CN107324379A - A kind of high power capacity lithium titanate material preparation method - Google Patents
A kind of high power capacity lithium titanate material preparation method Download PDFInfo
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- CN107324379A CN107324379A CN201710526344.XA CN201710526344A CN107324379A CN 107324379 A CN107324379 A CN 107324379A CN 201710526344 A CN201710526344 A CN 201710526344A CN 107324379 A CN107324379 A CN 107324379A
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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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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/485—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of mixed oxides or hydroxides for inserting or intercalating light metals, e.g. LiTi2O4 or LiTi2OxFy
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- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/11—Powder tap density
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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- C01P2006/40—Electric properties
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- 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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Abstract
The present invention relates to a kind of high power capacity lithium titanate material preparation method.The problem of lithium titanate material capacity is small in being produced present invention mainly solves existing technology at present.Specific method is：By lithium source, titanium source, fluxing agent and dispersant ball mill mixing by a certain percentage, low temperature presintering after drying, high-temperature calcination generates lithium titanate after cooling.The invention is characterized in that adding fluxing agent in mixing process, in high-temperature sintering process, the interfacial tension between the closer of particle contact, reduction particle can be made, crystal growth development is more intact, and then improves material volume density.This method technological process is simple, and raw material is easy to get, and the lithium titanate particle of preparation is big, capacity is high, and chemical property is good.
Description
Technical field
The present invention relates to the preparation field of energy and material, more particularly to a kind of system of lithium ionic cell cathode material lithium titanate
Preparation Method.
Background technology
Lithium ion battery because energy density is high, have extended cycle life, memory-less effect the advantages of, be always that field of batteries is ground
Study carefully the focus of exploitation, be applied in fields such as portable electronics, electric automobile, energy storage and have a good application prospect.At present,
The lithium ion battery negative material of commercialization typically uses carbon negative pole material, but carbon negative pole material is due to its oxidation-reduction potential
With the electrode potential of lithium closely, lithium ion separates out on Carbon anode surface and easily forms Li dendrite during over-charging of battery, is likely to result in
Battery short circuit and trigger safety problem, and carbon material can with nonaqueous electrolytic solution formation SEI films irreversible capacity is increased.And
Due to it, the skeleton structure during Lithium-ion embeding and abjection hardly changes lithium titanate with spinel structure, is a kind of
" zero strain " material, and intercalation potential is higher, will not cause Li dendrite, improves the security performance of battery.Its high security
And the advantages of the long-life be always the focus of research as novel anode material.
But lithium titanate also has weak point, the lithium titanate material obtained in existing research is small due to accumulation capacity, causes
Battery energy density is low, limits the application of lithium titanate, thus improve material tap density be lithium titanate main direction of studying it
One.
Patent CN201010177934.4 discloses a kind of preparation method of spherical lithium titanate, and this method can improve material
Tap density, but the method has particular/special requirement to equipment, and technical process is numerous and diverse so that production cost substantially increases.
The content of the invention
To solve the above problems, the present invention provides a kind of high power capacity lithium titanate material preparation method, this method raw material is inexpensive
It is easy to get, due to adding fluxing agent so that process operation is simple, the material property of synthesis is good.Concrete scheme is as follows：
A kind of high power capacity lithium titanate material preparation method, its step is as follows：
1) lithium source, titanium source, fluxing agent and dispersant are mixed, 1~8h of ball mill mixing；
2) said mixture is placed in vacuum drying oven be passed through oxygen content be 0.01%~21.6% gas, in 0 DEG C~
After being dried at 100 DEG C, 2~10h of pre-burning in the case where 300~800 DEG C of oxygen content is 0.01%~50% atmosphere；
3) after the cooling of pre-burning product, 4~20h is calcined in the case where 600~900 DEG C of oxygen content is 0.01%~99% atmosphere,
Obtain product Li4Ti5O12.
Wherein, step 1) in Li/Ti=0.76~0.86；Dispersant and solid content (total matter of lithium source, titanium source and fluxing agent
Amount) mass ratio be 0.5~1.5：1；Flux content is 0.1~5wt% of titanium dioxide quality.
Lithium source wherein of the present invention is one kind in lithium carbonate, lithium hydroxide or lithium nitrate；Titanium source is anatase titanium dioxide or gold
Red stone-type titanium dioxide；Fluxing agent be sodium tetraborate, Firebrake ZB, boric acid, lithium tetraborate, lithium hydroxide, lithium acetate, sodium carbonate,
One or more mixtures in lithium carbonate, lithium fluoride or vanadic anhydride,；Dispersant is in water, ethanol, methanol or acetone
One or more mixtures.
The present invention's is mainly characterized by：
The present invention adds fluxing agent in the feed, and batch mixing is sintered into lithium titanate material again after drying, and the process is simple, it is easy to
Operation, cost are effectively controlled.
The present invention at high temperature better contacts with two kinds of raw materials by adding fluxing agent, reduces the growth of crystal
Temperature, shortens crystal growth time, improves tap density, is sintered for a long time compared to conventional method high temperature, reduces energy consumption,
The loss of equipment is decreased, industrial production application is easier to.
