CN109279650A - The method that growth in situ prepares lithium titanate in metallic titanium powder fused salt - Google Patents
The method that growth in situ prepares lithium titanate in metallic titanium powder fused salt Download PDFInfo
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- CN109279650A CN109279650A CN201811399374.XA CN201811399374A CN109279650A CN 109279650 A CN109279650 A CN 109279650A CN 201811399374 A CN201811399374 A CN 201811399374A CN 109279650 A CN109279650 A CN 109279650A
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- lithium titanate
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/003—Titanates
- C01G23/005—Alkali titanates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
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Abstract
The invention belongs to lithium ion battery negative material fields in electrochmical power source, and in particular to the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt.Technical problem to be solved by the invention is to provide the methods that growth in situ in metallic titanium powder fused salt prepares lithium titanate, comprising the following steps: metal Ti, Li2CO3, NaCl and KCl mix gained mixture in 800~850 DEG C of oxidizing roastings, obtain lithium titanate after roasting.The method of the present invention not only contributes to form the uniform lithium titanate material of microscopic appearance, while being conducive to improve the chemical property of lithium titanate material.
Description
Technical field
The invention belongs to lithium ion battery negative material fields in electrochmical power source, and in particular in situ in metallic titanium powder fused salt
The method that growth prepares lithium titanate.
Background technique
Molten salt method for synthesizing, using alkali metal salt, alkaline-earth halide salt, nitrate etc. as reaction medium, high temperature item
Part temperature is in liquid phase molten state after reaching fused salt fusing point, has ionic liquid phase liquid reactions characteristic, and synthesis technology is simple, between
Synthetic method between solid phase and liquid phase has both solution phase and solid phase synthesis method advantage.After pyroreaction, it is cooled to room
Temperature removes recycled fused-salt medium using distilled water, obtains target synthetic product.Lithium titanate is synthesized using molten-salt growth method
(Li4Ti5O12), in high-temperature reaction process, titanium source may be implemented molecular scale with lithium source and mix, the reaction of molecular scale, more
The shortcomings that mending pure solid phase reaction, after the completion of synthetic reaction, the lithium titanate particle of generation is dispersed in the fused salt of molten condition, is inhibited
Its particle secondary is grown up and intergranular reunion, and the excellent micron order Li of dispersibility can be synthesized4Ti5O12Particle.
It is existing using molten-salt growth method prepare lithium titanate material method substantially steps are as follows: with molar ratio be 0.05 ﹕, 0.1 ﹕ 0.1
LiNO3, LiOH and Li2O2As mixing lithium source, with Ti [O (CH2)3CH3]4As titanium source, by above-mentioned lithium salt mixture in Ma
After being sufficiently mixed in Nao mortar, the Ti [O (CH of 0.5mol is dripped2)3CH3]4Slurry is formed, is dried in vacuo at 120 DEG C and obtains for 24 hours
To powdered substance, then vacuum drying powder product shape substance is put into Muffle furnace in 300 DEG C of roasting 3h, 400 DEG C of roastings
3h, 500 DEG C of roasting 3h, to obtain lithium titanate.This method is to keep lithium titanate product microscopic appearance uniform, and grain size is consistent,
Select liquid phase organic titanium source Ti [O (CH2)3CH3]4As initial feed, LiNO3、LiOH·H2O and Li2O2It is mixed as eutectic point
Fused salt keeps its original mixture more sensitive to moisture, it is desirable that water reduces as far as possible in initial feed, increases material preparation process
Difficulty, and Ti, Li ratio is caused to be not easy to be precisely controlled, contain TiO in the lithium titanate material of production2Phase.
Summary of the invention
Technical problem to be solved by the invention is to provide growth in situ in a kind of metallic titanium powder fused salt to prepare lithium titanate
Method.Method includes the following steps: metal Ti, Li2CO3, NaCl and KCl mix gained mixture and aoxidize at 800~850 DEG C
Roasting, obtains lithium titanate after roasting.
Preferably, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, the granularity of the metal Ti
For the screenings for crossing 120 mesh screens.
Preferably, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, and the NaCl and KCl's rubs
You are than being 1 ﹕ 1.
Preferably, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, the NaCl and KCl addition
Amount is Ti and Li2CO33~5 times of gross mass.
