CN101071853A - Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method - Google Patents
Nano lithium titanate for Negative electrode material of cell or electrochemical vessel, and its and titanium dioxide composite preparing method Download PDFInfo
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- CN101071853A CN101071853A CNA2007100544814A CN200710054481A CN101071853A CN 101071853 A CN101071853 A CN 101071853A CN A2007100544814 A CNA2007100544814 A CN A2007100544814A CN 200710054481 A CN200710054481 A CN 200710054481A CN 101071853 A CN101071853 A CN 101071853A
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 69
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 67
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title description 11
- 239000002131 composite material Substances 0.000 title description 4
- 239000007773 negative electrode material Substances 0.000 title 1
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 34
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 34
- 150000001875 compounds Chemical class 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011261 inert gas Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims abstract description 4
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 4
- 239000011734 sodium Substances 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000000463 material Substances 0.000 claims description 27
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 238000005406 washing Methods 0.000 claims description 22
- 230000004927 fusion Effects 0.000 claims description 20
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 17
- GROMGGTZECPEKN-UHFFFAOYSA-N sodium metatitanate Chemical compound [Na+].[Na+].[O-][Ti](=O)O[Ti](=O)O[Ti]([O-])=O GROMGGTZECPEKN-UHFFFAOYSA-N 0.000 claims description 17
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 10
- NJLLQSBAHIKGKF-UHFFFAOYSA-N dipotassium dioxido(oxo)titanium Chemical compound [K+].[K+].[O-][Ti]([O-])=O NJLLQSBAHIKGKF-UHFFFAOYSA-N 0.000 claims description 9
- 239000007789 gas Substances 0.000 claims description 8
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- HSZCZNFXUDYRKD-UHFFFAOYSA-M lithium iodide Chemical compound [Li+].[I-] HSZCZNFXUDYRKD-UHFFFAOYSA-M 0.000 claims description 6
- 238000004062 sedimentation Methods 0.000 claims description 6
- 229940031993 lithium benzoate Drugs 0.000 claims description 5
- 229940071264 lithium citrate Drugs 0.000 claims description 5
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 5
- LDJNSLOKTFFLSL-UHFFFAOYSA-M lithium;benzoate Chemical compound [Li+].[O-]C(=O)C1=CC=CC=C1 LDJNSLOKTFFLSL-UHFFFAOYSA-M 0.000 claims description 5
- QAZAAZKNSOCPBF-UHFFFAOYSA-N [Li].C(C=C)(=O)O Chemical compound [Li].C(C=C)(=O)O QAZAAZKNSOCPBF-UHFFFAOYSA-N 0.000 claims description 4
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 claims description 4
- 229910002113 barium titanate Inorganic materials 0.000 claims description 4
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 4
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 4
- INHCSSUBVCNVSK-UHFFFAOYSA-L lithium sulfate Inorganic materials [Li+].[Li+].[O-]S([O-])(=O)=O INHCSSUBVCNVSK-UHFFFAOYSA-L 0.000 claims description 4
- RBTVSNLYYIMMKS-UHFFFAOYSA-N tert-butyl 3-aminoazetidine-1-carboxylate;hydrochloride Chemical compound Cl.CC(C)(C)OC(=O)N1CC(N)C1 RBTVSNLYYIMMKS-UHFFFAOYSA-N 0.000 claims description 4
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical compound [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 4
- JCCYXJAEFHYHPP-OLXYHTOASA-L dilithium;(2r,3r)-2,3-dihydroxybutanedioate Chemical compound [Li+].[Li+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O JCCYXJAEFHYHPP-OLXYHTOASA-L 0.000 claims description 3
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- XQHAGELNRSUUGU-UHFFFAOYSA-M lithium chlorate Chemical compound [Li+].[O-]Cl(=O)=O XQHAGELNRSUUGU-UHFFFAOYSA-M 0.000 claims description 3
- JILPJDVXYVTZDQ-UHFFFAOYSA-N lithium methoxide Chemical compound [Li+].[O-]C JILPJDVXYVTZDQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 claims description 3
- AXHNANAHRZVDHS-KVVVOXFISA-N lithium;(z)-octadec-9-enoic acid Chemical compound [Li].CCCCCCCC\C=C/CCCCCCCC(O)=O AXHNANAHRZVDHS-KVVVOXFISA-N 0.000 claims description 3
- AZVCGYPLLBEUNV-UHFFFAOYSA-N lithium;ethanolate Chemical compound [Li+].CC[O-] AZVCGYPLLBEUNV-UHFFFAOYSA-N 0.000 claims description 3
- XKPJKVVZOOEMPK-UHFFFAOYSA-M lithium;formate Chemical compound [Li+].[O-]C=O XKPJKVVZOOEMPK-UHFFFAOYSA-M 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- -1 sodium (potassium) titanate compound Chemical class 0.000 abstract description 10
- 238000010438 heat treatment Methods 0.000 abstract description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052700 potassium Inorganic materials 0.000 abstract description 2
- 239000011591 potassium Substances 0.000 abstract description 2
- 229960005196 titanium dioxide Drugs 0.000 abstract 2
- 239000010406 cathode material Substances 0.000 abstract 1
