105118978B CN201510403002.XA CN201510403002A CN105118978B CN 105118978 B CN105118978 B CN 105118978B CN 201510403002 A CN201510403002 A CN 201510403002A CN 105118978 B CN105118978 B CN 105118978B
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lithium titanate
solution
preparation
added
freeze
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CN105118978A (en
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何丹农
王丹
张春明
吴晓燕
杨扬
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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Shanghai National Engineering Research Center for Nanotechnology Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/626—Metals
    • 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

Abstract

The invention relates to a preparation method of freeze-dried doped modified lithium titanate, and provides a preparation method for improving the electron conductivity, the charge and discharge performances and the cycle performances of a lithium ion battery negative material lithium titanate. The method comprises the following steps: dissolving soluble compounds of Li and Ti in distilled water, adding chitosan to an acetate acid gracial solution, and carrying out ultrasonic dissolving to form a uniform pale yellow solution; adding titanium dioxide powder and a Yb compound to the chitosan solution, and adding epichlorohydrin; and burdening according to a Ba:Sr:Co:Fe mole ratio of 0.5:0.5:0.8:0.2, adding an ethanol and water mixed liquid, premixing a double-component chelating agent with water, adding ammonia water, refrigerating at -60DEG C, putting the refrigerated material in a lyophilizer, carrying out vacuum drying, and calcining. The lithium ion secondary battery negative material, that is modified lithium titanate Ba0.5Sr0.5Co0.2Fe0.8O3 coated Li4YbpTi5-pO12, is prepared through a freeze-drying microemulsion technology, and the material has excellent rate performances, and is suitable for being used in power batteries.

