CN101826615B - Preparation method of lithium ion battery nanocrystalline lithium titanate anode material - Google Patents
Preparation method of lithium ion battery nanocrystalline lithium titanate anode material Download PDFInfo
- Publication number
- CN101826615B CN101826615B CN2010101994730A CN201010199473A CN101826615B CN 101826615 B CN101826615 B CN 101826615B CN 2010101994730 A CN2010101994730 A CN 2010101994730A CN 201010199473 A CN201010199473 A CN 201010199473A CN 101826615 B CN101826615 B CN 101826615B
- Authority
- CN
- China
- Prior art keywords
- lithium
- preparation
- nanocrystalline
- liquid
- lithium titanate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 59
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 33
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 26
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 239000010405 anode material Substances 0.000 title claims abstract description 24
- 238000005245 sintering Methods 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 94
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 62
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 62
- 239000007788 liquid Substances 0.000 claims description 60
- 235000019441 ethanol Nutrition 0.000 claims description 47
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 47
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 30
- 238000003760 magnetic stirring Methods 0.000 claims description 30
- 238000003756 stirring Methods 0.000 claims description 30
- 229920001400 block copolymer Polymers 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 16
- 238000000498 ball milling Methods 0.000 claims description 14
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 11
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 11
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- 239000002245 particle Substances 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 230000015572 biosynthetic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 238000003786 synthesis reaction Methods 0.000 abstract description 5
- 238000009826 distribution Methods 0.000 abstract description 3
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract 1
- 238000000227 grinding Methods 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000007873 sieving Methods 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 14
- 239000005030 aluminium foil Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 229910052596 spinel Inorganic materials 0.000 description 3
- 239000011029 spinel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 2
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
Images
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides a preparation method of lithium ion battery nanocrystalline lithium titanate anode material, relating to a preparation method of anode. The invention overcomes the defects that synthesis temperature of the existing lithium titanate preparation method is high, sintering time is long, particle size distribution of product is nonuniform and electrochemical activity is poor. The method includes that: firstly, raw material is weighed; secondly, solution A is prepared; thirdly, solution B is prepared; fourthly, the solution A and the solution B are mixed to form transparent gel, then the gel is dried, grinding is carried out for 12 hours, sintering is carried out for 12 hours at 700 DEG C, and sieving by a 400-meshes sieve is carried out, thus obtaining lithium titanate nanocrystalline. The synthesis temperature of lithium titanate preparation method of the invention is low, reaction time is short, particle of lithium titanate is tiny, particle size is between 120nm and 140nm, and the preparation method has the prominent uniformity and high electrochemical activity.
Description
Technical field
The present invention relates to a kind of preparation method of anode.
Background technology
Spinel-type Li
4Ti
5O
12Become present research focus owing to having in excellent cycle performance, outstanding security performance, the removal lithium embedded process the little and less cost of change in volume, classified as the negative material of second generation lithium-ion-power cell by USDOE.But as lithium ion battery negative material; Spinel type lithium titanate poorly conductive (intrinsic conductivity is
); Heavy-current discharge performance is poor, and this shortcoming has seriously hindered the application of spinel type lithium titanate.Usually the preparation method plays a crucial role spinel type lithium titanate (Li to the final performance of material
4Ti
5O
12) the traditional preparation process method mainly contain high-temperature solid phase reaction method and sol-gal process.High temperature solid phase synthesis wherein, synthesis temperature is high, and sintering time is long, and energy consumption is big, and production efficiency is low, and the particle size distribution of product is inhomogeneous, and consistency and reappearance are relatively poor.Traditional sol-gel process, because very easily hydrolysis of titanium salt, the very bad control of technology, and synthetic lithium titanate poor-performing.
Summary of the invention
Goal of the invention of the present invention is in order to solve the existing method synthesis temperature height for preparing lithium titanate; Sintering time is long; The problem of the inhomogeneous and electro-chemical activity difference of the particle size distribution of product provides a kind of preparation method of lithium ion battery nanocrystalline lithium titanate anode material.