Preferably, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, the metal Ti and Li2CO3
In lithium molar ratio be 5~6 ﹕ 4.
Further, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, the metal Ti with
Li2CO3In lithium molar ratio be 6 ﹕ 4,5.5 ﹕ 4 or 5 ﹕ 4.
Specifically, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, the oxidizing roasting atmosphere
For air atmosphere or oxygen atmosphere.It is preferred that oxidizing roasting ambient air atmosphere.
Further, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, and the air velocity is
Guarantee system has enough oxygen to be aoxidized.Flow velocity is 0.5~1.8m under the conditions of optimization experiment room3/h。
Specifically, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, the calcining time is 6~
8h。
Specifically, growth in situ is prepared in the method for lithium titanate in above-mentioned metallic titanium powder fused salt, after the roasting also
Including removing fused salt step.The fused salt is NaCl and KCl.The removing fused salt is the following steps are included: after roasting
In material plus water is impregnated, is filtered, washed, is dried.
The method of the present invention utilizes its growth in situ in NaCl-KCl fused salt mixt using metallic titanium powder as initial titanium source
Lithium titanate material is prepared, not only contributes to form the uniform lithium titanate material of microscopic appearance, while being conducive to improve lithium titanate
The chemical property of material.
Detailed description of the invention
The XRD comparison diagram of Fig. 1, the method for the present invention and simple molten-salt growth method preparation gained lithium titanate；LTO-Ti indicates the present invention
Method preparation gained lithium titanate；LTO-S indicates simple molten-salt growth method preparation gained lithium titanate；Simple molten-salt growth method refers to NaCl and KCl
As fused salt, titanium dioxide synthesizes the side of lithium titanate under the conditions of about 800 DEG C of temperature as lithium source as titanium source, lithium carbonate
Method.
The TEM figure of Fig. 2, the method for the present invention preparation gained lithium titanate；
The electrochemical properties figure of Fig. 3, the method for the present invention preparation gained lithium titanate and simple molten-salt growth method preparation gained lithium titanate；
LTO-Ti indicates the method for the present invention preparation gained lithium titanate；LTO-S indicates simple molten-salt growth method preparation gained lithium titanate.
Specific embodiment
The method that growth in situ prepares lithium titanate in metallic titanium powder fused salt of the present invention, comprising the following steps: metal Ti powder is made
For titanium source, Li2CO3As lithium source, titanium source and lithium source are put into after ground and mixed is uniform in mortar again and as fused salt mixt
NaCl-KCl is uniformly mixed, and mixture is put into silica crucible, is held in vertical single temperature zone vacuum atmosphere tube furnace, to earthenware
It is inserted into long quartz ampoule in crucible and is passed through air or oxygen, on the one hand effect is that agitation molten salt system fills it to the air or oxygen being passed through
Divide reaction, on the other hand effect is that metal Ti powder is made to have sufficient oxygen generation oxidation reaction in the synthesis process, then system
In 800~850 DEG C of 6~8h of oxidizing roasting, the post-processing steps such as roasting is dissolved in water after terminating, is filtered, washed, dries are removed
Fused salt obtains lithium titanate powder.
In the above method, since titanium valve has high reaction activity during the reaction, control titanium valve is excessive.The metal Ti
With Li2CO3In lithium molar ratio be 5~6 ﹕ 4.Preferred molar ratio is 6 ﹕ 4,5.5 ﹕ 4 or 5 ﹕ 4.
In the above method, in order to guarantee the safety of roasting, preferably calcination atmosphere is air.Being passed through air guarantee has abundance
Oxygen carry out oxidation reaction.
In the above method, as fused salt mixt NaCl-KCl be added when be solid, gradate during heating for
Molten state, to play the role of fused salt.It is preferred that fused salt NaCl-KCl additive amount is Ti and Li2CO33~5 times of gross mass.
The molar ratio of NaCl and KCl is 1 ﹕ 1.