Description

A kind of preparation method of lyophilization doping vario-property lithium titanate
Technical field
The present invention relates to a kind of preparation method of battery electrode material, particularly a kind of ion secondary battery cathode material lithium The preparation method of ytterbium doping vario-property lithium titanate.
Background technology
At present, the negative material of business-like lithium ion battery adopts carbon negative pole material mostly, but carbon negative pole material is deposited In some defects：React to form surface passivated membrane with electrolyte in discharge process first, cause consumption and the head of electrolyte Secondary coulombic efficiency is relatively low；Carbon electrode is close with the electrode potential of lithium metal, in battery overcharge, it would still be possible to can be in carbon electrode table Face precipitating metal lithium, and form dendrite and cause short circuit, cause safety problem etc..
Recently, spinel type lithium titanate is excellent with " zero strain ", good cycle etc. as a kind of new negative material Point, is increasingly becoming the focus of research." zero strain " material-lithium titanate is 1.55V relative to the current potential of lithium metal, far above many The recovery voltage of number electrolyte, can avoid the reduction of electrolyte and the generation of passivating film, while the generation of lithium metal can be prevented, have There are very excellent cycle performance and security performance.But, lithium titanate is a kind of insulant, its poorly conductive, in high current Capacity attenuation is fast during discharge and recharge, high rate performance is poor, limits its application.
The present invention is directed to existing preparation Li4Ti5O12Shortcoming, the modified of excellent performance is obtained by lyophilization microemulsion legal system Lithium titanate material.
The content of the invention
To overcome the deficiencies in the prior art, the present invention to provide a kind of preparation method of lyophilization doping vario-property lithium titanate, The lithium titanate anode material for being applied to lithium ion battery is prepared by this method.
A kind of preparation method of lyophilization doping vario-property lithium titanate, it is characterised in that comprise the steps：
(1) soluble compound of Li and Ti, addition distillation water dissolution are first weighed, then weighs shitosan and be added to glacial acetic acid In solution, ultrasound is to being completely dissolved as homogeneous weak yellow liquid；
(2) compound of titania powder and Yb, ultrasound, magnetic agitation 5 minutes are added into chitosan solution；To Add in chitosan solution in the solution that step (1) has dissolved, ultrasonic agitation 5 minutes；
(3) certain epoxychloropropane, continuing magnetic force is added to stir into step (2) solution 1 ~ 3 hour；
(4) by the soluble compound of Ba, Sr, Co and Fe, according to mol ratio Ba：Sr：Co：Fe：=0.5：0.5：0.8： 0.2 carries out dispensing, adds the ethanol and water mixed liquid for preparing in advance, stirs to being completely dissolved；
(5) double-component chelating agen and water are premixed, adds ammonia all to dissolve to chelating agen after mix homogeneously, be subsequently adding The mixed liquor of step (4)；
(6) will move in culture dish after step (5) and (3) mixing, covered with preservative film, freeze at -60 DEG C, will freeze Good sample is put into freezer dryer, and evacuation is dried 24 hours, and dried sample is put into crucible, 500 under feeding tube furnace ~ 700 DEG C are calcined 8 ~ 10 hours.
Described lithium titanate material is Ba0.5Sr0.5Co0.2Fe0.8O3The Li of cladding4YbpTi5-pO12, 0.1 ＜ p in formula≤ 0.2,0.01 ＜ Ba：Li ≤0.1.
Described Yb compounds are Ytterbium(III) nitrate. or ytterbium oxide.
The lithium titanate anode material prepared using the method for the present invention shows certain mesoporous characteristic, the lithium titanate anode Material has excellent big rate discharge characteristic.
Description of the drawings
Fig. 1 schemes for the TEM of the product of the embodiment of the present invention 1.
Specific embodiment
Embodiments of the invention are elaborated below：The present embodiment is carried out under premised on technical solution of the present invention Implement, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following enforcements Example.
Embodiment 1：3.915g lithium formates are weighed, the distillation water dissolution of 10ml is added；The shitosan for weighing 1.2575g again adds Enter in the glacial acetic acid solution of 42ml, ultrasound is to being completely dissolved as homogeneous weak yellow liquid；Add into chitosan solution The Ytterbium(III) nitrate. of 4.432g titania powders and 0.0862g, ultrasound, magnetic agitation 5 minutes;Add into chitosan solution molten The lithium acetate solution for having solved, stirs 5 minutes;In the epoxychloropropane that 0.4ml is added into above-mentioned solution, continuing magnetic force stirring 1h；The ferric nitrate for separately weighing the barium nitrate of 0.1307g, 0.1058 strontium nitrate, 0.0582g cobalt nitrates and 0.1935g is matched somebody with somebody Material, be dissolved in the mixing of 30 milliliters of ethanol and 3 milliliters of water it is easy in, stir to dissolving, then by 0.2g ethylenediaminetetraacetic acid and 0.3g citric acids are added in pre- mixed metal ion solution, add ammonia to adjust pH value to 8, and this solution is molten with above It is transferred to after liquid mixing and stirring in culture dish, is covered with preservative film, freeze at -60 DEG C, the sample for freezing is put into cold Lyophilizer, evacuation is dried 24h, obtains, in spongiform white pigmented samples, sample being put at 700 DEG C of formula stove and calcining 8h, makes It is standby to obtain final product.
Embodiment 2：3.6517g lithium carbonate is weighed, the distillation water dissolution of 10ml is added；The shitosan of 1.4281g is weighed again Add in the glacial acetic acid solution of 100ml, ultrasound is to being completely dissolved as homogeneous weak yellow liquid；Add into chitosan solution The Ytterbium(III) nitrate. of 3.468g titania powders and 0.1181g, ultrasound, magnetic agitation 5 minutes;Add into chitosan solution molten The lithium acetate solution for having solved, stirs 5 minutes;In the epoxychloropropane that 0.7ml is added into above-mentioned solution, continuing magnetic force stirring 3h, the ferric nitrate for separately weighing the barium nitrate of 0.1531g, 0.1482 strontium nitrate, 0.0582g cobalt nitrates and 0.1935g is matched somebody with somebody Material, be dissolved in the mixing of 30 milliliters of ethanol and 3 milliliters of water it is easy in, stir to dissolving, then by 0.2g ethylenediaminetetraacetic acid and 0.4g citric acids are added in pre- mixed metal ion solution, add ammonia to adjust pH value to 8, and this solution is molten with above It is transferred to after liquid mixing and stirring in culture dish, is covered with preservative film, freeze at -60 DEG C, the sample for freezing is put into cold Lyophilizer, evacuation is dried 24h, obtains, in spongiform white pigmented samples, sample being put at 600 DEG C of formula stove and calcining 10h, It is prepared into final product.
Embodiment 3：4.153g lithium acetate is weighed, the distillation water dissolution of 10ml is added；The shitosan for weighing 1.0748g again adds Enter in the glacial acetic acid solution of 50ml, ultrasound is to being completely dissolved as homogeneous weak yellow liquid；Add into chitosan solution The ytterbium oxide of 3.9278g titania powders and 0.239g, ultrasound, magnetic agitation 5 minutes;Add into chitosan solution molten The lithium acetate solution for having solved, stirs 5 minutes;In the epoxychloropropane that 0.5ml is added into above-mentioned solution, continuing magnetic force stirring 2h, the ferric nitrate for separately weighing the barium nitrate of 0.1307g, 0.1058 strontium nitrate, 0.0582g cobalt nitrates and 0.2035g is matched somebody with somebody Material, be dissolved in the mixing of 30 milliliters of ethanol and 3 milliliters of water it is easy in, stir to dissolving, then by 0.3g ethylenediaminetetraacetic acid and 0.4g citric acids are added in pre- mixed metal ion solution, add ammonia to adjust pH value to 8, and this solution is molten with above It is transferred to after liquid mixing and stirring in culture dish, is covered with preservative film, freeze at -60 DEG C, the sample for freezing is put into cold Lyophilizer, evacuation is dried 24h, obtains, in spongiform white pigmented samples, sample being put at 500 DEG C of formula stove and calcining 9h, makes It is standby to obtain final product.
Embodiment 4：4.8597g Lithium Citrate des are weighed, the distillation water dissolution of 10ml is added；The shell for weighing 1.5408g again gathers Sugar is added in the glacial acetic acid solution of 80ml, and ultrasound is to being completely dissolved as homogeneous weak yellow liquid；Add into chitosan solution The ytterbium oxide of 4.551g titania powders and 0.0227g, ultrasound, magnetic agitation 5 minutes;Add into chitosan solution molten The lithium acetate solution for having solved, stirs 5 minutes;In the epoxychloropropane that 0.6ml is added into above-mentioned solution, continuing magnetic force stirring 1h, the ferric nitrate for separately weighing the barium nitrate of 0.1307g, 0.1058 strontium nitrate, 0.0612g cobalt nitrates and 0.1935g is matched somebody with somebody Material, be dissolved in the mixing of 30 milliliters of ethanol and 3 milliliters of water it is easy in, stir to dissolving, then by 0.2g ethylenediaminetetraacetic acid and 0.6g citric acids are added in pre- mixed metal ion solution, add ammonia to adjust pH value to 8, and this solution is molten with above It is transferred to after liquid mixing and stirring in culture dish, is covered with preservative film, freeze at -60 DEG C, the sample for freezing is put into cold Lyophilizer, evacuation is dried 24h, obtains, in spongiform white pigmented samples, sample being put at 700 DEG C of formula stove and calcining 10h, It is prepared into final product.

