CN102515262A - Method for preparing carbon-coated nano lithium titanate by rheological phase method - Google Patents
Method for preparing carbon-coated nano lithium titanate by rheological phase method Download PDFInfo
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- CN102515262A CN102515262A CN2011104190035A CN201110419003A CN102515262A CN 102515262 A CN102515262 A CN 102515262A CN 2011104190035 A CN2011104190035 A CN 2011104190035A CN 201110419003 A CN201110419003 A CN 201110419003A CN 102515262 A CN102515262 A CN 102515262A
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 74
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 claims abstract description 52
- 239000000654 additive Substances 0.000 claims abstract description 4
- 238000000518 rheometry Methods 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 17
- 239000010936 titanium Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000005303 weighing Methods 0.000 claims description 10
- 238000000498 ball milling Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 229910003002 lithium salt Inorganic materials 0.000 claims description 5
- 159000000002 lithium salts Chemical class 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
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 3
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N Butyraldehyde Chemical compound CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 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
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 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
- 235000015110 jellies Nutrition 0.000 claims description 2
- 239000008274 jelly 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
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 claims description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000010453 quartz Substances 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000008569 process Effects 0.000 abstract description 8
- 230000000996 additive effect Effects 0.000 abstract description 2
- 238000009826 distribution Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract 1
- -1 slowly stir Substances 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 7
- 238000009413 insulation Methods 0.000 description 7
- 229910001416 lithium ion Inorganic materials 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000002904 solvent Substances 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000011029 spinel Substances 0.000 description 5
- 229910052596 spinel Inorganic materials 0.000 description 5
- 238000001354 calcination Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 230000002427 irreversible effect Effects 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
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 238000010532 solid phase synthesis reaction Methods 0.000 description 1
- 238000003836 solid-state method Methods 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000007669 thermal treatment Methods 0.000 description 1
- 230000003245 working effect Effects 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
The invention discloses a method for preparing a carbon-coated nano lithium titanate material by a rheological phase method. According to the invention, the rheological phase method is adopted, PVB is used as an additive, the particles of the prepared carbon-coated lithium titanate material are in a nanometer level, the appearance is perfect, the particle size distribution is uniform, and meanwhile, a uniform, compact and firm carbon-coated layer is formed on the surface of lithium titanate, so that the conductivity of the lithium titanate is greatly improved, and the cycle performance and the rate performance of the material are effectively improved. The preparation method is simple, the prepared material has stable performance, the process flow is simple and controllable, large-scale production can be realized, and the prepared carbon-coated nano lithium titanate material has excellent electrochemical performance and wide application prospect in the field of power batteries.
Description
Technical field
The invention belongs to the electrochemical power source technical field of material, particularly a kind of lithium ion battery negative material carbon clad nano lithium titanate (Li
4Ti
5O
12/ C) preparation method.Has wide application prospect at secondary lithium battery commonly used and power source cell negative electrode material field.
Background technology
The world today, along with global petroleum resources are nervous, the air environmental pollution aggravation, hybrid-electric car of energy-conserving and environment-protective (HEV) and pure electric automobile (EV) are current to be received people's concern especially and develops greatly.And electromobile is urgent to the increasing demand of the chemical power source of large vol, superpower, high safety.Lithium ion battery becomes one of main power resources of electromobile with advantages such as its high-energy-density, high working voltage, memory-less effects.At present, commercial lithium ion battery negative material mainly is the graphite-like carbon material.Though said material has bigger specific storage, the embedding lithium current potential that main problem is a carbon dioxide process carbon electrode and the current potential of metallic lithium are very approaching, in the large current charge process, very easily separate out Li dendrite, have potential safety hazard.Simultaneously owing to generate the SEI film on its surface in the carbon negative pole initial charge process; Not only consume a large amount of lithium salts; Cause irreversible capacity loss, and high temperature causes the SEI film destroy, the damaged material structure easily; Cause battery performance to descend, the characteristic of carbon negative pole itself can't satisfy the requirement of lithium ion battery high current charge-discharge simultaneously.