- BYTCDABWEGFPLT-UHFFFAOYSA-L potassium;sodium;dihydroxide Chemical compound [OH-].[OH-].[Na+].[K+] BYTCDABWEGFPLT-UHFFFAOYSA-L 0.000 abstract 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract 1
- 239000000047 product Substances 0.000 description 20
- 239000002071 nanotube Substances 0.000 description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 239000000243 solution Substances 0.000 description 12
- 229910010413 TiO 2 Inorganic materials 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 229910052799 carbon Inorganic materials 0.000 description 8
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 7
- 239000002253 acid Substances 0.000 description 7
- 238000000227 grinding Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229910052596 spinel Inorganic materials 0.000 description 6
- 239000011029 spinel Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 5
- 238000000967 suction filtration Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000003990 capacitor Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 238000003980 solgel method Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical class CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000004087 circulation Effects 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
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- 239000007772 electrode material Substances 0.000 description 1
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- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 1
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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
This invention discloses nano lithium titanate for cell cathode material and compound with titanium dioxide, its preparation method is that: (1) compound containing titanium and sodium hydroxide (potassium) react by heating, cool, wash by water to different pH value, dry to obtain sodium(potassium) titanate or sodium (potassium) titanate compound; (2) mix the product from step (1) and inorganic lithium salt, heat it up to 451- 1,000 degree C to fuse exchange react for 30minute -48 hours, or mix the product from step (1) and organic or inorganic lithium salt under inert gas and heat it to150-1,000 degree C to fuse exchange react for30 minute - 48 hours, then wash by water and dry to obtain the finished product.
Description
Technical field
The invention belongs to technical field of nano material, relate to the preparation method of the compound of a kind of nano lithium titanate that is used for battery or electrochemical vessel negative material, itself and titanium dioxide.
Background technology
Present commercial lithium ion battery negative material adopts various embedding lithium material with carbon elements mostly, there are some shortcomings in material with carbon element as lithium ion battery negative material: the one, and the current potential of material with carbon element and the current potential of lithium metal are very approaching, when over-charging of battery, lithium metal may be separated out and forms Li dendrite in carbon electrodes, thereby causes short circuit; The 2nd, first charge-discharge efficiency is low; The 3rd, have an effect with electrolyte; The 4th, there is tangible voltage delay phenomenon; The 5th, material with carbon element preparation method more complicated; The 6th, though the alloy type negative material generally has higher specific capacity, the embedding repeatedly of lithium is taken off and is caused the change in volume of alloy type negative pole in charge and discharge process bigger, and efflorescence was lost efficacy gradually, thereby cycle performance is relatively poor.Along with the rise of environmental-protecting type electric automotive research, electrochemical vessel has become another research focus behind lithium ion battery as a kind of energy storage device with high power density.It and secondary cell combination are used, can satisfy preferably that electric automobile starts, quickens, during climbing to high-power requirement, and reclaim the transient energy that electric automobile when brake produces rapidly, make secondary cell maintain work under the more stable current status all the time, prolong its cycle life.
Lithium titanate is that a kind of lithium inserts the zero strain material, and as lithium ion battery negative material not recurring structure change in charge and discharge process, good cycle has good charge and discharge platform; Do not react with electrolyte; Low price, preparation is compared with commercial carbon negative pole material easily, has better chemical property and fail safe usually.Can also be used to replace a utmost point of active carbon double electric layer capacitor, bring into play the advantage of its relative height ratio capacity; The big order of magnitude of its chemical diffusion coefficient ratio carbon electrode material becomes desirable hybrid electrochemical capacitor negative material simultaneously.
