CN102303902A - Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate - Google Patents
Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate Download PDFInfo
- Publication number
- CN102303902A CN102303902A CN201110223701A CN201110223701A CN102303902A CN 102303902 A CN102303902 A CN 102303902A CN 201110223701 A CN201110223701 A CN 201110223701A CN 201110223701 A CN201110223701 A CN 201110223701A CN 102303902 A CN102303902 A CN 102303902A
- Authority
- CN
- China
- Prior art keywords
- lithium
- preparation
- secondary battery
- lithium titanate
- reaction
- 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.)
- Pending
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses a preparation method of a lithium secondary battery negative electrode material nano spinel type lithium titanate. The preparation method comprises the following steps: (1) dispersing lithium carbonate or lithium hydroxide which is used as a lithium source in an ethanol aqueous solution so as to prepare a lithium dispersing liquid; (2) dissolving weighed and required lithium source in the lithium dispersing liquid in a molar ratio of titanium source to lithium source of (7:4)-(5:4), and strongly stirring; and (3) putting the solution in a reaction kettle for hydrothermal reaction, naturally cooling to room temperature after the reaction is finished, then washing and filtering so as to obtain a white precipitate, and roasting the filtered white precipitate in a muffle furnace so as to obtain lithium titanate powder. Compared with the existing lithium titanate preparation method, in the preparation method disclosed by the invention, reaction temperature is reduced, reaction time is shortened, preparation process is simple and is easy to operate, raw materials are easily available, and the obtained product is uniform, small in particle and good in product property.
Description
Technical field
The present invention relates to the lithium ion battery negative material technical field, be specifically related to a kind of preparation method of lithium secondary battery cathode material nano-grade spinel type lithium titanate.
Background technology
Practical research work to lithium ion battery negative material in recent years launches round how to improve the quality specific storage and volume and capacity ratio, first charge-discharge efficiency, cycle performance and these several respects that reduce cost basically.The successful commercialization of graphite cathode material, but also have some weakness that are difficult to overcome.This is because the carbon negative pole can form passivation layer in organic electrolyte, though this layer can transmit electronics and lithium ion, can cause the irreversible loss of initial capacity; And the current potential of carbon dioxide process carbon electrode and metallic lithium are very approaching, and when battery overcharge, carbon electrodes is prone to the precipitating metal lithium, thereby may form Li dendrite and cause short circuit; Secondly, at high temperature, the protective layer on the carbon negative pole possibly decompose and cause battery to catch fire.Compare with carbon material, the structural changes of lithium titanate with spinel structure charge and discharge process is very little, a kind of zero strain material of being known as, thereby have good cyclical stability, well charge and discharge platform, theoretical specific capacity greatly and not with characteristic such as electrolytic solution reaction.Lithium titanate (Li
4Ti
5O
12) preparation method mainly comprises two kinds, i.e. high temperature solid-state method and sol-gel method.High temperature solid-state is with TiO
2With Li
2CO
3Or raw material such as LiOH 800 ℃～1000 ℃ synthetic down, the reaction times is generally 18～24h, the advantage of this method is that technology is simple, enlarges easily and produces, shortcoming is the bad control of the particle diameter of product, and is micron order mostly, lack of homogeneity; Sol-gel method generally is that employing titanium and lithium salts are precursor, adopts sol-gel technology to prepare lithium titanate through hydrolysis, and this method is compared with the conventional high-temperature solid phase method, and the product chemical purity is high, particle is thin, good uniformity.The present invention attempts to provide a kind of novel preparation to have the lithium titanate Li of spinel structure
4Ti
5O
12Hydrothermal synthesis method, hope that simultaneously this preparation method has actual application value at other field.
Summary of the invention
To the deficiency that prior art exists, technical problem to be solved by this invention is, provides that a kind of technology is simple, chemical purity is high, particle is thin, the preparation method of the lithium secondary battery cathode material nano-grade spinel type lithium titanate of good uniformity.
