CN102820458A - Synthetic method for preparing nitrogen-carbon-containing coated lithium titanate composite material by introducing ionic liquid as carbon source - Google Patents
Synthetic method for preparing nitrogen-carbon-containing coated lithium titanate composite material by introducing ionic liquid as carbon source Download PDFInfo
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 112
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 108
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 107
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 106
- 239000002608 ionic liquid Substances 0.000 title claims abstract description 15
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000010189 synthetic method Methods 0.000 title claims abstract description 5
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title abstract 2
- 238000000498 ball milling Methods 0.000 claims abstract description 38
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 35
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000005303 weighing Methods 0.000 claims abstract description 27
- 238000005245 sintering Methods 0.000 claims abstract description 22
- 239000008367 deionised water Substances 0.000 claims abstract description 21
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 238000001291 vacuum drying Methods 0.000 claims abstract description 10
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 5
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 5
- 239000011164 primary particle Substances 0.000 claims abstract description 5
- 239000007789 gas Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims description 81
- 239000002002 slurry Substances 0.000 claims description 27
- 238000001035 drying Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 238000012545 processing Methods 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 12
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 10
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 10
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 10
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 10
- 238000002360 preparation method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 238000009413 insulation Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 9
- 238000001694 spray drying Methods 0.000 claims description 9
- 229910052719 titanium Inorganic materials 0.000 claims description 9
- 238000010792 warming Methods 0.000 claims description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 6
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 6
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical class NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- WLWHLUQQCLCFNE-UHFFFAOYSA-N 1-ethenyl-3-methyl-2h-imidazole Chemical compound CN1CN(C=C)C=C1 WLWHLUQQCLCFNE-UHFFFAOYSA-N 0.000 claims description 3
- IBZJNLWLRUHZIX-UHFFFAOYSA-N 1-ethyl-3-methyl-2h-imidazole Chemical compound CCN1CN(C)C=C1 IBZJNLWLRUHZIX-UHFFFAOYSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 3
- 229930006000 Sucrose Natural products 0.000 claims description 3
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 3
- 239000003822 epoxy resin Substances 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 229920001568 phenolic resin Polymers 0.000 claims description 3
- 239000005011 phenolic resin Substances 0.000 claims description 3
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 claims description 3
- 229920000647 polyepoxide Polymers 0.000 claims description 3
- 229920005989 resin Polymers 0.000 claims description 3
- 239000011347 resin Substances 0.000 claims description 3
- 239000005720 sucrose Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 10
- 239000003575 carbonaceous material Substances 0.000 abstract 2
- 239000002243 precursor Substances 0.000 abstract 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 239000011163 secondary particle Substances 0.000 abstract 1
- -1 carbon-modified lithium titanate Chemical class 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 7
- 238000007599 discharging Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 206010016766 flatulence Diseases 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000010298 pulverizing process Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000006181 electrochemical material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a synthetic method for preparing a nitrogen-carbon-containing coated lithium titanate composite material by introducing an ionic liquid as a carbon source. The method comprises the following steps: 1) weighing lithium salt, titanium dioxide and a carbon source according to a proportion, adding alcohol, performing ball milling dispersion treatment, and then performing vacuum drying to obtain a precursor; 2) sintering the prepared precursor for 8-20 hours under the protection of inert atmosphere at 750-950 ℃ to preliminarily obtain lithium titanate with the surface coated with a carbon material; 3) the carbon-coated lithium titanate obtained preliminarily is added with the ionic liquid and the deionized water according to the proportion for ball milling, stirring and sintering, the carbon-coated lithium titanate has the spherical shape of micron secondary particles formed by nano primary particles, the surface of the carbon-coated lithium titanate is uniformly coated with a layer of nitrogen-containing carbon material, the electronic conductivity of the carbon-coated lithium titanate is effectively improved, the surface stability of the carbon-coated lithium titanate is enhanced, the obtained carbon-coated lithium titanate has excellent rate performance and cycle performance, the problem of gas expansion of a lithium titanate system battery is effectively solved, and the carbon-coated lithium titanate has wide application prospect in the field of lithium ion.