The preparation method of lithium ion battery nanocrystalline lithium titanate anode material of the present invention is following: one, 2.4～2.8g lithium acetate or 1.3～2.6g lithium hydroxide are dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get A liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, 8.8～10ml butyl titanate or 9～12ml isopropyl titanate are added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid; Under strong magnetic stirring condition, add 3g～4.25g block copolymer then; Form the phase of homogeneous, divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get B liquid; Three, under strong magnetic stirring condition, A liquid and B liquid are mixed, leave standstill 10min; Continue stirring 5～10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 48～72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, it is nanocrystalline promptly to get lithium titanate; The mass concentration of red fuming nitric acid (RFNA) described in the step 3 is 69%; The mass concentration of concentrated hydrochloric acid described in the step 3 is 37.5%; Block copolymer described in the step 3 is block copolymer P123 or block copolymer F127.
The method synthesis temperature that the present invention prepares lithium titanate is low, and the reaction time is short, and the particle of lithium titanate is tiny, particle diameter between 120nm～140nm, have outstanding all once and very high electro-chemical activity.The lithium titanate size of the present invention preparation is little, and specific area is big, and diffusion length is short, diffusion rate fast, thus the storage lithium ability of electrode material, the rapid transportation ability, capability retention all is improved largely.
Description of drawings
Fig. 1 is the SEM photo of the lithium ion battery nanocrystalline lithium titanate anode material of embodiment seven preparations; Fig. 2 is the high rate performance curve of the lithium titanate of embodiment seven preparations; The discharge curve of
expression 0.5C (electric current is 85mA/g) among the figure;
expression 1C (electric current is 170mA/g) discharge curve;
expression 3C (electric current is 510mA/g) discharge curve;
expression 5C (electric current is 850mA/g) discharge curve;
expression 10C (electric current is 1700mA/g) discharge curve,
expression 15C (electric current is 1700mA/g) charging curve.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the combination in any between each embodiment.
Embodiment one: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, 2.4～2.8g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get A liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, with in 8.8～10ml butyl titanate 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 3g～4.25g block copolymer then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get B liquid; Three, under strong magnetic stirring condition, A liquid and B liquid are mixed, leave standstill 10min; Continue stirring 5～10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 48～72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate
Embodiment two: what this execution mode and embodiment one were different is that step 1 is dissolved in 2.5g lithium acetate or 2g lithium hydroxide in the mixed liquor of 20ml second alcohol and water.Other is identical with embodiment one.
Embodiment three: what this execution mode and embodiment one were different is that step 2 is added drop-wise to 9ml butyl titanate or 10ml isopropyl titanate in the 20ml absolute ethyl alcohol.Other is identical with embodiment one.
Embodiment four: what this execution mode was different with one of embodiment one to three is that block copolymer described in the step 3 is block copolymer P123 or block copolymer F127.Other is identical with one of embodiment one to three.
Embodiment five: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.4g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get C liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 8.8ml butyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 3g block copolymer P123 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get D liquid; Three, under strong magnetic stirring condition, C liquid and D liquid are mixed, leave standstill 10min; Continue stirring 5min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 48h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment six: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.8g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get C liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 10ml butyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 3g block copolymer P123 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get D liquid; Three, under strong magnetic stirring condition, C liquid and D liquid are mixed, leave standstill 10min; Continue stirring 10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment seven: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.5g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get C liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 9ml butyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 3g block copolymer P123 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get D liquid; Three, under strong magnetic stirring condition, C liquid and D liquid are mixed, leave standstill 10min; Continue stirring 8min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 60h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
It is tiny to find out that by Fig. 1 this execution mode prepares the particle of lithium titanate, particle diameter between 120nm～140nm, have outstanding all once.
With the lithium ion cell nano anode lithium titanate electrode material of this execution mode gained according to following method assemble: one, with NMP (N-methyl pyrrolidone; Mass concentration is 99%) be solvent; Lithium titanate: acetylene black: Kynoar (PVDF) mixes according to the mass ratio of 80:10:10; 6h mixes well into paste with magnetic stirrer, then paste is coated on the aluminium foil, aluminium foil is dried by the fire in 100 ~ 110 ℃ vacuum drying chamber took out aluminium foil in 12 hours; Two, will pass through then aluminium foil that step 1 handles use mould be washed into diameter as the 14mm disk as anode; With the metal lithium sheet is negative pole; Electrolyte is made up of LiPF6, ethylene carbonate and carbonic acid diethyl ester that (LiPF6 concentration is 1mol/L in the electrolyte; The volume ratio of ethylene carbonate and carbonic acid diethyl ester is 1:1), barrier film is the Celgard2400 microporous polypropylene membrane, in being full of the glove box of argon gas, is assembled into 2025 type button cells.