The synthetic method of lithium titanate adopts high-temperature solid phase reaction method and sol-gel process mostly at present.The high temperature solid-state synthesis technique of lithium titanate is similar to other composite oxide of metal, usually with TiO
2And LiOH (or LiCO
3) be raw material, by high temperature (800-1000 ℃), for a long time heat treatment forms product, and the shortcoming of this method is the energy consumption height, and product mostly is micron or submicron particles greatly, and big particle size is unfavorable for the quick embedding of lithium ion and deviates from.
Advantages such as sol-gel process is because to have a synthesis temperature low, and particle size is little, and homogeneity is good, and specific area is big and being widely adopted gradually.But sol-gel process need use expensive organic alkoxide as presoma, and complex process, therefore is difficult to realize that large-scale industrial production satisfies the wilderness demand of energy field.
Summary of the invention
The purpose of this invention is to provide that a kind of product crystal property is good, chemical property is excellent, technology is simple, be easy to the nano lithium titanate that is used for battery or electrochemical vessel negative material of suitability for industrialized production, the preparation method of itself and titanium dioxide compound.
The present invention realizes above-mentioned purpose by the following technical solutions: the preparation method of the compound of a kind of nano lithium titanate that is used for battery or electrochemical vessel negative material, itself and titanium dioxide may further comprise the steps:
(1), titanium-containing compound and NaOH or potassium hydroxide adds thermal response, reaction back mixed liquor cooling-sedimentation, water washing is to different pH values, dry nano barium titanate sodium or metatitanic acid-sodium titanate compound, perhaps dry nanometer potasium titanate or the metatitanic acid-potassium titanate compound of getting;
(2), the product of step (1) is mixed with inorganic lithium salt, be heated to 451～1000 ℃ of following fusion exchange reactions 30 minutes～48 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound;
Another kind method is that product with step (1) is under inert atmosphere or reducing atmosphere, mix with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 150～1000 ℃ of fusion exchange reactions 30 minutes～48 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound.
Inert gas is selected nitrogen or argon gas, and reducibility gas is selected hydrogen.
The method of the preferred following steps of above-mentioned preparation method: the product and the inorganic lithium salt of step (1) were mixed and heated to 451～700 ℃ of following fusion exchange reactions 2～12 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound.
Above-mentioned preparation method is the method for following steps preferably: under inert gas or reducibility gas, the product of step (1) is mixed with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 250～600 ℃ of fusion exchange reactions 2～12 hours, water washing, dry nano lithium titanate or itself and titanium dioxide compound.
In the step (1), the reaction after washing wash to the pH value be 6～12, step (2) product is lithium titanate-titanium dioxide compound.
In the step (1), the reaction after washing wash to the pH value greater than 12.5, step (2) product is a lithium titanate.
The mol ratio of sodium titanate, potassium titanate, metatitanic acid-sodium titanate compound or metatitanic acid-potassium titanate compound and lithium salts is 1: 0.5 to 1: 20.
Described inorganic lithium salt is a kind of, two or more the combination in lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide, the lithium iodide; Described organic lithium salt is a kind of, two or more the combination in lithium formate, lithium acetate, lithium oxalate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, lithium citrate, acrylic acid lithium, lithium methoxide, the lithium ethoxide.