In recent years, spinel type lithium titanate Li
4Ti
5O
12Come into one's own day by day as the novel energy-storing electrode materials; This is that crystalline structure can keep stability highly in the process because spinel type lithium titanate embeds at lithium ion～deviates from; Lithium ion all is a spinel structure before and after embedding; And lattice parameter changes very little, so lithium titanate is called as " zero strain " electrode materials.This can avoid in the charge and discharge cycles since electrode materials flexible two cause structural damage back and forth; Thereby improve the cycle performance and the work-ing life of electrode; Reduced with round-robin and increased the decay that brings the specific storage amplitude, made lithium titanate have excellent cycle performance.Compare with the carbon negative pole, the lithium titanate equilibrium potential is higher, has avoided the deposition of metallic lithium; And its platform capacity surpasses 85% of total volume, and current potential rose rapidly when charging finished, and this phenomenon can be used for indication and stops charging; Avoided overcharging, so the security of lithium titanate anode is higher than carbon negative pole material; The big one magnitude of chemical diffusion coefficient ratio carbon negative pole material of lithium titanate, the speed that discharges and recharges is very fast.The lithium titanate electrode also has heavy-current discharge performance.Advantages such as simultaneously, lithium titanate also has the anti-over-charging performance and thermal stability is good, safe, and the life-span is long have broad application prospects in fields such as electromobile, energy-storage batteries.
But conventional spinel type lithium titanate Li
4Ti
5O
12Use also relatively difficulty as EV and HEV negative material, reason is that the electronic conductivity of this material is very low, thereby causes high rate performance poor.Solve at present the problem of the high rate performance difference of lithium titanate, mainly contain two class methods: the one, improve the electronic conductivity of this material; The 2nd, the material of preparation small particle size.Lithium titanate belongs to insulating material, is easy to therefore expect that the method through improving electron conduction improves its high rate performance.The high rate performance that improves lithium titanate through the raising electron conduction has had a lot of reports at home and abroad.The reason that the lithium titanate of small particle size can make it the high rate performance raising is: the migration path that can shorten Li+ of small particle size; Small particle size can increase the contact area with electrolytic solution.In order to obtain the lithium titanate material of small particle size, adopt the method for colloidal sol-gel usually.Although this method can prepare the lithium titanate material of small particle size, the preparation process is complicated, and cost is higher.Solid-phase synthesis prepares lithium titanate material, and method is easy, and cost is low; But need to adopt high calcining temperature and long calcination time usually; The result makes the lithium titanate material particle for preparing big, serious agglomeration, and this obviously is unfavorable for the raising of the high rate performance of material.Therefore, the employing method is easy, and the low synthesis method of cost prepares small particle size and hangs down the difficult point that the lithium titanate material of reuniting remains present research.
Summary of the invention
The objective of the invention is to lithium titanate Li to traditional solid state reaction preparation
4Ti
5O
12The problems such as material high rate performance difference that the electronic conductivity difference band of the bigger and pure phase lithium titanate material of material particle size comes; Provide a kind of and can improve the material high rate performance; Has excellent chemical property; And technical process is simple, the preparation method of the synthetic carbon-coated nano lithium titanate material of the rheology phase method that is easy to accomplish scale production.
The technical scheme that adopts for the present invention of realization foregoing invention purpose is following:
A kind of rheology phase legal system is equipped with the method for carbon-coated nano lithium titanate, specifically may further comprise the steps:
1) Li:Ti=(0.80～0.86) in molar ratio: 1 ratio takes by weighing lithium salts and titanium oxide, and adds 2%～25% additives polyvinyl alcohol butyral PVB of theoretical yield, and in mixing tank ball milling 6-12 hour, the mixing raw material that obtains mixing;
2) in mixing raw material, add organic solvent, slowly stir,, mixture is modulated gluey rheology attitude through regulating the ratio of PVB and organic solvent;
3) place vacuum drying oven to carry out drying again rheology attitude jelly and make presoma, drying temperature is 80～100 ℃, and be 6-12h time of drying;
4) presoma that makes after the drying is put into quartz boat, place tube furnace, the temperature rise rate with 2～10 ℃/min under inert atmosphere protection heats, under temperature 700-900 ℃ condition, and roasting 6-18 hour;
5) product after the roasting is naturally cooled to room temperature, promptly obtain the carbon-coated nano lithium titanate material.