For solving the problems of the technologies described above, the technical scheme that the present invention taked is: a kind of preparation method of lithium secondary battery cathode material nano-grade spinel type lithium titanate may further comprise the steps:
(1), with Quilonum Retard or lithium hydroxide as the lithium source, be dispersed in the aqueous ethanolic solution, process the lithium dispersion liquid;
(2), according to the titanium source: the mol ratio in lithium source=7: 4～5: 4, take by weighing titanium source requirement, it is dissolved in the lithium dispersion liquid, carry out violent stirring then;
(3), solution is put in carries out hydro-thermal reaction in the reaction kettle, reaction naturally cools to room temperature after finishing, washing and filtering obtains Baise deposition then, and the white precipitate roasting in retort furnace that leaches is got the lithium titanate powder.
The preparation method of above-mentioned lithium secondary battery cathode material nano-grade spinel type lithium titanate, the concentration of volume percent of said aqueous ethanolic solution is 15%-19%.
The preparation method of above-mentioned lithium secondary battery cathode material nano-grade spinel type lithium titanate, said to carry out the violent stirring blended time be 2-4h.
The preparation method of above-mentioned lithium secondary battery cathode material nano-grade spinel type lithium titanate, the temperature of said hydro-thermal reaction are 120 ℃-180 ℃, reaction 8-14h;
The preparation method of above-mentioned lithium secondary battery cathode material nano-grade spinel type lithium titanate, said calcination process are meant that the heat-up rate with 5 ℃/min is warming up in 400 ℃-600 ℃ the scope roasting 6h-8h down from room temperature.
The preparing method's of lithium secondary battery cathode material nano-grade spinel type lithium titanate of the present invention advantage is: the present invention compares with the preparation method of existing lithium titanate; Reduced temperature of reaction; Shortened the reaction times; And preparation technology is simple; Easy handling, low in raw material cost is easy to get, and the product that obtains is even; Particle is less, and product performance are good.
Description of drawings
Fig. 1 is the SEM figure of lithium titanate with spinel structure;
Fig. 2 is the XRD figure of the lithium titanate of spinel structure;
Fig. 3 is the size distribution figure of lithium titanate with spinel structure;
Fig. 4 is the lithium titanate electrode cycle characteristics graphic representation of spinel structure;
Fig. 5 is the first charge-discharge graphic representation of the lithium titanate of spinel structure.
Embodiment
Below in conjunction with accompanying drawing and specific embodiment the present invention is explained further details;
Embodiment 1:
(1) weighing 7.282g Quilonum Retard is dispersed in the 500mL aqueous ethanolic solution, and wherein the concentration of aqueous ethanolic solution is 15%, processes the lithium dispersion liquid.
(2) according to according to the titanium source: the mol ratio in lithium source=5: 4, take by weighing titanium source 101.4g, it is dissolved in (1) described lithium dispersion liquid, carry out violent stirring 2h then.
(3) solution is put in the reaction kettle, reacts 8h down at 120 ℃, reaction naturally cools to room temperature after finishing, and then the product washing and filtering is obtained Baise deposition.The white precipitate heat-up rate with 5 ℃/min in retort furnace that leaches is warming up to 400 ℃ of following roasting 6h from room temperature, and roasting gets the lithium titanate powder.
(4) powder is done the XRD analysis test, as shown in Figure 1, product is the lithium titanate material of single spinel structure.
Embodiment 2:
(1) weighing 7.282g lithium hydroxide is dispersed in the 500mL aqueous ethanolic solution, and wherein the concentration of aqueous ethanolic solution is 17%, processes the lithium dispersion liquid.
(2) according to according to the titanium source: the mol ratio in lithium source=6: 4, take by weighing titanium source 121.3g, it is dissolved in (1) described lithium dispersion liquid, carry out violent stirring 3h then.