Lithium titanate particle obtained by present invention preparation is big, and capacity is more than 1.2g/cm3, and 0.1C charge specific capacities are more than
160mAh/g。
On the basis of lithium titanate prepared by the method, ion doping or carbon coating can also be carried out, be can further improve
The electric conductivity of material.
Brief description of the drawings
Fig. 1 is the SEM figures of the lithium titanate prepared by the embodiment of the present invention three；
Fig. 2 is the first charge-discharge curve map of the lithium titanate prepared by the embodiment of the present invention three.
Embodiment
It is described in more detail with reference to the embodiment preparation method for improving lithium titanate tap density a kind of to the present invention.
But the present invention is not limited to following examples.
Embodiment one
It is raw material from lithium carbonate, anatase titanium dioxide, lithium fluoride is fluxing agent, is by Li/Ti (mol%) ratio
0.80：1st, fluorination lithium content carries out dispensing, using ethanol as dispersant, ethanol for the 1wt% of TiO2 mass：Solid powder (wt%)
=0.7：1, the ball milling after 6 hours on ball mill is passed through dry presoma at oxygen-containing 21.6% 40 DEG C of gas in baking oven.
By presoma in elder generation is at 500 DEG C under the atmosphere of oxygen content 10%, high-temperature process 2 hours is warming up to 800 DEG C, Yu Han after cooling
8 hours are incubated under the atmosphere of oxygen amount 21.6%, is finally down to after room temperature and obtains Li4Ti5O12 samples.Resulting materials granular size is equal
One, tap density 1.20g/cm3, the lithium titanate tap density prepared with being not added with fluxing agent under other identical conditions
(0.78g/cm3) is compared, and density is significantly improved.Using metal lithium sheet to prepare button cell to electrode, material 0.1C charging specific volumes
Measure as 165mAh/g.
Embodiment two
It is raw material from lithium nitrate, rutile titanium dioxide, boric acid is fluxing agent, is by Li/Ti (mol%) ratio
0.82：1st, boric acid content carries out dispensing, using ethanol as dispersant, ethanol for the 0.5wt% of TiO2 mass：Solid powder (wt%)
=0.8：1 on ball mill ball milling after 6 hours, dry presoma at oxygen-containing 0.1% 60 DEG C of gas is passed through in baking oven.Will
Presoma is in elder generation is at 500 DEG C under the atmosphere of oxygen content 0.01%, and high-temperature process 2 hours is warming up to 800 DEG C in oxygen-containing after cooling
8 hours are incubated under the atmosphere of amount 99%, is finally down to after room temperature and obtains Li4Ti5O12 samples.Resulting materials particle is round and smooth, size is equal
One, tap density is 1.36g/cm3, the lithium titanate tap density prepared with being not added with fluxing agent under other identical conditions
(0.80g/cm3) is compared, and density is significantly improved.Using metal lithium sheet to prepare button cell, the 0.1C charge ratios of material to electrode
Capacity is 161mAh/g.
Embodiment three
It is raw material from lithium hydroxide, anatase titanium dioxide, lithium tetraborate is fluxing agent, is by Li/Ti (mol%) ratio
0.84：Lithium tetraborate content carries out dispensing, using methanol as dispersant, methanol for the 0.5wt% of TiO2 mass：Solid powder
(wt%)=1：1 on ball mill ball milling after 6 hours, dry forerunner at oxygen-containing 21.6% 50 DEG C of gas is passed through in baking oven
Body.By presoma in elder generation is at a temperature of 500 DEG C under the atmosphere of oxygen content 21.6%, high-temperature process 2 hours is warming up to after cooling
800 DEG C, in being incubated 8 hours under the atmosphere of oxygen content 0.1%, are finally down to after room temperature and obtain Li4Ti5O12 samples.Resulting materials
The round and smooth, size of grain is homogeneous, and tap density is 1.48g/cm3, the titanium prepared with being not added with fluxing agent under other identical conditions
Sour lithium tap density (0.82g/cm3) is compared, and density is significantly improved.Using metal lithium sheet to prepare button cell, material to electrode
0.1C charge specific capacities be 160mAh/g.
Example IV
It is raw material from lithium hydroxide, anatase titanium dioxide, vanadic anhydride is fluxing agent, is by Li/Ti ratios
(mol%) 0.84：Pentoxide content carries out dispensing, using acetone as dispersant, acetone for the 1wt% of TiO2 mass：Solid
Powder (wt%)=0.8：1 on ball mill ball milling after 6 hours, be passed through in baking oven dry at oxygen-containing 10% 50 DEG C of gas
Presoma.By presoma in first at a temperature of 500 DEG C under the atmosphere of oxygen content 21.6%, high-temperature process 2 hours, heating after cooling
To 750 DEG C in being incubated 8 hours under the atmosphere of oxygen content 99%, finally it is down to after room temperature and obtains Li4Ti5O12 samples.Resulting materials
The round and smooth, size of grain is homogeneous, and tap density is 1.25g/cm3, the titanium prepared with being not added with fluxing agent under other identical conditions
Sour lithium tap density (0.84g/cm3) is compared, and density is significantly improved.Using metal lithium sheet to prepare button cell, material to electrode
0.1C charge specific capacities be 163mAh/g.