The preparation method of nano barium titanate sodium (potassium) or metatitanic acid-sodium titanate (potassium) presoma:
Titanium-containing compound is mixed in container with NaOH or the potassium hydroxide aqueous solution of percentage by weight 20-80%, with mode reflux such as hydro-thermal reaction in routine heating, microwave heating or the autoclave pressure 30 minutes to 72 hours; Reaction back mixed liquor cooling-sedimentation, and control washing degree get nano barium titanate sodium or metatitanic acid-sodium titanate compound, perhaps get nanometer potasium titanate or metatitanic acid-potassium titanate compound;
It is presoma that the present invention adopts the sodium titanate of one-dimensional nano structure or metatitanic acid-sodium titanate nanotubes, potassium titanate or metatitanic acid-Nano lines of potassium titanate compound, by control washing degree, presoma is washed different pH values, regulate the ratio of titanate and metatitanic acid in the presoma, and then the ratio of lithium titanate and titanium dioxide in the control end product.As lithium ion battery material, lithium titanate has good cyclical stability, but its theoretical specific capacity is lower; Titanium dioxide is compared with lithium titanate has higher theoretical specific capacity, by controlling the two content to suitable ratio, can make product both have cyclical stability preferably, has higher specific capacity again.In addition, metatitanic acid-titanate of the present invention and inorganic lithium salt are mixed and heated to 451～1000 ℃ of following fusion exchange reactions, perhaps nano barium titanate-titanate compound mixes with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 150～1000 ℃ of fusion exchange reactions, these two kinds of reactions are to carry out the fusion exchange under higher temperature, hot conditions helps obtaining the better lithium titanate of crystal property, has good stability as negative material, have long useful life, and shortened the reaction time.Reaction raw materials is except selecting inorganic lithium salt, also select to use organic lithium salt, when organic lithium salt carries out the fusion exchange, in inert atmosphere (as nitrogen, argon gas) or reducing atmosphere (as hydrogen) organic substance generation carbonization down, be coated on the lithium titanate surface, improve the conductivity of lithium titanate, improved the performance of battery.Nano lithium titanate, the lithium titanate-titanium dioxide compound of the present invention's preparation have showed excellent chemical property as electrochemical energy storage materials, lithium titanate-titanium dioxide compound charge-discharge test shows that the simulated battery specific discharge capacity reaches 171mAh/g, near theoretical value 175mAh/g, discharge platform is near 1.6～1.8; The nano lithium titanate charge-discharge test shows that the simulated battery first discharge specific capacity reaches 160mAh/g, and discharge platform all has charge and discharge cycles stability preferably near 1.5V.In new type lithium ion battery and electrochemical capacitor, have wide practical use.
Method of the present invention is raw materials used cheap and easy to get, and is simple to operate, productive rate height, easy realization of large-scale production.
Description of drawings
Fig. 1 is the Electronic Speculum figure of embodiment 1 lithium titanate;
Fig. 2 is the Electronic Speculum figure of embodiment 2 lithium titanates-titanium dioxide compound;
Fig. 3 is the X-ray diffractogram that embodiment 2 lithium titanates, titanium dioxide mix phase;
Fig. 4 is the X-ray diffractogram of embodiment 4 pure phase lithium titanates;
Fig. 5 is the charging and discharging curve of four circulations of compound of nano lithium titanate-titanium dioxide;
Fig. 6 is the charging and discharging curve of four circulations of nano lithium titanate.
The used instrument of tem analysis is the JEM-100CX II type transmission electron microscope (TEM) of NEC (JEOL), and accelerating voltage is 100kV, and sample preparation is adopted the ultrasonic dispersion of absolute ethyl alcohol back to drip and born on the copper mesh of carbon film air drying.
The used instrument of XRD analysis is X ' pert pro type x-ray diffractometer (XRD, Holland Philips company), adopt CuK α line excitaton source, λ=0.15418366nm, voltage 40kV, electric current 40mA, sample can be powder and place pressing of sample stage groove or sample dispersion to drip on slide in acetone, dry the back and become film, directly detect.
The used instrument of charge-discharge test is the Land battery test system that the blue electric Electronics Co., Ltd. in Wuhan produces, and model is CT2001A, carries out the 0.2C multiplying power and carry out electro-chemical test in 0.8～2.6V scope.
Embodiment
Embodiment 1, gets 3g TiO
2Slowly add and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 3mol/L, the control temperature is 120 ℃, stirs and adds the backflow condenser pipe, reacts 24 hours, get the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 13 to pH, suction filtration, drying then, and then and 12g lithium nitrate mixed grinding, and added heat exchange 2.5 hours in 500 ℃ of following fusions, wash dry spinel lithium titanate product; As shown in Figure 1, the diameter of nano lithium titanate is approximately 8～10nm, and length is about 100nm.
Embodiment 5; get metatitanic acid 10g (industrial slurry; weight content 44.04%; benefit reaches Fine Chemical Co., Ltd and produces); slowly add and fill in the polytetrafluoroethylene reaction vessel of KOH solution that 100ml concentration is 10mol/L; place microwave oven; low fire in being set to (750W, work 10s stops 12s); mechanical agitation; add the backflow condenser pipe, reaction behind the 6h diameter be the Nano lines of potassium titanate of several nanometers, wash to pH be 7.5; and it is dry; get 20g lithium citrate and lithium chloride mixture (weight ratio is 1: 3) and dried potassium titanate/metatitanic acid composite fibre mixed grinding then, and place sintering furnace, under the nitrogen protection; 600 ℃ of fusions add heat exchange 8h, get lithium titanate-titanium dioxide compound.