Description
Technical field
The present invention relates to the preparation method that the nitrogenous carbon of a kind of lithium ion battery negative material coats lithium titanate composite material; Be particularly related to the method for in the material building-up process, taking the secondary coating and introduce ionic liquid and the lithium titanate surface is coated processing as carbon source; This coating layer is nitrogenous material with carbon element; Realize the raising of the cycle performance and the high rate performance of material, and effectively improved the flatulence problem of lithium titanate system battery, belonged to electrochemical material technology of preparing and new energy field.
Background technology
Along with environmental problem and energy crisis paid more and more attention, the development clean energy resource is imperative.In new forms of energy development, lithium ion battery is just towards direction develop activelies such as power vehicle and electrical network energy storage, develops to have high security, and the long life can realize that the lithium ion battery of fast charging and discharging has become the emphasis problem of industry research.
Present commercial lithium ion battery adopts material with carbon element as negative material mostly, but material with carbon element itself has some shortcomings: (1) can form the SEI film, and its first charge-discharge efficiency is low; (2) it is approaching by current potential and lithium metal current potential, can form Li dendrite during over-charging of battery, causes short circuit, causes safety problem; (3) has tangible voltage delay phenomenon; (4) be easy to electrolyte and react, cause the loss of electrolyte; The spinel lithium titanate material comes into one's own as lithium ion battery negative material day by day, and it is compared with business-like material with carbon element has incomparable advantage: it has higher Ti
4+/ Ti
3+(1.55V vs Li
+/ Li) redox potential, its surface can not form the SEI film; It has spinel structure, and volume changes hardly in charge and discharge process, thereby it has the cycle life that is superior to carbon negative pole material; It has three-dimensional lithium ion diffusion admittance, and the high rate charge-discharge excellent performance is reacted in the embedding of taking off fast that helps lithium ion; It also has desirable charge and discharge platform, and charging finishes to have tangible voltage jump characteristic; Wide, the cleaning of its preparation raw material sources.This shows that lithium titanate material has characteristics such as cycle life is longer, safer, charging process is faster as lithium ion battery negative material of future generation, it has huge researching value and commercial application prospect as lithium ion battery negative material.
But the electronic conductivity of pure phase lithium titanate is very low, has influenced the charge-discharge performance as lithium ion battery electrode material, and especially therefore the poor-performing of its fast charging and discharging will be realized with carrying out modification to it with level.The common modified measures of taking mainly comprises two aspects at present: (1) synthesis of nano size lithium titanate material, the specific area of increase electrode material, the migration path of shortening lithium ion.Can increase the diffusion velocity of lithium ion in embedding process, guarantee the fast charging and discharging ability of lithium ion battery; (2) lithium titanate material is carried out metal cation and mix, it is right in the solid structure of material, to increase the duplet hole, increases the carrier concentration of material, to improve the electronic conductivity of lithium titanate.Research shows the conductivity that can improve lithium titanate through cation doping preferably, obviously improves the high-rate charge-discharge capability of lithium titanate anode; (3) introduce high conductive materials; In lithium titanate powdery, introduce the material (like metal, carbon etc.) of high conductivity, serve as conducting medium, evenly disperse or be coated on the particle surface of lithium titanate material; Form conductive network, improve the electric conductivity of combination electrode material.
In the prior art; Patent CN101777645A discloses a kind of preparation method of lithium titanate of carbon modification; Titanium dioxide, lithium carbonate, coating are mixed pulverizing with organic carbon source, doping with inorganic carbon source; Sintering under atmosphere protection obtains the pre-burning product and obtains the carbon-modified lithium titanate material through pulverizing mixing and sintering processes again, can effectively improve the cycle performance and the high rate performance of material; Patent CN102013476A discloses and in the lithium titanate building-up process, has introduced solid-state nitrogenous source, obtains a kind of lithium titanate/titanium nitride composite material, has improved the high rate during charging-discharging of lithium titanate material; It is the logical superheated nitrogen of nitrogenous source one deck TiN film that has been reflected at the lithium titanate surface preparation that patent CN101728517A discloses with urea;
Above-mentioned preparation method has realized the modification of independent carbon or nitride, has certain feasibility, has realized among the present invention that kind nitrogen and carbon modifies the lithium titanate material surface simultaneously.
