CN104269524A - Preparation and application of phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12 - Google Patents

Preparation and application of phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12 Download PDF

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CN104269524A
CN104269524A CN201410522892.1A CN201410522892A CN104269524A CN 104269524 A CN104269524 A CN 104269524A CN 201410522892 A CN201410522892 A CN 201410522892A CN 104269524 A CN104269524 A CN 104269524A
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李宏斌
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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
    • H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
    • H01M4/139—Processes of manufacture
    • 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
    • H01M4/362—Composites
    • 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
    • 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
    • H01M4/625—Carbon or graphite
    • 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 discloses preparation and application of aluminium-phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12. The preparation method for the aluminium-phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12 comprises the following steps: firstly, preparing spinel type rare-earth-doped Li4Ti5O12, and then preparing spinel type carbon-cladded rare-earth-doped Li4Ti5O12 to obtain spinel type carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12; and uniformly cladding the surface of the obtained spinel type carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12 with a layer of aluminium phosphate to obtain the aluminium-phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12. The preparation process of the preparation method disclosed by the invention is simple, the equipment requirements are low, no pollution is reaction is achieved, the product homogeneity is good, and the prepared aluminium-phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12 has is high in gram volume, good in circulation rate performance and safety performance, and has a good industrial application prospect.

Description

The preparations and applicatio of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating
Technical field
The invention belongs to field of nanometer material technology, be specifically related to the preparations and applicatio of the coated lithium titanate of the rear-earth-doped carbon of nitrogenize of Phosphate coating.
Background technology
Lithium titanate with spinel structure (Li 4ti 5o 12) lithium rechargeable battery made as negative pole has the features such as long-life, high magnification, high-low temperature resistant and fail safe are good, the application prospect that pure electric bus (EV), hybrid vehicle (HEV) and energy storage have had.
But Li 4ti 5o 12self-conductive rate about 10 -13s/cm, belongs to insulator, and therefore improving lithium titanate conductivity needs to modify or modification lithium titanate 1.
Titanium nitride TiN has good electric conductivity, and primarily of ionic bond, covalent bond and metallic bond mixing composition, 20 DEG C time, its conductance is 8.7 μ Sm -1(not fear, Deng Guozhu, Luo Fangcheng. titanium is metallurgical. Beijing: metallurgical industry publishing house, 1998:97-99).Doped titanium nitride structure or in the coated titanium nitride of lithium titanate particle surface lithium titanate crystal structure, can increase lithium titanate conductivity, improves high rate performance.
Carbon is coated is a kind of method of conventional raising electrode material conductivity.
In lithium titanate with spinel structure crystal, containing transition metal atom can improve conductivity (the Preparation and characterization of W-doped Li of lithium titanate crystal 4ti 5o 12anodematerial for enhancing the high rate performance, Qianyu Zhanga, Chengli Zhanga, Bo Lia, Dongdong Jiangc, Shifei Kanga, Xi Lia, Yangang Wang, Electrochimica Acta, 107,2013,139 – 146).
Although lithium titanate does not generate solid electrolyte film (Solid Electrolyte Interface, SEI) as negative pole in electrochemical reaction process.In charging process, Li 4ti 5o 12crystal embeds 3 lithium ions, generates blue Li 7ti 5o 12crystal structure, is not overcharging under condition, and impossible precipitating metal Li dendrite, has good fail safe in theory.
But in actual application, lithium titanate battery is overcharging under condition, also there will be the precipitation of negative metal lithium and phenomenon on fire of smoldering.Therefore, improving the fail safe of lithium titanate anode material is an important research topic.
Adopt Phosphate coating battery plus-negative plate material can reduce hexafluorophosphate (LiPF in electrolyte 6) decompose hydrofluoric acid (HF) concentration produced, reduce the dissolved corrosion side reaction to positive electrode.Meanwhile, in phosphate radical polyanion, phosphorus oxygen is two strong very stable, can the stability of guard electrode material in electrochemical reaction process.
The at high temperature pyrolysis of Nitrogen element ionic liquid can generate carbonitride CN x.