The nanocrystalline lithium titanate that as can be seen from Figure 2 prepares in this execution mode has very high electro-chemical activity.
Embodiment eight: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 1.3g lithium hydroxide is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get E liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 9ml isopropyl titanate is added drop-wise in the 20ml absolute ethyl alcohol, adding 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid add 3g block copolymer P123 then under strong magnetic stirring condition, form the phase of homogeneous, divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get F liquid; Three, under strong magnetic stirring condition, E liquid and F liquid are mixed, leave standstill 10min; Continue stirring 5min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 48h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment nine: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.6g lithium hydroxide is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get E liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 12ml isopropyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 3g block copolymer P123 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get F liquid; Three, under strong magnetic stirring condition, E liquid and F liquid are mixed, leave standstill 10min; Continue stirring 10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment ten: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.0g lithium hydroxide is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get E liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 10ml isopropyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 3g block copolymer P123 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get F liquid; Three, under strong magnetic stirring condition, E liquid and F liquid are mixed, leave standstill 10min; Continue stirring 8min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 68h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
The specific embodiment 11: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in the present embodiment: one, the 1.3g lithium hydroxide is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get G liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 8.8ml butyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 4.25g block copolymer F127 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get H liquid; Three, under strong magnetic stirring condition, G liquid and H liquid are mixed, leave standstill 10min; Continue stirring 5min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 50h; Form transparent gel; Then gel is dried 12h in 120 ℃ vacuum drying chamber, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment 12: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.6g lithium hydroxide is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get G liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 10ml butyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 4.25g block copolymer F127 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get H liquid; Three, under strong magnetic stirring condition, G liquid and H liquid are mixed, leave standstill 10min; Continue stirring 10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment 13: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2g lithium hydroxide is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get G liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 9.2ml butyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 4.25g block copolymer F127 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get H liquid; Three, under strong magnetic stirring condition, G liquid and H liquid are mixed, leave standstill 10min; Continue stirring 6min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 66h; Form transparent gel, then gel dried 12h in 120 ℃ vacuum drying chamber,, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment 14: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.4g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get I liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 9ml isopropyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 4.25g block copolymer F127 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get J liquid; Three, under strong magnetic stirring condition, I liquid and J liquid are mixed, leave standstill 10min; Continue stirring 5min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 48h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment 15: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.8g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get I liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 12ml isopropyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 4.25g block copolymer F127 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get J liquid; Three, under strong magnetic stirring condition, I liquid and J liquid are mixed, leave standstill 10min; Continue stirring 10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Embodiment 16: the preparation method of lithium ion battery nanocrystalline lithium titanate anode material is following in this execution mode: one, the 2.6g lithium acetate is dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get I liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, the 10ml isopropyl titanate is added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid, under strong magnetic stirring condition, add 4.25g block copolymer F127 then, form the phase of homogeneous; Divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get J liquid; Three, under strong magnetic stirring condition, I liquid and J liquid are mixed, leave standstill 10min; Continue stirring 8min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 70h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, promptly get lithium titanate.
Claims (4)
1. the preparation method of lithium ion battery nanocrystalline lithium titanate anode material; The preparation method who it is characterized in that lithium ion battery nanocrystalline lithium titanate anode material is following: one, 2.4～2.8g lithium acetate or 1.3～2.6g lithium hydroxide are dissolved in the mixed liquor of 20ml second alcohol and water; Stir 10min; Get A liquid, the volume ratio of ethanol and water is 3:1 in the mixed liquor of second alcohol and water; Two, 8.8～10ml butyl titanate or 9～12ml isopropyl titanate are added drop-wise in the 20ml absolute ethyl alcohol; Add 2ml red fuming nitric acid (RFNA) or 2ml concentrated hydrochloric acid; Under strong magnetic stirring condition, add 3g～4.25g block copolymer then; Form the phase of homogeneous, divide four times again and add 4ml red fuming nitric acid (RFNA) or 4ml concentrated hydrochloric acid, get B liquid; Three, under strong magnetic stirring condition, A liquid and B liquid are mixed, leave standstill 10min; Continue stirring 5～10min, is that 40 ℃, humidity are under 60% the condition in temperature then, cultivates 48～72h; Form transparent gel, then gel is dried 12h in 120 ℃ vacuum drying chamber, ball milling 12h; 700 ℃ of following sintering 12 hours, cross 400 mesh sieves then, it is nanocrystalline promptly to get lithium titanate.