Above-mentioned steps 1) TiO described in
2Be the anatase type nano structure; Described lithium salts is a kind of in Quilonum Retard, Lithium Hydroxide MonoHydrate, Lithium Acetate, lithium oxalate, lithium chloride and the lithium fluoride; Described organic solvent is one or more mixed solvents in methyl alcohol, ethanol, the acetone etc.
Above-mentioned steps 4) rare gas element described in is a kind of or its mixed gas in helium, argon gas and the nitrogen.
Technological merit of the present invention is:
Adopt the carbon-coated nano lithium titanate material of rheology phase method preparation; This method makes solid reactant be in the rheology state at a lower temperature; Characteristics such as strengthened the effective contact between solids, it is lower to have a synthesis temperature, and calcination time is short, particle is thin and be evenly distributed.Improve the electroconductibility of material greatly, had higher charge/discharge capacity, good high rate performance and excellent cycle performance.The inventive method raw material sources are extensive, and production technique is simple, and the preparation process is controlled easily, are easy to realize commercial scale prodn.
The additive PVB that the inventive method adds can be dissolved in the organic solvent preferably, and have better cohesiveness and film-forming properties; Through mixing, can be dispersed in uniformly between the surface and particle of material, effectively stoped the reunion between the particle, its distinctive cohesiveness can make contact more closely between the particle; When sintering, can promote that raw material fully reacts, can suppress the lithium titanate particulate again and grow up and reunite, effectively controlled the particle diameter and the pattern that finally make material product; Thermal treatment simultaneously can form evenly and the carbon coating layer of close and firm on the lithium titanate surface afterwards, and the carbon encapsulated material existence that has overcome the conventional solid-state method preparation coats the blind area, coats unequal shortcoming.
Description of drawings
Fig. 1 is the X-ray diffractogram of carbon-coated nano lithium titanate material;
Fig. 2 is the TEM figure of carbon-coated nano lithium titanate material;
Fig. 3 is first charge-discharge (0.2C) graphic representation of carbon-coated nano lithium titanate material;
Fig. 4 is carbon-coated nano lithium titanate material ground cycle performance figure under different multiplying.
Embodiment
Embodiment 1:
A, be that 0.84:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 2%) of 2wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 6 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 900 ℃, behind the insulation 12h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
Embodiment 2:
A, be that 0.83:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 6%) of 6wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 8 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 850 ℃, behind the insulation 14h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
Embodiment 3:
A, be that 0.85:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 10%) of 10wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 8 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 800 ℃, behind the insulation 16h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
Embodiment 4:
A, be that 0.84:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 12%) of 12wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 10 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 750 ℃, behind the insulation 10h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
Embodiment 5:
A, be that 0.85:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 14%) of 14wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 12 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 850 ℃, behind the insulation 12h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
Embodiment 6:
A, be that 0.84:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 16%) of 16wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 10 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 800 ℃, behind the insulation 14h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
Embodiment 7:
A, be that 0.83:1 takes by weighing Li by lithium, titanium elements mol ratio
2CO
3With Detitanium-ore-type TiO
2, and add the PVB (theoretical synthetic lithium titanate quality 18%) of 18wt%, in mixing tank with the rotating speed ball milling of 400 rev/mins of kinds 8 hours.
B, add an amount of anhydrous ethanol solvent, slowly stir, mixture is transferred to gluey rheology attitude, then in vacuum drying oven 80 ℃ obtained presoma down in dry 6-12 hour.