The people such as Paraknowitsch adopt the ionic liquid 1-ethyl-3-methylimidazole dintrile amine salt (C of hydrogeneous, carbon and nitrogen 8h 11n 5) and 1-butyl-3-methvl-pyridinium dintrile amine salt (C 12h 16n 4) calcining rear generation N doping RESEARCH OF PYROCARBON, by measuring conductivity, the N doping RESEARCH OF PYROCARBON of generation has high conductivity, and has non-oxidizability (Jens Peter Paraknowitsch, Jian Zhang, Dangsheng Su, Arne Thomas, and Markus Antonietti, Ionic Liquids as Precursors for Nitrogen-Doped Graphitic Carbon, Adv.Mater.2010,22,87 – 92).
Up to the present, the method preparing the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating have not been reported.
Summary of the invention
In order to improve conductivity and the fail safe of lithium titanate material simultaneously, the present invention proposes the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating, and rear-earth-doped for coated for the carbon of prepared Phosphate coating nitrogenize metatitanic acid lithium is applied in ion secondary battery cathode material lithium.
The present invention adopts following technical scheme:
The preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating, its special character is: comprise the following steps:
1) titanium dioxide, lithium carbonate and rare-earth salts are mixed, be placed in vacuum or protective gas atmosphere is calcined, cooling, obtains spinel structure rear-earth-doped metatitanic acid lithium naturally; The mol ratio of the rare earth element in described rare-earth salts and the titanium elements in titanium dioxide is 1 ~ 10:100;
2) by carbon source and the mixing of rear-earth-doped metatitanic acid lithium, calcine in vacuum or protective gas atmosphere, naturally cool, obtain the coated rear-earth-doped metatitanic acid lithium of carbon;
3) by nitrogenous source and the coated rear-earth-doped metatitanic acid lithium mixing of carbon, calcine in vacuum or protective gas atmosphere, make the nitrogen element of rear-earth-doped metatitanic acid lithium surface portion and titanium elements form titanium nitrogen bond TiN, naturally cool, obtain the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon; The rear-earth-doped metatitanic acid lithium of nitrogenize is expressed as Li 4ti 5-xm xo 12/ TiN, M are doped with rare-earth elements, 0≤x≤1;
4) coated for carbon rare earth nitrogenize doped lithium titanate even particulate dispersion is become suspension-turbid liquid; aluminium salt and phosphate is added in suspension-turbid liquid; the aluminum phosphate generated evenly is coated on the coated nitrogenize of carbon rear-earth-doped metatitanic acid lithium particle surface; filtering solution; coated for carbon coated for aluminum phosphate nitrogenize rear-earth-doped metatitanic acid lithium particle is placed in vacuum or protective gas atmosphere is calcined; naturally cool; obtain the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the coated carbon of aluminum phosphate, wherein phosphate and the coated rear-earth-doped nitrogenize lithium titanate mass percent of carbon are 0.1 ~ 20:100.
Above-mentioned titanium dioxide crystal form is rutile-type, Detitanium-ore-type, brookite type or unformed;
Described rare-earth salts comprises lanthanide rare salt, and described lanthanide rare salt comprises one or more in group of the lanthanides sulfate, nitrate, carbonate, chlorate and acetate;
Described carbon source comprises one or more in pitch, starch, glucose, maltose, citric acid, cyclodextrin, acetate fiber, epoxy resin, phenolic resins, Lauxite, furfural resin, polyvinyl alcohol and polyvinylidene;
Described nitrogenous source comprise urea, contracting two urine, acetonitrile, cyanamide, cyanamid dimerization, melamine and Nitrogen element ionic liquid in one or more;
Described protective gas is one or more in nitrogen, helium and argon gas;
Described aluminium salt be aluminum sulfate, aluminum nitrate and aluminum acetate one or more.
Above-mentioned Nitrogen element ionic liquid comprises imidazoles, pyridines, quaternary amines, pyrrolidines, piperidines He one or more in quaternary phosphine class; Described imidazoles is one or both in disubstituted imidazole class and tri-substituted imidazole class; Described pyridines is one or both in disubstituted pyridines class and three substituted-pyridines; Described functionalized ion liquid is one or more in N-alkyl imidazole, functional amido class, sulfonic acid funtionalized class, hydroxy functionalized class, cyano group functionalization class, thiazolinyl functionalization class, ether functionalization class, benzyl functionalization class, carboxyl-functional class, ester group functionalization class and guanidine class ionic liquid.