Claims (9)
1. a kind of preparation method of high power capacity lithium titanate material, it is characterised in that following steps：
1) lithium source, titanium source, fluxing agent and dispersant are mixed, 1~8h of ball mill mixing；
2) said mixture is placed in vacuum drying oven to the gas for being passed through that oxygen content is 0.01%~21.6%, in 0 DEG C~100 DEG C
After lower drying, 2~10h of pre-burning in the case where 300~800 DEG C of oxygen content is 0.01%~50% atmosphere；
3) after the cooling of pre-burning product, 4~20h is calcined in the case where 600~900 DEG C of oxygen content is 0.01%~99% atmosphere, is obtained
Product Li4Ti5O12；The capacity of the lithium titanate material is more than 1.2g/cm3.
2. preparation method according to claim 1, it is characterised in that：The lithium source is lithium carbonate, lithium hydroxide or nitric acid
Lithium.
3. preparation method according to claim 1, it is characterised in that：The titanium source is the dioxy of anatase titanium dioxide or rutile-type
Change titanium.
4. preparation method according to claim 1, it is characterised in that：Step 1) in raw material in lithium titanium mol ratio be Li/
Ti=0.76~0.86.
5. preparation method according to claim 1, it is characterised in that：The fluxing agent is sodium tetraborate, Firebrake ZB, boron
One or more mixtures in acid, lithium tetraborate, lithium hydroxide, lithium acetate, lithium fluoride or vanadic anhydride.
6. preparation method according to claim 1 or 5, it is characterised in that：The content of the fluxing agent is titanium dioxide matter
0.05~10wt% of amount.
7. preparation method according to claim 1, it is characterised in that：The dispersant and solid content mass ratio be 0.5~
1.5：1.
8. the preparation method according to claim 1 or 7, it is characterised in that：Dispersant is in water, ethanol, methanol or acetone
One or more mixing.
9. preparation method as claimed in claim 1, it is characterised in that：Also include step 4)：
4) by step 3) middle gained lithium titanate further carries out coated modified carbon processing or ion doping is handled, and obtains modification
Li4Ti5O12。
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109119622A (en) * | 2018-09-25 | 2019-01-01 | 上海电气集团股份有限公司 | Lithium-titanium composite oxide, modified lithium titanate material and preparation method thereof, application |
| CN114408965A (en) * | 2022-03-11 | 2022-04-29 | 昆明理工大学 | Method for preparing lithium titanate |
| CN115744972A (en) * | 2023-01-09 | 2023-03-07 | 河北格力钛新能源有限公司 | Preparation method of high-compaction lithium titanate material and high-compaction lithium titanate material |
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| CN102842706A (en) * | 2011-06-22 | 2012-12-26 | 比亚迪股份有限公司 | Preparation method of lithium titanate material, lithium titanate material, and lithium ion battery |
| CN103441257A (en) * | 2013-08-12 | 2013-12-11 | 四川大学 | Preparation method for lithium titanate material |
| CN103682292A (en) * | 2012-09-11 | 2014-03-26 | 中信国安盟固利动力科技有限公司 | Preparation method of high-tap-density lithium titanate material |
| CN104852034A (en) * | 2015-04-10 | 2015-08-19 | 珠海银隆新能源有限公司 | Preparation method for lithium titanate material, lithium titanate cathode pole piece and lithium ion battery |
-
2017
- 2017-06-30 CN CN201710526344.XA patent/CN107324379A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102842706A (en) * | 2011-06-22 | 2012-12-26 | 比亚迪股份有限公司 | Preparation method of lithium titanate material, lithium titanate material, and lithium ion battery |
| CN103682292A (en) * | 2012-09-11 | 2014-03-26 | 中信国安盟固利动力科技有限公司 | Preparation method of high-tap-density lithium titanate material |
| CN103441257A (en) * | 2013-08-12 | 2013-12-11 | 四川大学 | Preparation method for lithium titanate material |
| CN104852034A (en) * | 2015-04-10 | 2015-08-19 | 珠海银隆新能源有限公司 | Preparation method for lithium titanate material, lithium titanate cathode pole piece and lithium ion battery |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109119622A (en) * | 2018-09-25 | 2019-01-01 | 上海电气集团股份有限公司 | Lithium-titanium composite oxide, modified lithium titanate material and preparation method thereof, application |
| CN114408965A (en) * | 2022-03-11 | 2022-04-29 | 昆明理工大学 | Method for preparing lithium titanate |
| CN115744972A (en) * | 2023-01-09 | 2023-03-07 | 河北格力钛新能源有限公司 | Preparation method of high-compaction lithium titanate material and high-compaction lithium titanate material |
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Application publication date: 20171107 |