Summary of the invention
Technical problem to be solved by this invention provides a kind of nitrogen and material with carbon element is modified the lithium titanate material surface simultaneously; And owing to adopt the synthesis technique that secondary coats and introduced ionic liquid as carbon source, make lithium titanate material coated with uniform the nitrogenous material with carbon element of one deck.
In order to achieve the above object, the technical scheme taked of the present invention is:
A kind of ionic liquid of introducing prepares the synthetic method that nitrogenous carbon coats lithium titanate composite material as carbon source, and this lithium titanate composite material has the nanometer primary particle and forms a micron offspring spherical morphology, its coated with uniform the nitrogenous material with carbon element of one deck.
May further comprise the steps:
(1) mol ratio according to lithium, titanium, carbon is (4～4.4): 5: (greater than zero～2) takes by weighing lithium salts, titanium dioxide and organic carbon source; Adding dispersant places ball mill to carry out the stirring ball-milling processing; The ball milling time is 3-12 hour; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 80～120 degree, and be 8-16 hour drying time;
(2) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 750 ℃～950 ℃ with the heating rate of 2～25 ℃/min, is incubated 8～20 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats;
(3) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing ionic liquid according to 5%～30% the percentage that carbon coats the lithium titanate quality; And be blended into proper amount of deionized water and carry out once more Ball milling and handle; Slurries after finishing dealing with add appropriate amount of deionized water again or dispersant adjustment solid content of slurry is 10%～50%, carry out spray drying treatment again;
The dry powder that (4) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 500～900 ℃ of insulations 5-16 hour with the heating rate of 2～25 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
The described titanium dioxide of step (1) is the nanostructured anatase structure; Said lithium salts is selected from one or more combinations in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, the lithium fluoride; Said organic carbon source is selected from one or more combinations in glucose, sucrose, polyvinyl butyral resin, phenolic resins, epoxy resin, the polyvinyl alcohol.
Dispersant described in step (1) and the step (3) is selected from one or more combinations in absolute ethyl alcohol, acetone, the deionized water.
Ionic liquid described in the step (3) is selected from one or more combinations in the acetate, nitrate, dicyandiamide salt of acetate, nitrate, dicyandiamide salt or the 1-vinyl-3-methylimidazole of 1-ethyl-3-methylimidazole; The above ion liquid purity is more than or equal to 98%, and wherein the mol ratio of nitrogen and carbon is 2/8～5/8.
Protective atmosphere is selected from one or more combinations in helium, nitrogen, argon gas, the carbon dioxide described in step (2) and (4).
Nitrogenous carbon described in the step (4) coats lithium titanate material and has a nanometer primary particle composition micron offspring spherical morphology, the nitrogenous material with carbon element of coated with uniform one deck.
The present invention has not only effectively improved the electronic conductivity of lithium titanate material but also has strengthened the surface stability of this material, and the material that is obtained has excellent high rate performance and cycle performance, and has effectively improved the flatulence problem of lithium titanate system battery.
Description of drawings
Fig. 1 is that nitrogenous carbon coats the X-ray diffractogram of lithium titanate material and the comparison diagram of standard card.
(a) nitrogenous carbon coats lithium titanate composite material; (b) standard card (JCPD490207)
Fig. 2 is the SEM figure that the nitrogenous carbon that obtained among the embodiment 3 coats lithium titanate material.
Fig. 3 is the first charge-discharge curve (0.2C) that pure phase lithium titanate, carbon coat lithium titanate and nitrogenous carbon coating lithium titanate material, and voltage range is 1.0～2.5V.
The pure phase lithium titanate of Fig. 4, carbon coat lithium titanate and nitrogenous carbon coats the cycle performance comparison diagram of lithium titanate material under different multiplying, and charge-discharge magnification is 0.2C, 1.0C, 5.0C, 10.0C.