2. according to the preparation method of the said lithium ion battery nanocrystalline lithium titanate anode material of claim 1, it is characterized in that step 1 is dissolved in 2.5g lithium acetate or 2g lithium hydroxide in the mixed liquor of 20ml second alcohol and water.
3. according to the preparation method of the said lithium ion battery nanocrystalline lithium titanate anode material of claim 1, it is characterized in that step 2 is added drop-wise to 9ml butyl titanate or 10ml isopropyl titanate in the 20ml absolute ethyl alcohol.
4. according to the preparation method of claim 1,2 or 3 said lithium ion battery nanocrystalline lithium titanate anode materials, it is characterized in that block copolymer described in the step 2 is block copolymer P123 or block copolymer F127.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101994730A CN101826615B (en) | 2010-06-13 | 2010-06-13 | Preparation method of lithium ion battery nanocrystalline lithium titanate anode material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101994730A CN101826615B (en) | 2010-06-13 | 2010-06-13 | Preparation method of lithium ion battery nanocrystalline lithium titanate anode material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101826615A CN101826615A (en) | 2010-09-08 |
| CN101826615B true CN101826615B (en) | 2012-05-23 |
Family
ID=42690407
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101994730A Expired - Fee Related CN101826615B (en) | 2010-06-13 | 2010-06-13 | Preparation method of lithium ion battery nanocrystalline lithium titanate anode material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101826615B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10106431B2 (en) * | 2013-04-12 | 2018-10-23 | Tsinghua University | Method for making anode active material of lithium ion battery |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105390690B (en) * | 2015-10-20 | 2017-12-22 | 合肥工业大学 | A kind of ultra-thin Li of surfactant auxiliary4Ti5O12The preparation method of nanometer sheet and its application method in lithium battery and sode cell |
| CN110429324A (en) * | 2019-08-05 | 2019-11-08 | 安徽相源新能源有限公司 | A kind of preparation method of the modified compound lithium cell of high capacity |
| CN112185642A (en) * | 2020-09-23 | 2021-01-05 | 江西艾特磁材有限公司 | Method for coating magnetic powder core with ball milling modified sol-gel |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101593830A (en) * | 2009-07-03 | 2009-12-02 | 郑州大学 | The preparation method of lithium ionic cell cathode material spinelle lithium titanate |
-
2010
- 2010-06-13 CN CN2010101994730A patent/CN101826615B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101593830A (en) * | 2009-07-03 | 2009-12-02 | 郑州大学 | The preparation method of lithium ionic cell cathode material spinelle lithium titanate |
Non-Patent Citations (2)
| Title |
|---|
| Chunhai Jiang et.al.Effect of particle dispersion on high rate performance of nano-sized Li4Ti5O12 anode.《Electrochimica Acta》.2007,第52卷6470-6475. * |
| 王瑾等.高分散纳米晶Li4Ti5O12电极材料的制备及电化学性能的研究.《无机材料学报》.2010,第25卷(第3期),235-241. * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10106431B2 (en) * | 2013-04-12 | 2018-10-23 | Tsinghua University | Method for making anode active material of lithium ion battery |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101826615A (en) | 2010-09-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103066280B (en) | spherical lithium iron phosphate anode material and preparation method thereof | |
| CN102969489B (en) | A kind of Si-C composite material and preparation method thereof, lithium ion battery containing this material | |
| CN105355880B (en) | A kind of LiFePO4/ C is modified the preparation method of tertiary cathode material | |
| CN102306759B (en) | Silicon monoxide composite cathode material for lithium ion battery, and preparation method thereof | |
| CN102169996B (en) | Micro-sphere compound anode material with core-shell structure and preparation method thereof | |