(3) solution is put in the reaction kettle, reacts 11h down at 150 ℃, reaction naturally cools to room temperature after finishing, and then the product washing and filtering is obtained Baise deposition.The white precipitate heat-up rate with 5 ℃/min in retort furnace that leaches is warming up to 500 ℃ of following roasting 7h from room temperature, and roasting gets the lithium titanate powder.
(4) powder is done scanning electron microscope analysis, in conjunction with sreen analysis, the result shows that the median size of powder is 300nm, wherein in the Electronic Speculum picture bigger particle be the particle distance that leaves eyeglass too near due to.
Embodiment 3:
(1) weighing 7.282g lithium hydroxide is dispersed in the 500mL aqueous ethanolic solution, and wherein the concentration of aqueous ethanolic solution is 19%, processes the lithium dispersion liquid.
(2) according to according to the titanium source: the mol ratio in lithium source=7: 4, take by weighing titanium source 141.6g, it is dissolved in (1) described lithium dispersion liquid, carry out violent stirring 4h then.
(3) solution is put in the reaction kettle, reacts 14h down at 180 ℃, reaction naturally cools to room temperature after finishing, and then the product washing and filtering is obtained Baise deposition.The white precipitate heat-up rate with 5 ℃/min in retort furnace that leaches is warming up to 600 ℃ of following roasting 8h from room temperature, and roasting gets the lithium titanate powder.
(4) lithium manganate is done positive electrode material, lithium titanate is done negative material and is made button cell, the test chemical property, and loading capacity is 160mAh/g.
Certainly, above-mentioned explanation is not to be limitation of the present invention, and the present invention also is not limited to above-mentioned giving an example; Those skilled in the art; In essential scope of the present invention, the variation of making, remodeling, interpolation or replacement all should belong to protection scope of the present invention.
Claims (5)
1. the preparation method of a lithium secondary battery cathode material nano-grade spinel type lithium titanate is characterized in that: may further comprise the steps:
(1), with Quilonum Retard or lithium hydroxide as the lithium source, be dispersed in the aqueous ethanolic solution, process the lithium dispersion liquid;
(2), according to the titanium source: the mol ratio in lithium source=7: 4～5: 4, take by weighing titanium source requirement, it is dissolved in the lithium dispersion liquid, carry out violent stirring then;
(3), solution is put in carries out hydro-thermal reaction in the reaction kettle, reaction naturally cools to room temperature after finishing, washing and filtering obtains Baise deposition then, and the white precipitate roasting in retort furnace that leaches is got the lithium titanate powder.
2. the preparation method of lithium secondary battery cathode material nano-grade spinel type lithium titanate according to claim 1 is characterized in that: the concentration of volume percent of said aqueous ethanolic solution is 15%-19%.
3. the preparation method of lithium secondary battery cathode material nano-grade spinel type lithium titanate according to claim 1 is characterized in that: said to carry out the violent stirring blended time be 2-4h.
4. the preparation method of lithium secondary battery cathode material nano-grade spinel type lithium titanate according to claim 1 is characterized in that: the temperature of said hydro-thermal reaction is 120 ℃-180 ℃, reaction 8-14h.