Embodiment
Embodiment 1
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.2 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 5 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 80 degree, and be 8 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 800 ℃ with the heating rate of 2 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 30% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 10% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 500 insulations 15 hours with the heating rate of 2 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 2
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.5 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 8 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 90 degree, and be 10 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 850 ℃ with the heating rate of 5 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 25% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 25% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 800 insulations 10 hours with the heating rate of 5 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.8 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 10 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 12 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 880 ℃ with the heating rate of 8 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 15% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 40% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 600 insulations 8 hours with the heating rate of 8 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 4
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:1.2 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 12 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 120 degree, and be 8 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 900 ℃ with the heating rate of 10 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 10% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 45% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 800 insulations 7 hours with the heating rate of 10 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 5
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:1.5 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 6 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 10 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 950 ℃ with the heating rate of 15 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 5% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 50% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 950 insulations 6 hours with the heating rate of 20 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
Embodiment 6
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:2 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 10 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 12 hours drying time.
B) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 880 ℃ with the heating rate of 8 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats.
C) take by weighing the lithium titanate material that a certain amount of carbon coats, add proper amount of deionized water and carry out once more the Ball milling processing, it is 40% that the slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 600 insulations 8 hours with the heating rate of 8 ℃/min, obtains carbon and coats lithium titanate material.
The comparative example
A) mol ratio according to lithium, titanium, carbon is that 4.2:5:0.8 takes by weighing lithium carbonate, titanium dioxide and polyvinyl alcohol; Adding a certain amount of alcohol places ball mill to carry out the stirring ball-milling processing; The ball milling time is 10 hours; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 100 degree, and be 12 hours drying time.
B) drying is good presoma places air furnace to carry out sintering, is warming up to 880 ℃ with the heating rate of 8 ℃/min, is incubated 12 hours, naturally cools to room temperature, obtains lithium titanate material.
C) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA) according to 15% the percentage that carbon coats the lithium titanate quality; Add proper amount of deionized water and carry out once more the Ball milling processing; It is 40% that slurries after finishing dealing with add appropriate amount of deionized water adjustment solid content of slurry again, carries out spray drying treatment again.
The dry powder that d) will pass through aftertreatment places air furnace to carry out sintering, rises to 600 insulations 8 hours with the heating rate of 8 ℃/min, obtains pure phase lithium titanate material.
The lithium titanate material of gained in the foregoing description is assembled into button cell, and material proportion is Li in the button cell
4Ti
5O
12: SP:PVDF=80:10:10; Adopting Clgard2300 type barrier film, is metal lithium sheet to electrode, carries out the charge-discharge performance test; Pure phase lithium titanate, carbon coat lithium titanate and nitrogenous carbon coating lithium titanate material 0.2C charging and discharging curve is as shown in Figure 3, and the charging/discharging voltage scope is 1.0-2.5V.Fig. 4 is that pure phase lithium titanate, carbon coat lithium titanate and nitrogenous carbon coats the cycle performance comparison diagram of lithium titanate material under different multiplying; From above-mentioned two width of cloth figure, can find out; Though the charge/discharge capacity under the pure phase lithium titanate 0.2C multiplying power is higher; It is less that but nitrogenous carbon coats the polarization of lithium titanate, and the charge/discharge capacity conservation rate is higher under high magnification.Shown in Figure 1 is the XRD figure that nitrogenous carbon coats lithium titanate material, and the result shows that the coating of nitrogenous carbon does not change the spinel structure of lithium titanate; Shown in Figure 2 is the sem photograph that nitrogenous carbon coats lithium titanate composite material, can find out that material demonstrates the pattern of micron-size spherical second particle;
Embodiment result shows, the synthesis technique that coats through secondary is also introduced ionic liquid as the part carbon source, obtains the surface and coats uniform nitrogenous carbon and coat lithium titanate material.This lithium titanate material has the nanometer primary particle and forms micron offspring spherical morphology; Its coated with uniform the nitrogenous material with carbon element of one deck; Not only effectively improved its electronic conductivity but also strengthened the surface stability of this material, the material that is obtained has excellent high rate performance and cycle performance.Use the battery system of this material and since the coated with uniform of this lithium titanate composite material the nitrogenous material with carbon element of one deck, avoided lithium titanate material directly and the haptoreaction of electrolyte, can effectively improve the flatulence problem of lithium titanate system battery.
