CN101624212B - Preparation method for lithium titanate composite material - Google Patents
Preparation method for lithium titanate composite material Download PDFInfo
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- CN101624212B CN101624212B CN2008101305849A CN200810130584A CN101624212B CN 101624212 B CN101624212 B CN 101624212B CN 2008101305849 A CN2008101305849 A CN 2008101305849A CN 200810130584 A CN200810130584 A CN 200810130584A CN 101624212 B CN101624212 B CN 101624212B
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- lithium titanate
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Abstract
The invention relates to a preparation method for a lithium titanate composite material. The preparation method for the lithium titanate composite material comprises the following steps of: calcining a mixture containing a transition metal compound, a carbone source, titanium dioxide, a lithium source and a low-temperature molten salt in inert atmosphere; and removing the low-temperature molten salt, wherein the low-temperature molten salt is a salt which is molten under a calcining condition and does not react with the other components in the mixture. The preparation method for the lithium titanate composite material has a simple production process and causes no pollution. The lithium titanate composite material prepared by the method of the invention has a high first discharge specific capacity.
Description
Technical field
The invention relates to a kind of preparation method of lithium titanate composite material.
Background technology
Along with fast development of information technology, various electronic products improve constantly the requirement of power supply.Lithium ion battery since energy density big, have extended cycle life, advantage such as memory-less effect, be the focus that people research and develop always.Current, the negative material of lithium ion battery mainly with graphite as research focus, but the lithium cell of graphite cathode preparation has a lot of shortcomings in the process of using, for example there is Li dendrite to produce in the charge and discharge process, battery short circuit takes place easily, hidden danger on fire and blast is arranged, and also easy and electrolytic solution reacts and shortens the work-ing life that makes battery.By contrast, lithium titanate material has remarkable advantages, in the insertion of lithium ion with take off in the embedding process, crystalline network changes very little, and repeatedly charge-discharge performance is good, does not react with electrolytic solution, compare with carbon negative pole material, have better chemical property and security.
But, can't satisfy the requirement of scale operation at present for the research and development of lithium titanate.
Disclosing a kind of among the open CN1919736A of Chinese patent is the method that medium prepares lithium titanate with the low-temperature molten salt, can accelerated reaction by this method, shorten the reaction times, but the requirement that does not reach the battery material of desirable first discharge specific capacity according to the material that this method obtains.
Disclose a kind of preparation method of lithium titanate battery material among the open CN101118965A of Chinese patent, this method adds monose or polysaccharide and prepares lithium titanate submicron lithium titanate by re-baking.But, unsatisfactory by the first discharge specific capacity of the actual lithium titanate material that makes of this method.
Summary of the invention
The objective of the invention is to overcome the dissatisfactory shortcoming of the first discharge specific capacity of lithium titanate material in the prior art, a kind of preparation method with lithium titanate composite material of high first discharge specific capacity is provided.
The invention provides a kind of preparation method of lithium titanate composite material, this method comprises calcines and removes low-temperature molten salt with the mixture that contains transistion metal compound, carbon source, titanium dioxide, lithium source and low-temperature molten salt in rare gas element, wherein, described low-temperature molten salt be can fusion under the calcination condition and not with mixture in the material of other composition reaction.
Preparation method's production technique of lithium titanate composite material provided by the invention is simple, pollution-free.The lithium titanate composite material that makes according to method provided by the invention has high first discharge specific capacity.
Embodiment
Preparation method according to lithium titanate composite material provided by the invention, this method comprises calcines and removes low-temperature molten salt with the mixture that contains transistion metal compound, carbon source, titanium dioxide, lithium source and low-temperature molten salt in rare gas element, wherein, described low-temperature molten salt be can fusion under the calcination condition and not with mixture in the material of other composition reaction.
In the described mixture, the mol ratio of titanium dioxide, lithium source, transistion metal compound, carbon source and low-temperature molten salt can be 1: 0.8-0.9: 0.01-0.15: 0.1-0.5: 0.5-1 is preferably 1: 0.8-0.85: 0.01-0.15: 0.1-0.5: 0.5-1.
With titanium dioxide, lithium source, transistion metal compound, carbon source and low-temperature molten salt blended method is ordinary method, for example can use stirring method to mix.
Described lithium source can be the oxyhydroxide of organic salt, inorganic salt or the lithium of lithium, and for example, the inorganic salt of described lithium can be lithium nitrate, Quilonum Retard (LiCO
3); The organic salt of described lithium can be lithium oxalate, Lithium Acetate; The oxyhydroxide of described lithium can be lithium hydroxide, hydronium(ion) oxidation lithium.Under the preferable case, described lithium source can be in Quilonum Retard, lithium hydroxide and the lithium nitrate one or more.