Above-mentioned steps 4) suspension-turbid liquid solvent is the mixed solution of water and alcohol; Described alcohol comprises one or more in ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol and ethylene glycol, and the volume ratio of described water and alcohol is 100 ~ 40:1 ~ 60.
Above-mentioned steps 1) calcination condition be: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature; and then continue to be warmed up to 500 ~ 950 DEG C with the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
Above-mentioned steps 2) calcination condition is: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature; and then continue to be warmed up to 500 ~ 950 DEG C with the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
Above-mentioned steps 3) calcination condition is: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
Above-mentioned steps 4) calcination condition is: in vacuum or protective gas atmosphere; 300 ~ 800 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 5 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
The application of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon in ion secondary battery cathode material lithium of the Phosphate coating prepared by said method.
A kind of structure of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating, its special character is: comprise kernel coated successively from the inside to the outside, the first coating layer, the second coating layer, described kernel is the rear-earth-doped lithium titanate that surface distributed has titanium nitride, described first coating layer is carbon coating layer or the carbon coating layer containing carbonitride, and described second coating layer is phosphate.
The invention has the beneficial effects as follows:
1, the present invention is the preparation method that ion secondary battery cathode material lithium adds that a kind of new material provides this material simultaneously, and this obtained material has high gram volume, circulation ratio performance and security performance.
2, first the present invention prepares the lithium titanate that rare earth ion 2 adulterates, prepare the coated rear-earth-doped metatitanic acid lithium of carbon again, then the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon is prepared, prepare the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating again, preparation process is simple, equipment requirement is low, course of reaction is pollution-free, product uniformity is good, the coated nitrogenize of the carbon rear-earth-doped metatitanic acid lithium of the Phosphate coating prepared has high gram volume, circulation ratio performance and security performance, has good prospects for commercial application.
3, the present invention is when selecting carbon containing and nitrogen element ion liquid as nitrogenous source, and the carbon coating layer of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of Formed contains carbon and carbonitride (CN x) compound, and carbonitride (CN x) compound has high conductivity, makes the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon can obtain application in high current charge-discharge.
Accompanying drawing explanation
Fig. 1 is the XRD figure of the coated coated cerium nitride doped lithium titanate of carbon of spinel-type aluminum phosphate that embodiment 1 step 4 generates;
Fig. 2 is the XRD figure of the coated carbon coated nitrogenize La doped lithium titanate of spinel-type aluminum phosphate that embodiment 2 step 4 generates;
Fig. 3 is the SEM figure of the coated carbon coated cerium nitride doped titanic acid lithium powder of spinel-type aluminum phosphate that embodiment 1 step 4 generates;
Fig. 4 is the X-ray energy scattering EDS spectrum of the coated carbon coated cerium nitride doped titanic acid lithium powder of spinel-type aluminum phosphate that embodiment 1 step 4 generates;
Fig. 5 is the SEM figure of the coated carbon coated nitrogenize La doped lithium titanate of spinel-type aluminum phosphate that embodiment 2 step 4 generates;
Fig. 6 is the X-ray energy scattering EDS spectrum of the coated carbon coated nitrogenize La doped lithium titanate powder of spinel-type aluminum phosphate that embodiment 2 step 4 generates;
Fig. 7 is the electrochemistry cyclic voltammetry curve figure of the coated carbon coated nitrogenize La doped lithium titanate of spinel structure aluminum phosphate that embodiment 2 prepares;
Fig. 8 is the structural representation of the coated rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of aluminum phosphate that the present invention generates, wherein 1-lithium titanate, 2-rare earth ion, 3-titanium nitride, 4-RESEARCH OF PYROCARBON, 5-carbonitride, 6-aluminum phosphate.
Embodiment
Below in conjunction with specific embodiment, the present invention is further illustrated, but the present invention is not limited thereto.
Embodiment raw materials, is analysis pure, content >=99.9%.
Embodiment 1
The preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon of Phosphate coating, comprises the following steps:
Step 1): the preparation of cerium dopping lithium titanate
Lithium carbonate 3.8 grams, rutile titanium dioxide 5 grams and six water cerous nitrates 0.55 gram are taken by Li:Ti:Ce mol ratio 4:4.9:0.1, with 20 milliliters of absolute ethyl alcohol mixing, add agate abrading-ball 300 grams, be placed in Nanjing Univ. Instrument Factory QM-2SP12 type ball mill argon gas atmosphere, rotating speed 300rpm, ball milling 2 hours.