5. the preparation method of lithium secondary battery cathode material nano-grade spinel type lithium titanate according to claim 1 is characterized in that: said calcination process is meant that the heat-up rate with 5 ℃/min is warming up in 400 ℃-600 ℃ the scope roasting 6h-8h down from room temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110223701A CN102303902A (en) | 2011-08-05 | 2011-08-05 | Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110223701A CN102303902A (en) | 2011-08-05 | 2011-08-05 | Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102303902A true CN102303902A (en) | 2012-01-04 |
Family
ID=45377846
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110223701A Pending CN102303902A (en) | 2011-08-05 | 2011-08-05 | Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102303902A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103682296A (en) * | 2013-08-16 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method for nanoscale lithium titanate material with high specific capacity |
| CN104370303A (en) * | 2014-11-27 | 2015-02-25 | 陕西科技大学 | Preparing method of lithium titanate with good rate performance |
| CN104852028A (en) * | 2015-04-08 | 2015-08-19 | 合肥工业大学 | Lithium titanate/graphene composite cathode material for lithium ion battery |
| CN105358485A (en) * | 2013-06-05 | 2016-02-24 | 庄信万丰股份有限公司 | Process for the preparation of lithium titanium spinel and its use |
| CN112103494A (en) * | 2020-08-07 | 2020-12-18 | 华北电力大学 | Preparation method of high-purity lithium titanate material with controllable nano structure |
| CN112374536A (en) * | 2020-10-19 | 2021-02-19 | 中国工程物理研究院材料研究所 | Rapid preparation of spinel type Li at low temperature4Ti5O12Method for preparing lithium titanate material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1282180A1 (en) * | 2001-07-31 | 2003-02-05 | Xoliox SA | Process for producing Li4Ti5O12 and electrode materials |
| CN1868891A (en) * | 2006-06-12 | 2006-11-29 | 北京科技大学 | Method of synthesizing lithium ion cathode material lithium titanium oxide using solvent heating method |
| CN101409341A (en) * | 2008-11-20 | 2009-04-15 | 上海交通大学 | Method for preparing lithium titanate cathode material of lithium ion battery |
| CN101967009A (en) * | 2010-11-09 | 2011-02-09 | 中国海洋石油总公司 | Method for preparing lithium titanate cathode material for lithium ion power batteries |
-
2011
- 2011-08-05 CN CN201110223701A patent/CN102303902A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1282180A1 (en) * | 2001-07-31 | 2003-02-05 | Xoliox SA | Process for producing Li4Ti5O12 and electrode materials |
| CN1868891A (en) * | 2006-06-12 | 2006-11-29 | 北京科技大学 | Method of synthesizing lithium ion cathode material lithium titanium oxide using solvent heating method |
| CN101409341A (en) * | 2008-11-20 | 2009-04-15 | 上海交通大学 | Method for preparing lithium titanate cathode material of lithium ion battery |
| CN101967009A (en) * | 2010-11-09 | 2011-02-09 | 中国海洋石油总公司 | Method for preparing lithium titanate cathode material for lithium ion power batteries |
Non-Patent Citations (1)
| Title |
|---|
| YUFENG TANG ET AL.: "Template-free synthesis of mesoporous spinel lithium titanate microspheres and their application in high-rate lithium ion batteries", 《J. MATER. CHEM.》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105358485A (en) * | 2013-06-05 | 2016-02-24 | 庄信万丰股份有限公司 | Process for the preparation of lithium titanium spinel and its use |
| CN103682296A (en) * | 2013-08-16 | 2014-03-26 | 东莞上海大学纳米技术研究院 | Preparation method for nanoscale lithium titanate material with high specific capacity |
| CN103682296B (en) * | 2013-08-16 | 2015-12-09 | 东莞上海大学纳米技术研究院 | A kind of preparation method of nanoscale lithium titanate material with high specific capacity |
| CN104370303A (en) * | 2014-11-27 | 2015-02-25 | 陕西科技大学 | Preparing method of lithium titanate with good rate performance |
| CN104852028A (en) * | 2015-04-08 | 2015-08-19 | 合肥工业大学 | Lithium titanate/graphene composite cathode material for lithium ion battery |
| CN112103494A (en) * | 2020-08-07 | 2020-12-18 | 华北电力大学 | Preparation method of high-purity lithium titanate material with controllable nano structure |