Described transistion metal compound can be the oxyhydroxide of the oxide compound of transition metal, transition metal and in the transition metal salt one or more.Described transition metal salt can be organic salt, as in acetate and the oxalate one or more, also can be inorganic salt, as in carbonate and the nitrate one or more.Described transition metal is preferably one or more in scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, the cadmium, more preferably one or more in manganese, nickel and the copper.Under the preferable case, transistion metal compound of the present invention is one or more in acetate, oxalate and the nitrate, more preferably acetate and/or nitrate.
Described carbon source can be carbon simple substance, as in graphite, acetylene black and the gac one or more, also can be for can thermo-cracking producing carbon compound, for example one or more in carbohydrate, pitch, resol, polyacrylonitrile, Walocel MT 20.000PV and the polyoxyethylene glycol.Described carbohydrate is preferably one or more in glucose, sucrose and the starch.Under the preferable case, can be for can thermo-cracking producing in the carbon compound one or more, glucose more preferably.
Described low-temperature molten salt can for various can fusion under the calcination condition and not with mixture in the salt of other composition reaction, be preferably in lithium chloride, sodium-chlor, Repone K, SODIUMNITRATE and the saltpetre one or more.
Described rare gas element is not for participating in the gas of reaction of the present invention, for example one or more in zero group gas and the nitrogen.
Described incinerating condition can for, temperature of reaction is 500 ℃-1200 ℃, the reaction times is 1-24 hour.Under the optimum condition, temperature of reaction is 700 ℃-900 ℃, and the reaction times is 8-16 hour.
Described method of removing low-temperature molten salt is an ordinary method, for conventionally known to one of skill in the art.For example can wash with water, the consumption of described water is enough to remove fully described low-temperature molten salt and gets final product.
Under the preferable case, after described calcining, also return burning, described return burning can described remove the low temperature dissolved salt before, also can described remove the low temperature dissolved salt after, preferably after removing the low temperature dissolved salt, return burning.The described condition of returning burning comprises that temperature of reaction is 500 ℃-1200 ℃, and the reaction times is 1-24 hour.Under the optimum condition, temperature of reaction is 750-850, and the reaction times is 8-16 hour.
Under the preferable case, also carry out ball milling after removing the low temperature dissolved salt, when the step of burning was returned in existence, described ball milling can be before returning burning, also can be after returning burning, preferably before returning burning.The method of described ball milling is an ordinary method, for conventionally known to one of skill in the art.The dispersion agent that can add this area routine in the mechanical milling process is as ethanol.Can it be under 100-300 rev/min the condition ball milling 1-10 hour for example at rotating speed; Being preferably at rotating speed is under 200-300 rev/min the condition ball milling 4-6 hour.
According to preferred implementation of the present invention, after calcining, remove low-temperature molten salt, ball milling returns burning then, can further improve the first discharge specific capacity of the battery of lithium titanate composite material formation obtained by this method.
The present invention is described further below by specific embodiment.
Embodiment 1
(1) preparation of lithium titanate composite material
With 79.2 gram TiO
2, 34.4 the gram LiOHH
2O, 2.45 gram MnAc
24H
2O, 30 grams lithium chlorides and 34 gram glucose (C
6H
12O
6H
2O) mix, in argon gas atmosphere, under 800 ℃ the temperature, calcined 8 hours, with 500ml deionized water wash resultant, add dehydrated alcohol as dispersion agent, at rotating speed ball milling 5 hours under 300 rev/mins the condition, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate composite material M1.
(2) preparation of pole piece
80 weight part lithium titanate composite materials, 10 weight part tackiness agent polytetrafluoroethylene (PTFE)s, 10 weight part conductive agent carbon blacks are joined in 110 parts by weight of deionized water, stir then and form cathode size stable, homogeneous., take out after 24 hours at 65 ℃ vacuum drying oven inner dryings, being pressed into thickness under the pressure of 4MPa is 0.03 millimeter, and size is the pole piece of 15 millimeters of diameters.
(3) preparation of battery
With LiPF
6Be mixed with the solution that concentration is 1 mol with NSC 11801 and methylcarbonate, obtain electrolytic solution.
Protect in argon gas atmosphere; moisture content is in the following glove box of 1ppm; with the above-mentioned pole piece that makes; diameter is 15.8 millimeters, the metal lithium sheet of purity 99.9% as counter electrode and diameter is that 16 millimeters Cellgard diaphragm paper is formed battery battery core; add 0.2 milliliter of electrolytic solution, make CR2016 type button cell A1.After assembling, shift out glove box, with electronic stamping machine pressure seal.