The sample mixed is placed in vacuum drying oven, and under 80 DEG C of conditions, heating, drying 15 hours, vacuum cooled is to room temperature.Sample is placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then be warmed up to 500 DEG C with the speed of 5 DEG C/min, and keep 1 hour at this temperature, and then continue to be warmed up to 850 DEG C with the speed of 2 DEG C/min; and keep 1 hour at this temperature; naturally, after cooling, stop passing into nitrogen, obtain faint yellow cerium dopping lithium titanate powder.
Step 2): the preparation of the coated cerium dopping lithium titanate of carbon
Cerium dopping lithium titanate powder step 1 prepared and glucose is 100:10 Homogeneous phase mixing in mass ratio, and grinding evenly.Uniform for grinding blend sample is placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then be warmed up to 450 DEG C with the speed of 5 DEG C/min, and keep 1 hour at this temperature, and then continue to be warmed up to 900 DEG C with the speed of 2 DEG C/min; and keep 2 hours at this temperature; naturally, after cooling, stop passing into nitrogen, obtain the coated cerium dopping lithium titanate powder of black carbon.
Step 3): the preparation of the coated cerium nitride doped lithium titanate of carbon
The coated cerium dopping lithium titanate particle of carbon step 2 prepared 6.46 grams is 5:100 and 0.323 gram of urea mixing by mass percentage, puts into crucible after grinding evenly.Blend sample will be mixed and be placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then 500 DEG C are warmed up to the speed of 5 DEG C/min; and keep 1 hour at this temperature; and then continue to be warmed up to 850 DEG C with the speed of 2 DEG C/min; and keep 30 minutes at this temperature; the nitrogen element of rear-earth-doped metatitanic acid lithium surface portion and titanium elements is made to form titanium nitrogen bond TiN (titanium nitride 3); naturally after cooling; stop passing into nitrogen, obtain black carbonitride coated cerium dopping nitrogenize lithium titanate powder.The chemical constituent of carbon coating layer is RESEARCH OF PYROCARBON 4.
Step 4): the preparation of the coated cerium nitride doped lithium titanate of carbon that aluminum phosphate is coated
Carbonitride step 3 prepared coated cerium dopping nitrogenize lithium titanate 3 grams, adds 20 ml waters and 20 milliliters of absolute ethyl alcohols, ultrasonic disperse 30 minutes, forms suspension-turbid liquid.
By 0.184 gram of ANN aluminium nitrate nonahydrate (AlPO 4covering amount 2% mass ratio), soluble in water, add suspension-turbid liquid under vigorous stirring, continue ultrasonic disperse 20 minutes.
Claim 0.065 gram of diammonium hydrogen phosphate, soluble in water, dropwise add suspension-turbid liquid under vigorous stirring, continue ultrasonic 20 minutes, then suction filtration, solid 80 DEG C of dryings 16 hours under vacuo.Vacuum cooled is to room temperature.
By dried particle Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then 350 DEG C are warmed up to the speed of 5 DEG C/min; and keep 3 hours at this temperature; naturally, after cooling, stop passing into nitrogen, obtain the coated carbon of grey aluminum phosphate coated cerium nitride doped lithium titanate particle.
Embodiment 2
The reaction environment of embodiment 2 and condition are with embodiment 1.
Difference is, rare-earth salts adopts lanthanum nitrate.
Step 1): the preparation of La doped lithium titanate
Lithium carbonate 3.8 grams, rutile titanium dioxide 5 grams and six water cerous nitrates 0.55 gram are taken by Li:Ti:La mol ratio 4:4.9:0.1, with 20 milliliters of absolute ethyl alcohol mixing, add agate abrading-ball 300 grams, be placed in Nanjing Univ. Instrument Factory QM-2SP12 type ball mill argon gas atmosphere, rotating speed 300rpm, ball milling 2 hours.
To mix sample and be placed in vacuum drying oven 80 DEG C, heating, drying 15 hours, vacuum cooled is to room temperature.Sample is placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then be warmed up to 500 DEG C with the speed of 5 DEG C/min, and keep 1 hour at this temperature, and then continue to be warmed up to 850 DEG C with the speed of 2 DEG C/min; and keep 1 hour at this temperature; naturally, after cooling, stop passing into nitrogen, obtain white La doped lithium titanate powder.