| CN103280574A (en) | Lithium-enriched ternary anode material of power lithium-ion battery and preparation method of lithium-enriched ternary anode material | |
| CN107069020A (en) | A kind of preparation method of lithium ion battery nickel doping vanadic anhydride nano-sheet positive electrode | |
| CN103151528A (en) | Method for preparing aluminum-doped zinc oxide coated lithium-ion battery positive-pole material | |
| CN101719546A (en) | Method for preparing lithium ion battery anode material doped with nanometer oxide | |
| CN113948681B (en) | Biomass-based hard carbon compound composite material and preparation method and application thereof | |
| CN103560243A (en) | Preparation method for synthesizing LiNi1/3Co1/3Mn1/3O2 nanometer fiber by using electro-spinning technique | |
| CN101967055A (en) | Method for preparing Co-Ni-Mn ternary anode materials by microwave sintering | |
| CN108110324A (en) | A kind of preparation method of solid lithium ion battery | |
| CN107200358A (en) | A kind of iron system CuFe for sodium-ion battery2O4The preparation method of material | |
| CN101826615B (en) | Preparation method of lithium ion battery nanocrystalline lithium titanate anode material | |
| CN103390748A (en) | Preparation method for cladding lithium cobaltoxide cathode material with alumina | |
| CN108054350A (en) | Lithium-sulfur battery composite cathode material and preparation method thereof | |
| CN105185978A (en) | Manganese-containing oxygen compound used as negative active substance, and preparation method and use thereof | |
| CN106784657A (en) | A kind of method that sodium and iron codope prepare High-performance lithium manganate anode material | |
| CN107946564A (en) | Rich sodium manganese base Na4Mn2O5/Na0.7MnO2Composite material and its preparation method and application | |
| CN103094557A (en) | Preparing method for lithium ion cell anode material with surface coated with ZnO | |
| CN104425816A (en) | Lithium ion battery cathode active material, lithium ion battery cathode material and lithium ion power battery | |
| CN111816924A (en) | Preparation method of lithium manganate battery | |
| CN1562771A (en) | Spherical shaped lithium manganate and preparation method | |
| CN102723478A (en) | Octahedral lithium manganate micron single crystal electrode material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU FIRST NEW ENERGY CO., LTD. Free format text: FORMER OWNER: HARBIN INDUSTRY UNIVERSITY Effective date: 20130516 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 150001 HARBIN, HEILONGJIANG PROVINCE TO: 225300 TAIZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20130516 Address after: 225300 Taizhou Road, Binjiang Industrial Park, Jiangsu 18, China Patentee after: Jiangsu First New Energy Co., Ltd. Address before: 150001 Harbin, Nangang, West District, large straight street, No. 92 Patentee before: Harbin Institute of Technology |
|
| ASS | Succession or assignment of patent right |
Owner name: JIANGSU ZHIHANG NEW ENERGY CO., LTD. Free format text: FORMER OWNER: JIANGSU FIRST NEW ENERGY CO., LTD. Effective date: 20150311 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| COR | Change of bibliographic data |
Free format text: CORRECT: ADDRESS; FROM: 225300 TAIZHOU, JIANGSU PROVINCE TO: 225321 TAIZHOU, JIANGSU PROVINCE |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20150311 Address after: 225321, No. 213, long Garden Road, new energy industrial park, Jiangsu, Taizhou Patentee after: JIANGSU ZHIHANG NEW ENERGY CO., LTD. Address before: 225300 Taizhou Road, Binjiang Industrial Park, Jiangsu 18, China Patentee before: Jiangsu First New Energy Co., Ltd. |
|
| PP01 | Preservation of patent right | ||
| PP01 | Preservation of patent right |
Effective date of registration: 20190507 Granted publication date: 20120523 |
|
| PD01 | Discharge of preservation of patent | ||
| PD01 | Discharge of preservation of patent |
Date of cancellation: 20210507 Granted publication date: 20120523 |
|
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20120523 Termination date: 20190613 |