Embodiment 6, get 3g TiO
2Slowly add and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L; get the nanotube sodium titanate behind the microwave heating 5h; centrifugal sedimentation and to wash to pH be that filter 13 backs; with this pastel and 4g lithium benzoate mixed grinding; under the argon shield, and behind 250 ℃ of following heat exchange 12h, get the nanotube-shaped lithium titanate of product.
Embodiment 7, get the 3g metatitanic acid; slowly add and fill in the polytetrafluoroethylcontainer container of KOH solution that 300ml concentration is 10mol/L; get the nano wire potassium titanate behind the microwave heating 5h; centrifugal sedimentation and to wash to pH be that filter 13 backs; with this pastel and 4g lithium acetate mixed grinding; under the nitrogen protection, and, get the nanometer fibrous lithium titanate of product after the washing in 150 ℃ of following heat exchange 48h.
Embodiment 8, get metatitanic acid 10g, slowly add and fill in the polytetrafluoroethylene reaction vessel of NaOH solution that 100ml concentration is 10mol/L, place microwave oven, low fire (750W in being set to, work 10s, stop 12s), mechanical agitation adds the backflow condenser pipe, reaction behind the 6h sodium titanate nanotubes, wash to pH be 13; Get the mixture (weight ratio is 1: 5: 5) and the dried presoma mixed grinding of 20g acrylic acid lithium, lithium chloride and lithium sulfate, and place sintering furnace, under the nitrogen protection, 1000 ℃ of fusions add heat exchange 30min, get the product lithium titanate.
Embodiment 9, get 3g TiO
2, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 12 to pH, suction filtration, drying then; And then and the lithium bromide of 5g grind, and add heat exchange 2h in 700 ℃ of following fusions, wash dry must the product spinel lithium titanate and the compound of titanium dioxide.
Embodiment 10, get 3g TiO
2, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 8 to pH, suction filtration, drying then; And then and the lithium phosphate of 5g grind, and add heat exchange 30min in 1000 ℃ of following fusions, wash dry must the product spinel lithium titanate and the compound of titanium dioxide.
Embodiment 11, get 3g TiO
2, slowly adding and fill in the polytetrafluoroethylcontainer container of NaOH solution that 300ml concentration is 10mol/L, the control temperature is 120 ℃, stirring also adds the backflow condenser pipe, reacts 24 hours, gets the nanotube sodium titanate, washing above-mentioned sodium titanate nanotubes is 13 to pH, suction filtration, drying then; And then and the lithium hydroxide of 5g grind, and add heat exchange 12h in 600 ℃ of following fusions, wash dry must the product spinel lithium titanate.
The chemical property of the nano lithium titanate of embodiment 2 preparations---constant current charge-discharge test:
Utilize the mixed of the black and bonding agent Kynoar (PVDF) of nano lithium titanate-titanium dioxide compound, the conductive acetylene of embodiment 2 preparation according to weight ratio 80%: 10-12%: 8-10%, with N-methyl-pyrrolidones (NMP) is solvent, fully stirring becomes pastel even, good fluidity, be coated on equably then on the Copper Foil collector, form electrode diaphragm.Be placed in the electric heating constant temperature air dry oven pole piece that coats following dry 12 hours at 110 ℃.As negative pole, use 1mol/L LiPF with metal lithium sheet
6/ (EC+DMC) be electrolyte, electrode diaphragm is assembled into simulated battery for anodal in the glove box that is full of Ar gas, carry out the constant current charge-discharge test then on the LAND test macro.As can be seen from Figure 5 this simulated battery first discharge specific capacity reaches 171mAh/g, and near theoretical value 175mAh/g, discharge platform and has charge and discharge cycles stability preferably near 1.6～1.8.