| CN112374536A (en) * | 2020-10-19 | 2021-02-19 | 中国工程物理研究院材料研究所 | Rapid preparation of spinel type Li at low temperature4Ti5O12Method for preparing lithium titanate material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xin et al. | Li–Nb–O coating/substitution enhances the electrochemical performance of the LiNi0. 8Mn0. 1Co0. 1O2 (NMC 811) cathode | |
| Reddy et al. | Preparation and characterization of LiNi0. 5Co0. 5O2 and LiNi0. 5Co0. 4Al0. 1O2 by molten salt synthesis for Li ion batteries | |
| Reddy et al. | Molten synthesis of ZnO. Fe3O4 and Fe2O3 and its electrochemical performance | |
| CN102832389B (en) | High-nickel positive active material of surface-modified lithium ion battery and preparation method of positive active material | |
| CN104124467B (en) | A kind of method utilizing lithium lanthanum zirconium oxygen presoma coated powder to prepare solid electrolyte | |
| CN104393277B (en) | Ternary material coated with metal oxide on surface and used for lithium ion battery, and preparation method of ternary material | |
| CN104485452A (en) | High-temperature type lithium manganate anode material for power lithium ion battery and preparation method of high-temperature type lithium manganate anode material | |
| CN105870409B (en) | A kind of preparation method and lithium ion battery of nickel-cobalt-manganternary ternary anode material | |
| CN102569807A (en) | Coated-modified lithium manganese positive electrode material and preparation method thereof | |
| KR20090120482A (en) | New titanium oxide, process for producing the titanium oxide, and lithium rechargeable battery using the titanium oxide as active material | |
| CN108899480A (en) | A kind of long circulation life height ratio capacity nickel cobalt aluminium positive electrode and preparation method thereof | |
| CN104218243A (en) | Highly stable lithium nickel cobalt aluminate positive electrode material and its preparation method | |
| CN102303902A (en) | Preparation method of lithium secondary battery negative electrode material nano spinel type lithium titanate | |
| CN102683668B (en) | Spinel nickel manganese-base oxide positive electrode and preparation method thereof | |
| CN104466160A (en) | Preparation method of lithium enriched ternary system nanometer material | |
| CN102683667A (en) | Lithium-manganese-aluminum oxygen anode material and preparation method thereof | |
| CN109411735A (en) | A kind of positive electrode and preparation method thereof and lithium ion battery | |
| WO2007000075A1 (en) | Method for preparing spherical nickelous hydroxide which is dopped and multiple metal oxides, and lithium ion secondary battery | |
| CN103618069A (en) | Preparation method of lithium titanate-coated ferric oxide anode material of lithium ion battery | |
| CN103682292B (en) | The lithium titanate material preparation method of high-tap density | |
| CN101704681B (en) | Method for preparing lithium titanate with spinel structure | |
| Shuai et al. | Electrochemically Modulated LiNi1/3Mn1/3Co1/3O2 Cathodes for Lithium‐Ion Batteries | |
| CN105280912A (en) | Preparation method of oxide-cladding lithium ion battery positive material | |
| CN106207253B (en) | A kind of aqueous solution lithium ion secondary battery negative pole, electrolyte and battery | |
| CN104681808A (en) | Method for preparing strontium salt doped lithium nickel manganese oxide cathode material of lithium ion battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| ASS | Succession or assignment of patent right |
Owner name: QINGDAO QIANYUN HIGH-TECH. NEW MATERIAL CO., LTD. Free format text: FORMER OWNER: QINGDAO QIANYUN GAOKE NEW MATERIAL CO., LTD. Effective date: 20120428 |
|
| C41 | Transfer of patent application or patent right or utility model | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20120428 Address after: Chengyang Qingda Industrial Park, 266111 Shandong middle road Fengyuan City in Qingdao Province Applicant after: QingDao Qianyun High-tech New Material Co., Ltd. Address before: Chengyang Qingda Industrial Park, 266111 Shandong middle road Fengyuan City in Qingdao Province Applicant before: Qingdao Qianyun Gaoke New Material Co., Ltd. |
|
| C12 | Rejection of a patent application after its publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20120104 |