Step 2): the preparation of the coated La doped lithium titanate of carbon
La doped lithium titanate powder step 1 prepared and glucose is 100:10 Homogeneous phase mixing in mass ratio, and grinding evenly.Uniform for grinding blend sample is placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then be warmed up to 450 DEG C with the speed of 5 DEG C/min, and keep 1 hour at this temperature, and then continue to be warmed up to 900 DEG C with the speed of 2 DEG C/min; and keep 2 hours at this temperature; naturally, after cooling, stop passing into nitrogen, obtain the coated La doped lithium titanate powder of black carbon.
Step 3): the preparation of carbon coated nitrogenize La doped lithium titanate
The coated La doped lithium titanate particle of carbon step 2 prepared 6.46 grams 5:100 by mass percentage, and 0.323 gram of urea mixing, put into crucible after grinding evenly.Blend sample will be mixed and be placed in Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then 500 DEG C are warmed up to the speed of 5 DEG C/min; and keep 1 hour at this temperature; and then continue to be warmed up to 850 DEG C with the speed of 2 DEG C/min; and keep 30 minutes at this temperature; the nitrogen element of rear-earth-doped metatitanic acid lithium surface portion and titanium elements is made to form titanium nitrogen bond TiN (titanium nitride 3); naturally after cooling; stop passing into nitrogen, obtain black carbonitride coated La doped nitrogenize lithium titanate powder.The chemical constituent of carbon coating layer is RESEARCH OF PYROCARBON.
Step 4): the preparation of the carbon coated nitrogenize La doped lithium titanate that aluminum phosphate is coated
Carbonitride step 3 prepared coated La doped nitrogenize lithium titanate 3 grams, adds 20 ml waters and 20 milliliters of absolute ethyl alcohols, ultrasonic disperse 30 minutes, forms suspension-turbid liquid.
By 0.184 gram of ANN aluminium nitrate nonahydrate (AlPO4 covering amount 2% mass ratio), soluble in water, add suspension-turbid liquid under vigorous stirring, continue ultrasonic disperse 20 minutes.
Claim 0.065 gram of diammonium hydrogen phosphate, soluble in water, dropwise add suspension-turbid liquid under vigorous stirring, continue ultrasonic 20 minutes, then suction filtration, solid 80 DEG C of dryings 16 hours under vacuo, vacuum cooled is to room temperature.
By dried particle Shanghai Jiu Gong Electrical Appliances Co., Ltd high-temperature atmosphere electric furnace; vacuumize; logical 99.9% nitrogen protection gas; then 350 DEG C are warmed up to the speed of 5 DEG C/min; and keep 3 hours at this temperature; naturally, after cooling, stop passing into nitrogen, obtain the coated carbon of grey aluminum phosphate 6 coated nitrogenize La doped lithium titanate powder.
Embodiment 3
The reaction environment of embodiment 3 and condition are with embodiment 1.
Ionic liquid 1-butyl-pyridinium dintrile amine salt (C is adopted unlike nitrogenous source 11h 14n 4).
Prepare the coated carbon of grey aluminum phosphate coated cerium nitride doped lithium titanate particle, carbon coating layer contains the carbonitride 5 (CN generated in nitrogen element and carbon pyrolytic process in ionic liquid x).
Material property characterizes
1) crystal structure test is carried out on Japanese Shimadzu X-ray diffractometer XRD-7000, adopts copper target, sweep speed 2 °/minute, measuring accuracy ± 0.04 °, sweep limits 5 ~ 90 °.
The carbon coated cerium nitride doped lithium titanate XRD spectra that the spinel structure aluminum phosphate of embodiment 1 step 4 generation is coated is shown in Fig. 1.
The carbon coated nitrogenize La doped lithium titanate XRD spectra that the spinel structure aluminum phosphate of embodiment 2 step 4 generation is coated is shown in Fig. 2.
2) material surface pattern carries out on Zeiss, Germany company EV018 type scanning electron microscopy SEM, and X-ray energy scattering EDS spectrum and Element area profile carry out on Oxford X-MAX 20 type energy disperse spectroscopy.
The SEM image of the coated cerium nitride doped lithium titanate of carbon that the spinel structure aluminum phosphate that embodiment 1 step 4 prepares is coated is shown in Fig. 3.Fig. 4 is the X-ray energy scattering EDS spectrum of the coated coated cerium nitride doped lithium titanate of carbon of spinel structure aluminum phosphate, measures carbon containing, nitrogen, phosphorus, oxygen, cerium and titanium elements.