(4) performance test
With battery ability meter (blue strange BK-6064A) test battery performance, the charging stopping potential is 2.5 volts, and discharge cut-off voltage is 1.0 volts, and current density is 0.15 milliampere/centimetre
2, measure loading capacity first, the loading capacity first that usefulness obtains obtains first discharge specific capacity divided by the quality of lithium titanate composite material, and the result is as shown in table 1.
Embodiment 2
Prepare battery A2 according to the mode identical with embodiment 1, difference is that the preparation method of lithium titanate composite material is, with 76 gram TiO
2, 34.4 the gram LiOHH
2O, 12.25 gram MnAc
24H
2O, 30 grams lithium chlorides and 34 gram C
6H
12O
6H
2O mixes, and in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, at rotating speed ball milling 5 hours under 300 rev/mins the condition, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate composite material M2.
According to the mode identical with embodiment 1 battery A2 is carried out performance test, the result is as shown in table 1.
Embodiment 3
Prepare battery A3 according to the mode identical with embodiment 1, difference is that the preparation method of lithium titanate composite material is, with 72 gram TiO
2, 34.4 the gram LiOHH
2O, 24.5 gram MnAc
24H
2O, 30 grams lithium chlorides and 34 gram C
6H
12O
6H
2O mixes, and in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, at rotating speed ball milling 5 hours under 300 rev/mins the condition, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate composite material M3.
According to the mode identical with embodiment 1 battery A3 is carried out performance test, the result is as shown in table 1.
Embodiment 4
Prepare battery A4 according to the mode identical with embodiment 1, difference is that the preparation method of lithium titanate composite material is, with 76 gram TiO
2, 34.4 the gram LiOHH
2O, 14.6 gram Ni (NO
3)
26H
2O, 30 grams lithium chlorides and 34 gram C
6H
12O
6H
2O mixes, and in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, at rotating speed ball milling 5 hours under 300 rev/mins the condition, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate composite material M4.
According to the mode identical with embodiment 1 battery A4 is carried out performance test, the result is as shown in table 1.
Embodiment 5
Prepare battery A5 according to the mode identical with embodiment 1, difference is that the preparation method of lithium titanate composite material is, with 76 gram TiO
2, 34.4 the gram LiOHH
2O, 12.1 gram Cu (NO
3)
23H
2O, 30 grams lithium chlorides and 34 gram C
6H
12O
6H
2O mixes, and in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, at rotating speed ball milling 5 hours under 300 rev/mins the condition, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate composite material M5.
According to the mode identical with embodiment 1 battery A5 is carried out performance test, the result is as shown in table 1.
Embodiment 6
Prepare battery A6 according to the method identical with embodiment 1, difference is to use 4.6 gram carbon blacks to replace 34 gram C
6H
12O
6H
2O.
According to the mode identical with embodiment 1 battery A6 is carried out performance test, the result is as shown in table 1.
Embodiment 7
Prepare battery A7 according to the mode identical with embodiment 1, difference is, in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, finally makes lithium titanate composite material M7.
According to the mode identical with embodiment 1 battery A7 is carried out performance test, the result is as shown in table 1.
Embodiment 8
Prepare battery A8 according to the mode identical with embodiment 1, difference is, in argon gas atmosphere, under 800 ℃ the temperature, calcined 8 hours, in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours then, with 500ml deionized water wash resultant, adding dehydrated alcohol as dispersion agent, is ball milling 5 hours under 300 rev/mins the condition at rotating speed, obtains lithium titanate composite material M8.
According to the mode identical with embodiment 1 battery A8 is carried out performance test, the result is as shown in table 1.
Comparative Examples 1
Prepare battery B1 according to the mode identical with embodiment 1, difference is that the preparation method of lithium titanate composite material is, with 80 gram TiO
2, 34.4 the gram LiOHH
2O, 30 grams lithium chlorides mix, in argon gas atmosphere, under 800 ℃ the temperature, calcining 8 hours, behind 500ml deionized water wash resultant, is ball milling 5 hours under 300 rev/mins the condition at rotating speed, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate material N1.
According to the mode identical with embodiment 1 battery B1 is carried out performance test, the result is as shown in table 1.
Comparative Examples 2
Prepare battery B2 according to the mode identical with embodiment 1, difference is that the preparation method of lithium titanate composite material is, with 80 gram TiO
2, 34.4 the gram LiOHH
2O, 30 grams lithium chlorides and 34 gram C
6H
12O
6H
2O mixes, and in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, at rotating speed ball milling 5 hours under 300 rev/mins the condition, then in argon gas atmosphere, under 800 ℃ the temperature, return and burnt 16 hours, obtain lithium titanate composite material N2.
According to the mode identical with embodiment 1 battery B2 is carried out performance test, the result is as shown in table 1.