Embodiment 1
Weigh 1.22g metallic titanium powder, 0.62g Li2CO3(molar ratio Ti ﹕ Li=6 ﹕ 4) be put into mortar grind 20min with
Uniformly mixing, then the NaCl-KCl fused salt mixt of 1 ﹕ 1 of 7g molar ratio is weighed, it is uniformly mixed again using mortar.By fused salt with before
The mixture for driving body is put into silica crucible, is held in vertical single temperature zone vacuum atmosphere tube furnace, and long quartz is inserted into crucible
Pipe is to be passed through enough air, 800 DEG C of sintering 6h.When fire box temperature is cooled to room temperature reaction terminate, take out crucible be placed in from
In sub- water, the fused salt mixt being dipped in crucible is separated with crucible, then by subsequent processing steps such as washing, filterings, removal is mixed
Fused-salt medium is closed, after drying 12h in a vacuum drying oven, obtains lithium titanate powder.
Embodiment 2
Weigh 2.14g metallic titanium powder, 1.2gLi2CO3(molar ratio Ti ﹕ Li=5.5 ﹕ 4), be put into mortar grind 20min with
Uniformly mixing, then the NaCl-KCl fused salt mixt of 1 ﹕ 1 of 15g molar ratio is weighed, it is uniformly mixed again using mortar.By fused salt with before
The mixture for driving body is put into silica crucible, is held in vertical single temperature zone vacuum atmosphere tube furnace, and long quartz is inserted into crucible
Pipe is to be passed through enough air, 850 DEG C of sintering 8h.When fire box temperature is cooled to room temperature reaction terminate, take out crucible be placed in from
In sub- water, the fused salt mixt being dipped in crucible is separated with crucible, then by subsequent processing steps such as washing, filterings, removal is mixed
Fused-salt medium is closed, after drying 12h in a vacuum drying oven, obtains lithium titanate powder.
Claims (10)
1. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt, it is characterised in that: the following steps are included: metal Ti,
Li2CO3, NaCl and KCl mix gained mixture in 800~850 DEG C of oxidizing roastings, obtain lithium titanate after roasting.
2. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 1, it is characterised in that: institute
The granularity for stating metal Ti was the screenings of 120 mesh screens.
3. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 1, it is characterised in that: institute
The molar ratio for stating NaCl and KCl is 1 ﹕ 1.
4. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 1 or 3, feature exist
In: NaCl the and KCl additive amount is Ti and Li2CO33~5 times of gross mass.
5. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 1, it is characterised in that: institute
State metal Ti and Li2CO3In lithium molar ratio be 5~6 ﹕ 4.
6. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 5, it is characterised in that: institute
State metal Ti and Li2CO3In lithium molar ratio be 6 ﹕ 4,5.5 ﹕ 4 or 5 ﹕ 4.
7. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 1, it is characterised in that: institute
Stating oxidizing roasting atmosphere is air atmosphere or oxygen atmosphere；It is preferred that the oxidizing roasting atmosphere is air atmosphere.
8. the method that growth in situ prepares lithium titanate in described in any item metallic titanium powder fused salts according to claim 1~7, special
Sign is: the calcining time is 6~8h.
9. the method that growth in situ prepares lithium titanate in described in any item metallic titanium powder fused salts according to claim 1~8, special
Sign is: further including removing fused salt step after the roasting.
10. the method that growth in situ prepares lithium titanate in metallic titanium powder fused salt according to claim 9, it is characterised in that:
It is described remove fused salt the following steps are included: roasting after material in plus water impregnated, be filtered, washed, dried.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201811399374.XA CN109279650A (en) | 2018-11-22 | 2018-11-22 | The method that growth in situ prepares lithium titanate in metallic titanium powder fused salt |
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| CN201811399374.XA CN109279650A (en) | 2018-11-22 | 2018-11-22 | The method that growth in situ prepares lithium titanate in metallic titanium powder fused salt |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624212A (en) * | 2008-07-10 | 2010-01-13 | 上海比亚迪有限公司 | Preparation method for lithium titanate composite material |
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- 2018-11-22 CN CN201811399374.XA patent/CN109279650A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101624212A (en) * | 2008-07-10 | 2010-01-13 | 上海比亚迪有限公司 | Preparation method for lithium titanate composite material |
Non-Patent Citations (1)
| Title |
|---|
| WEI-WEI MENG等: "In situ nano-sized spinel Li4Ti5O12 powder fabricated by a one-step roasting process in molten salts", 《JOURNAL OF ALLOYS AND COMPOUNDS》 * |
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Application publication date: 20190129 |