C, presoma is placed tube furnace, in nitrogen atmosphere, carry out temperature programming, be warmed up to 850 ℃, behind the insulation 12h, naturally cool to room temperature, promptly obtain the carbon-coated nano lithium titanate material with 5 ℃/min.
The XRD spectra of test gained material is seen Fig. 1, and the reference standard card is a spinel type lithium titanate, and the material that embodiment is obtained prepares electrode as follows and is assembled into battery, tests its electrical property.
Take by weighing the material of embodiment gained respectively with the mass ratio of 80:10:10: acetylene black: tetrafluoroethylene, process electrode after the grinding evenly, the employing microporous polypropylene membrane is a barrier film, metal lithium sheet is a negative pole, is assembled into button cell.Carry out the charge-discharge performance test with 0.2C, 1C, 5C, 10C multiplying power respectively, the charging/discharging voltage scope is 1.0-2.5V.The first charge-discharge curve (0.2C) that records the lithium titanate that embodiment 4 obtained is like Fig. 3, and the charge-discharge performance under the different multiplying is as shown in Figure 4.
The result of embodiment shows: the carbon-coated nano lithium titanate material that utilizes rheology phase method of the present invention to make; Particle diameter is little; The distribution homogeneous, the stability of product and high conformity, and the material of preparation contains evenly, perfect carbon coating layer; Conductivity is excellent, has shown excellent high rate performance and cycle performance.Preparing method of the present invention is simple simultaneously, and the material property of preparation is stable, the technical process simple controllable, can accomplish scale production, and helps commercial exploitation.
Claims (5)
1. a rheology phase legal system is equipped with the method for carbon-coated nano lithium titanate material, it is characterized in that: specifically comprise the following steps:
1) Li:Ti=(0.80～0.86) in molar ratio: 1 ratio takes by weighing lithium salts and titanium oxide, and adds 2%～25% additives polyvinyl alcohol butyral PVB of theoretical yield, and in mixing tank ball milling 6-12 hour, the mixing raw material that obtains mixing;
2) in mixing raw material, add organic solvent, slowly stir,, mixture is modulated gluey rheology attitude through regulating the ratio of PVB resin and organic solvent;
3) place vacuum drying oven to carry out drying again rheology attitude jelly, make presoma, drying temperature is 80～100 ℃, and be 6-12h time of drying;
4) presoma that makes after the drying is put into quartz boat, place tube furnace, the temperature rise rate with 2～10 ℃/min under inert atmosphere protection heats, under temperature 700-900 ℃ condition, and roasting 6-18 hour;
5) product after the roasting is naturally cooled to room temperature, promptly obtain the carbon-coated nano lithium titanate material.
2. rheology phase legal system as claimed in claim 1 is equipped with the method for carbon-coated nano lithium titanate, it is characterized in that: the lithium salts described in the step 1) is a kind of in Quilonum Retard, Lithium Hydroxide MonoHydrate, Lithium Acetate, lithium oxalate, lithium chloride, the lithium fluoride etc.
3. rheology phase legal system as claimed in claim 1 is equipped with the method for carbon-coated nano lithium titanate, it is characterized in that: the titanium oxide described in the step 1) is anatase titanium dioxide.
4. rheology phase legal system as claimed in claim 1 is equipped with the method for carbon-coated nano lithium titanate, it is characterized in that: step 2) described in organic solvent be one or more mixing in methyl alcohol, ethanol, the acetone.
5. rheology phase legal system as claimed in claim 1 is equipped with the method for carbon-coated nano lithium titanate, it is characterized in that: the inert atmosphere described in the step 4) is a kind of or its mixed gas in helium, argon gas, the nitrogen.
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| CN111183539B (en) * | 2018-09-13 | 2023-05-23 | 株式会社东芝 | Secondary battery, battery pack, vehicle, and stationary power supply |
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