Comparative Examples 3
Prepare battery B3 according to the method identical with embodiment 1, difference is, with 80 gram TiO
2, 34.4 the gram LiOHH
2O, 30 grams lithium chlorides and 34 gram C
6H
12O
6H
2O mixes, and in argon gas atmosphere, under 800 ℃ the temperature, calcines 8 hours, behind 500ml deionized water wash resultant, finally makes lithium titanate composite material N3.
According to the mode identical with embodiment 1 battery B3 is carried out performance test, the result is as shown in table 1.
Table 1
| The battery numbering | Doped element | Whether return burning | First discharge specific capacity (mAh/g) | |
| Embodiment 1 | A1 | Mn、C | Be | 168 |
| Embodiment 2 | A2 | Mn、C | Be | 173 |
| Embodiment 3 | A3 | Mn、C | Be | 165 |
| Embodiment 4 | A4 | Ni、C | Be | 166 |
| Embodiment 5 | A5 | Cu、C | Be | 162 |
| Embodiment 6 | A6 | Mn、C | Be | 169 |
| Embodiment 7 | A7 | Mn、C | Not | 155 |
| Embodiment 8 | A8 | Mn、C | Be | 163 |
| Comparative Examples 1 | B1 | / | Be | 145 |
| Comparative Examples 2 | B2 | C | Be | 150 |
| Comparative Examples 3 | B3 | / | Not | 140 |
From the result of table 1 as can be seen, the battery A1-A8 that makes of the lithium titanate composite material that is made by method provided by the invention and the battery B1-B3 of Comparative Examples 1-3 are than higher first discharge specific capacity.
Claims (7)
1. the preparation method of a lithium titanate composite material, it is characterized in that, this method comprises calcines and removes low-temperature molten salt with the mixture that contains transistion metal compound, carbon source, titanium dioxide, lithium source and low-temperature molten salt in rare gas element, wherein, described low-temperature molten salt be can fusion under the calcination condition and not with mixture in the salt of other composition reaction, in described mixture, the mol ratio of described titanium dioxide, lithium source, transistion metal compound, carbon source and low-temperature molten salt is 1: 0.8-0.9: 0.01-0.15: 0.1-0.5: 0.5-1.
2. method according to claim 1, wherein, described transistion metal compound is one or more in oxide compound, oxyhydroxide and the salt of scandium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc and cadmium.
3. method according to claim 1, wherein, described carbon source is one or more in graphite, acetylene black, gac, carbohydrate, pitch, resol, polyacrylonitrile, Walocel MT 20.000PV and the polyoxyethylene glycol.
4. method according to claim 1, wherein, described lithium source is one or more in Quilonum Retard, lithium hydroxide and the lithium nitrate, described low-temperature molten salt is one or more in lithium chloride, sodium-chlor, Repone K, SODIUMNITRATE, the saltpetre.
5. method according to claim 1, wherein, described incinerating condition comprises that temperature of reaction is 500 ℃-1200 ℃, the reaction times is 1-24 hour.
6. method according to claim 1 wherein, is describedly also returned burning after removing the low temperature dissolved salt, and the described condition of returning burning comprises that temperature of reaction is 500 ℃-1200 ℃, and the reaction times is 1-24 hour.
7. method according to claim 6 wherein, is also carried out ball milling described before returning burning, and it is under 100-300 rev/min the condition ball milling 1-10 hour that the method for described ball milling is included in rotating speed.
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| CN102234101B (en) * | 2010-04-26 | 2014-04-30 | 深圳市比克电池有限公司 | Micron nano structure Li3V2(PO4)3/C compound as well as preparation method and application thereof |
| CN102315427A (en) * | 2010-06-29 | 2012-01-11 | 比亚迪股份有限公司 | Cathode active substance for lithium ion secondary battery, preparation method and lithium ion secondary battery |
| US10170758B2 (en) * | 2013-06-05 | 2019-01-01 | Johnson Matthey Public Limited Company | Process for the preparation of lithium titanium spinel and its use |
| CN104617285B (en) * | 2014-12-16 | 2017-02-22 | 天津大学 | Lithium ion battery negative electrode material Li2ZnTi3O8 preparation method |
| CN109279650A (en) * | 2018-11-22 | 2019-01-29 | 成都先进金属材料产业技术研究院有限公司 | The method that growth in situ prepares lithium titanate in metallic titanium powder fused salt |
| CN110451482B (en) * | 2019-08-19 | 2021-04-20 | 北京理工大学 | Preparation method of nitrogen and sulfur co-doped carbon nanosheet material |
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| CN101118965A (en) * | 2007-09-14 | 2008-02-06 | 南开大学 | Submicron secondary battery material and method for making same |
Non-Patent Citations (3)
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