The chemical property of the nano lithium titanate of embodiment 8 preparations---constant current charge-discharge test:
Black and bonding agent Kynoar (PVDF) is according to the mixed of weight ratio 80%: 10-12%: 8-10% with nano lithium titanate, the conductive acetylene of embodiment 8 preparation, with N-methyl-pyrrolidones (NMP) is solvent, fully stirring becomes pastel even, good fluidity, be coated on equably then on the Copper Foil collector, form electrode diaphragm.Be placed in the electric heating constant temperature air dry oven pole piece that coats following dry 12 hours at 110 ℃.As negative pole, use 1mol/L LiPF with metal lithium sheet
6/ (EC+DMC) be electrolyte, electrode diaphragm is assembled into simulated battery for anodal in the glove box that is full of Ar gas, carry out the constant current charge-discharge test then on the LAND test macro.As can be seen from Figure 6 this simulated battery first discharge specific capacity reaches 160mAh/g, and discharge platform has discharge platform and charge and discharge cycles stability preferably preferably near 1.5V.
Claims (9)
1, the preparation method of the compound of a kind of nano lithium titanate that is used for battery or electrochemical vessel negative material, itself and titanium dioxide is characterized in that, may further comprise the steps:
(1), titanium-containing compound and NaOH or potassium hydroxide adds thermal response, reaction back mixed liquor cooling-sedimentation, water washing is to different pH values, dry nano barium titanate sodium or metatitanic acid-sodium titanate compound, perhaps dry nanometer potasium titanate or the metatitanic acid-potassium titanate compound of getting;
(2), the product of step (1) is mixed with inorganic lithium salt, be heated to 451～1000 ℃ of following fusion exchange reactions 30 minutes～48 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide; Perhaps with the product of step (1) under inert gas or reducibility gas, mix with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 150～1000 ℃ of fusion exchange reactions 30 minutes～48 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide.
2, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 1, itself and titanium dioxide, it is characterized in that, the product and the inorganic lithium salt of step (1) were mixed and heated to 451～700 ℃ of following fusion exchange reactions 2～12 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide.
3, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 1, itself and titanium dioxide, it is characterized in that, under inert gas or reducibility gas, the product of step (1) is mixed with the mixture of organic lithium salt or organic lithium salt and inorganic lithium salt, be heated to 250～600 ℃ of fusion exchange reactions 2～12 hours, water washing, the compound of dry nano lithium titanate or itself and titanium dioxide.
4, as the preparation method of the compound of any described nano lithium titanate that is used for battery or electrochemical vessel negative material of claim 1～3, itself and titanium dioxide, it is characterized in that, in the step (1), the reaction after washing wash to the pH value be 6～12, step (2) product is lithium titanate-titanium dioxide compound.
5, as the preparation method of the compound of any described nano lithium titanate that is used for battery or electrochemical vessel negative material of claim 1～3, itself and titanium dioxide, it is characterized in that, in the step (1), the reaction after washing wash to the pH value greater than 12.5, step (2) product is a lithium titanate.
6, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 4, itself and titanium dioxide, it is characterized in that the mol ratio of sodium titanate, potassium titanate, metatitanic acid-sodium titanate compound or metatitanic acid-potassium titanate compound and lithium salts is 1: 0.5 to 1: 20.
7, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 5, itself and titanium dioxide, it is characterized in that the mol ratio of sodium titanate, potassium titanate, metatitanic acid-sodium titanate compound or metatitanic acid-potassium titanate compound and lithium salts is 1: 0.5 to 1: 20.
8, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 6, itself and titanium dioxide, it is characterized in that described inorganic lithium salt is a kind of, two or more the combination in lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide, the lithium iodide; Described organic lithium salt is a kind of, two or more the combination in lithium formate, lithium acetate, lithium oxalate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, lithium citrate, acrylic acid lithium, lithium methoxide, the lithium ethoxide.
9, the preparation method of the compound of the nano lithium titanate that is used for battery or electrochemical vessel negative material as claimed in claim 7, itself and titanium dioxide, it is characterized in that described inorganic lithium salt is a kind of, two or more the combination in lithium hydroxide, lithia, lithium carbonate, lithium nitrate, lithium sulfate, lithium phosphate, lithium chlorate, lithium fluoride, lithium chloride, lithium bromide, the lithium iodide; Described organic lithium salt is a kind of, two or more the combination in lithium formate, lithium acetate, lithium oxalate, lithium tartrate, lithium benzoate, oleic acid lithium, lithium stearate, lithium citrate, acrylic acid lithium, lithium methoxide, the lithium ethoxide.
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