Claims (3)

1. a kind of preparation method of lyophilization doping vario-property lithium titanate, it is characterised in that comprise the steps：
(1) soluble compound of Li, addition distillation water dissolution are first weighed, then weigh shitosan and be added in glacial acetic acid solution, Ultrasound is to being completely dissolved as homogeneous weak yellow liquid；
(2) compound of titania powder and Yb, ultrasound, magnetic agitation 5 minutes are added into chitosan solution；It is poly- to shell Add in sugar juice in the solution that step (1) has dissolved, ultrasonic agitation 5 minutes；
(3) certain epoxychloropropane, continuing magnetic force is added to stir into step (2) solution 1 ~ 3 hour；
(4) by the soluble compound of Ba, Sr, Co and Fe, according to mol ratio Ba：Sr：Co：Fe：=0.5：0.5：0.8：0.2 enters Row dispensing, adds the ethanol for preparing in advance and water mixed liquid, stirs to being completely dissolved；
(5) ethylenediaminetetraacetic acid and citric acid double-component chelating agen are premixed with water, ammonia is added after mix homogeneously to chelating agen All dissolving, is subsequently adding the mixed liquor of step (4)；
(6) will move in culture dish after step (5) and (3) mixing, covered with preservative film, freeze at -60 DEG C, by what is freezed Sample is put into freezer dryer, and evacuation is dried 24 hours, and dried sample is put into crucible, sends into 500 ~ 700 under tube furnace DEG C calcining 8 ~ 10 hours.
2. a kind of preparation method of lyophilization doping vario-property lithium titanate according to claim 1, it is characterised in that described Lithium titanate material is Ba0.5Sr0.5Co0.2Fe0.8O3The Li of cladding4YbpTi5-pO12, 0.1 ＜ p≤0.2 in formula.
3. a kind of preparation method of lyophilization doping vario-property lithium titanate according to claim 1, it is characterised in that described Yb compounds are Ytterbium(III) nitrate. or ytterbium oxide.
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CN109473670A (en) * 2018-12-18 2019-03-15 上海纳米技术及应用国家工程研究中心有限公司 The preparation method and product of ion secondary battery cathode material lithium fluorine richness lithium titanate and application
CN110563031A (en) * 2019-09-16 2019-12-13 广东工业大学 Lithium titanate negative electrode material, preparation method thereof and battery
CN111092219A (en) * 2019-12-20 2020-05-01 上海纳米技术及应用国家工程研究中心有限公司 Preparation method of modified lithium titanate negative electrode material applied to lithium ion battery

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