Organic carbon source has only been enumerated polyvinyl alcohol in the foregoing description, selects one or more combinations in other the organic carbon source glucose, sucrose, polyvinyl butyral resin, phenolic resins, epoxy resin for use, and experimental result is similar; Ionic liquid has only been enumerated 1-ethyl-3-methylimidazole dicyandiamide salt (EMIM-DCA); Select one or more combinations in the acetate, nitrate, dicyandiamide salt of acetate, nitrate or the 1-vinyl-3-methylimidazole of other ionic liquids 1-ethyl-3-methylimidazole for use, experimental result is similar.
Claims (6)
1. introduce ionic liquid and prepare the synthetic method that nitrogenous carbon coats lithium titanate composite material for one kind, it is characterized in that may further comprise the steps as carbon source:
(1) mol ratio according to lithium, titanium, carbon is (4～4.4): 5: (greater than zero～2) takes by weighing lithium salts, titanium dioxide and organic carbon source; Adding dispersant places ball mill to carry out the stirring ball-milling processing; The ball milling time is 3-12 hour; The slurry that ball milling finishes places vacuum drying oven to carry out dried again, and temperature is 80～120 degree, and be 8-16 hour drying time;
(2) drying is good presoma places the atmosphere protection stove to carry out sintering, is warming up to 750 ℃～950 ℃ with the heating rate of 2～25 ℃/min, is incubated 8～20 hours, naturally cools to room temperature, obtains the lithium titanate material that carbon coats;
(3) take by weighing the lithium titanate material that a certain amount of carbon coats; And take by weighing ionic liquid according to 5%～30% the percentage that carbon coats the lithium titanate quality; And be blended into proper amount of deionized water and carry out once more Ball milling and handle; Slurries after finishing dealing with add appropriate amount of deionized water again or dispersant adjustment solid content of slurry is 10%～50%, carry out spray drying treatment again;
The dry powder that (4) will pass through aftertreatment places the atmosphere protection stove to carry out sintering, rises to 500～900 ℃ of insulations 5-16 hour with the heating rate of 2～25 ℃/min, obtains nitrogenous carbon and coats lithium titanate material.
2. preparation method according to claim 1 is characterized in that: the described titanium dioxide of step (1) is the nanostructured anatase structure; Said lithium salts is selected from one or more combinations in lithium carbonate, lithium hydroxide, lithium acetate, lithium oxalate, the lithium fluoride; Said organic carbon source is selected from one or more combinations in glucose, sucrose, polyvinyl butyral resin, phenolic resins, epoxy resin, the polyvinyl alcohol.
3. preparation method according to claim 1 is characterized in that the dispersant described in step (1) and the step (3) is selected from one or more combinations in absolute ethyl alcohol, acetone, the deionized water.
4. preparation method according to claim 1; It is characterized in that: the ionic liquid described in the step (3) is selected from one or more combinations in the acetate, nitrate, dicyandiamide salt of acetate, nitrate, dicyandiamide salt or the 1-vinyl-3-methylimidazole of 1-ethyl-3-methylimidazole; The above ion liquid purity is more than or equal to 98%, and wherein the mol ratio of nitrogen and carbon is 2/8～5/8.
5. preparation method according to claim 1 is characterized in that: protective atmosphere is selected from one or more combinations in helium, nitrogen, argon gas, the carbon dioxide described in step (2) and (4).
6. preparation method according to claim 1,, it is characterized in that: nitrogenous carbon described in the step (4) coats lithium titanate material and has a nanometer primary particle composition micron offspring spherical morphology, the nitrogenous material with carbon element of coated with uniform one deck.
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