The SEM image of the carbon coated nitrogenize La doped lithium titanate that the spinel structure aluminum phosphate that embodiment 2 step 4 prepares is coated is shown in Fig. 5.Fig. 6 is the X-ray energy scattering EDS spectrum of the coated carbon coated nitrogenize La doped lithium titanate of spinel structure aluminum phosphate, measures carbon containing, nitrogen, phosphorus, oxygen, lanthanum and titanium elements.
Electrochemical property test
90:2:8 gets the coated cerium nitride of the coated carbon of aluminum phosphate or La doped lithium titanate, super P and PVDF (HSV900) in mass ratio; add appropriate 1-METHYLPYRROLIDONE as solvent; in glove box under argon shield; by magnetic stirrer 15 hours, prepare the required slurry of button electricity.Coating machine is Shenzhen Ke Jingzhida Science and Technology Ltd. MSK-AFA-III automatic spray dryer, coating clearance 25 microns, speed 5 cm per minute, slurry is evenly coated in 9 micron thickness that Jinxiang Copper Foil Co., Ltd., Mei County produces, on purity 99.8% shiny copper foil, vacuumize 12 hours at 120 DEG C, then strikes out at Shenzhen section brilliant MSK-T06 button cell sheet-punching machine the electrode foil that diameter is about 16 millimeter.CR2032 button cell is assembled in and carries out homemade being full of in 99.9% high-purity argon gas glove box, adopts Shenzhen section brilliant MSK-110 small-sized hydraulic button cell packaging machine.Negative pole is the high purity lithium sheet of purity 99.99% diameter 15.8 millimeters, and barrier film is thickness 16 microns of U.S. ENTEK LP16 type PE barrier films, and electrolyte is EC:DMC:EMC (30:30:40, volume ratio), adds 1%VC (volume ratio), 1.3MLiPF 6.Button cell circulation and multiplying power test are carried out on the CT2001A tester of Wuhan Lan electricity Electronics Co., Ltd..
Electrochemistry cyclic voltammetry experiment carries out on the Huachen CHI604E of Shanghai, and work electrode is the coated coated cerium nitride of carbon of the spinel structure aluminum phosphate for preparing or La doped lithium titanate, and be lithium sheet to electrode and reference electrode, sweep speed is 200 μ V/s.Fig. 7 is the electrochemistry cyclic voltammetry curve of the coated carbon coated nitrogenize La doped lithium titanate of spinel structure aluminum phosphate that embodiment 2 prepares.
The coated coated nitrogenize of the carbon rear-earth-doped metatitanic acid lithium of spinel structure aluminum phosphate prepared by the present invention has good gram volume, has good application prospect at lithium rechargeable battery.

Claims (10)

1. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating, is characterized in that: comprise the following steps:
1) titanium dioxide, lithium carbonate and rare-earth salts are mixed, be placed in vacuum or protective gas atmosphere is calcined, cooling, obtains spinel structure rear-earth-doped metatitanic acid lithium naturally; The mol ratio of the rare earth element in described rare-earth salts and the titanium elements in titanium dioxide is 1 ~ 10:100;
2) by carbon source and the mixing of rear-earth-doped metatitanic acid lithium, calcine in vacuum or protective gas atmosphere, naturally cool, obtain the coated rear-earth-doped metatitanic acid lithium of carbon;
3) by nitrogenous source and the coated rear-earth-doped metatitanic acid lithium mixing of carbon, calcine in vacuum or protective gas atmosphere, make the nitrogen element of rear-earth-doped metatitanic acid lithium surface portion and titanium elements form titanium nitrogen bond TiN, naturally cool, obtain the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon; The rear-earth-doped metatitanic acid lithium of nitrogenize is expressed as Li 4ti 5-xm xo 12/ TiN, M are doped with rare-earth elements, 0≤x≤1;
4) by coated for carbon nitrogenize rear-earth-doped metatitanic acid lithium particle dispersed one-tenth suspension-turbid liquid in suspension-turbid liquid solvent; aluminium salt and phosphate is added in suspension-turbid liquid; the aluminum phosphate generated evenly is coated on the coated nitrogenize of carbon rear-earth-doped metatitanic acid lithium particle surface; filtering solution; coated for carbon coated for aluminum phosphate nitrogenize rear-earth-doped metatitanic acid lithium particle is placed in vacuum or protective gas atmosphere is calcined; naturally cool; obtain the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the coated carbon of aluminum phosphate, wherein phosphate and the coated rear-earth-doped nitrogenize lithium titanate mass percent of carbon are 0.1 ~ 20:100.
2. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Described titanium dioxide crystal form is rutile-type, Detitanium-ore-type, brookite type or unformed;
Described rare-earth salts comprises lanthanide rare salt, and described lanthanide rare salt comprises one or more in group of the lanthanides sulfate, nitrate, carbonate, chlorate and acetate;
Described carbon source comprises one or more in pitch, starch, glucose, maltose, citric acid, cyclodextrin, acetate fiber, epoxy resin, phenolic resins, Lauxite, furfural resin, polyvinyl alcohol and polyvinylidene;
Described nitrogenous source comprise urea, contracting two urine, acetonitrile, cyanamide, cyanamid dimerization, melamine and Nitrogen element ionic liquid in one or more;
Described protective gas is one or more in nitrogen, helium and argon gas;
Described aluminium salt is one or more in aluminum sulfate, aluminum nitrate and aluminum acetate.
3. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Described Nitrogen element ionic liquid comprises imidazoles, pyridines, quaternary amines, pyrrolidines, piperidines He one or more in quaternary phosphine class; Described imidazoles is one or both in disubstituted imidazole class and tri-substituted imidazole class; Described pyridines is one or both in disubstituted pyridines class and three substituted-pyridines; Described functionalized ion liquid is one or more in N-alkyl imidazole, functional amido class, sulfonic acid funtionalized class, hydroxy functionalized class, cyano group functionalization class, thiazolinyl functionalization class, ether functionalization class, benzyl functionalization class, carboxyl-functional class, ester group functionalization class and guanidine class ionic liquid.
4. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Step 4) suspension-turbid liquid solvent is the mixed solution of water and alcohol; Described alcohol comprises one or more in ethanol, propyl alcohol, isopropyl alcohol, butanols, isobutanol and ethylene glycol, and the volume ratio of described water and alcohol is 100 ~ 40:1 ~ 60.
5. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Step 1) calcination condition be: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature; and then continue to be warmed up to 500 ~ 950 DEG C with the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
6. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Step 2) calcination condition is: in vacuum or protective gas atmosphere; 300 ~ 500 DEG C are warmed up to the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature; and then continue to be warmed up to 500 ~ 950 DEG C with the speed of 2 ~ 5 DEG C/min; and keep 0.5 ~ 2 hour at this temperature, in vacuum or protective gas atmosphere, naturally cool to room temperature after reaction terminates.
7. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Step 3) calcination condition is: in vacuum or protective gas atmosphere, is warmed up to 300 ~ 500 DEG C with the speed of 2 ~ 5 DEG C/min, and keeps 0.5 ~ 2 hour at this temperature, after reaction terminates, in vacuum or protective gas atmosphere, naturally cool to room temperature.
8. the preparation method of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of Phosphate coating according to claim 1, is characterized in that:
Step 4) calcination condition is: in vacuum or protective gas atmosphere, is warmed up to 300 ~ 800 DEG C with the speed of 2 ~ 5 DEG C/min, and keeps 0.5 ~ 5 hour at this temperature, after reaction terminates, in vacuum or protective gas atmosphere, naturally cool to room temperature.
9. the application of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of carbon in ion secondary battery cathode material lithium of the Phosphate coating prepared by any one of claim 1 ~ 9.
10. the structure of the rear-earth-doped metatitanic acid lithium of the coated nitrogenize of the carbon of a Phosphate coating, it is characterized in that: comprise kernel coated successively from the inside to the outside, the first coating layer, the second coating layer, described kernel is the rear-earth-doped lithium titanate that surface distributed has titanium nitride, described first coating layer is carbon coating layer or the carbon coating layer containing carbonitride, and described second coating layer is phosphate.
CN201410522892.1A 2014-09-30 2014-09-30 Preparation and application of phosphate-cladded carbon-cladded nitrogenized rare-earth-doped Li4Ti5O12 Pending CN104269524A (en)

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