CN103633370A - Lithium titanate battery non-water electrolyte and lithium titanate battery - Google Patents
Lithium titanate battery non-water electrolyte and lithium titanate battery Download PDFInfo
- Publication number
- CN103633370A CN103633370A CN201310649658.0A CN201310649658A CN103633370A CN 103633370 A CN103633370 A CN 103633370A CN 201310649658 A CN201310649658 A CN 201310649658A CN 103633370 A CN103633370 A CN 103633370A
- Authority
- CN
- China
- Prior art keywords
- lithium
- lithium titanate
- titanate battery
- additive
- organic solvent
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Classifications
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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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0568—Liquid materials characterised by the solutes
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium titanate battery non-water electrolyte and a lithium titanate battery, and aims to provide the lithium titanate battery non-water electrolyte and the lithium titanate battery which can restrain the lithium titanate battery from generating gas to prevent the battery from gas expansion at a high temperature. The lithium titanate battery comprises a cathode material, an anode material and an electrolyte, wherein the anode material is lithium titanate; the electrolyte comprises lithium, an organic solvent and an additive; the additive is selected from at least one of difluoro bis(oxalato) lithium phosphate, tetra-fluoro (oxalato) lithium phosphate, tris-oxalate lithium phosphate, 1,8-naphthalene sulfonic acid lactone, and 1,3-propene sulfonic acid lactone; the use mass of the additive is equivalent to 1-5% of the total mass of the lithium and the organic solvent. The lithium titanate battery non-water electrolyte and the lithium titanate battery can be widely applied to the lithium titanate battery field.
Description
Technical field
The present invention relates to a kind of lithium titanate battery nonaqueous electrolytic solution and lithium titanate battery.
Background technology
Current commercial lithium ion battery negative material is embedding lithium material with carbon element mostly, due to the current potential of carbon electrode after embedding lithium and the current potential of lithium metal very approaching, when over-charging of battery, the easy precipitating metal lithium of carbon electrodes, it reacts with electrolyte and produces combustible gas mixture, thereby causes very large potential safety hazard to battery, particularly electrokinetic cell.Meanwhile, also there is the common imbedding problem of electrolyte in graphite electrode, and this also will affect the cyclical stability of electrode.Lithium titanate material is the lithium secondary battery cathode material of a kind of high-performance, high magnification type.At Li, embed or deviate from process, crystal formation does not change, change in volume is less than 1%, therefore be called as " zero strain material ", this is significant, can avoid in charge and discharge cycles because the flexible back and forth of electrode material causes structural damage, thereby cycle performance and the useful life of improving electrode there is the cycle performance better than carbon negative pole.And lithium titanate material electromotive force is than the height of pure metal lithium, is difficult for producing lithium dendrite arm, for ensureing that the safety of lithium battery provides the foundation, and is considered to thoroughly to solve the fail safe of lithium battery.Lithium titanate material and PC have good compatibility, can not cause lithium titanate material to peel off because large molecule embeds.Li
4ti
5o
12current potential with respect to lithium electrode is 1.55V, and theoretical specific capacity is 175mAh/g, actual specific capacity 150～160mAh/g.At 25 ℃, Li
4ti
5o
12chemical diffusion coefficient be 2 * 10
-8cm2/s, than the large order of magnitude of the diffusion coefficient in carbon negative pole material, high diffusion coefficient makes this negative material can quick, many cycle charge-discharges.But, it is found that and take battery easy flatulence when high temperature that lithium titanate is negative pole, this kind of phenomenon is particularly evident for flexible-packed battery, and its reason is to contain trace impurity in lithium titanate, plays the effect of catalysis solvolysis aerogenesis when high temperature.
Therefore, in the urgent need to finding suitable film for additive, make it in negative terminal surface film forming, and then stop the catalytic decomposition of electrolyte, thereby solve the inflatable problem of lithium titanate battery.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, provides a kind of lithium titanate battery aerogenesis that can suppress to avoid lithium titanate battery nonaqueous electrolytic solution and the battery of battery flatulence when the high temperature.
The technical scheme that a kind of lithium titanate battery nonaqueous electrolytic solution of the present invention adopts is: lithium titanate battery nonaqueous electrolytic solution of the present invention comprises lithium salts, organic solvent and additive, described additive is selected from difluoro (two oxalates close) lithium phosphate, tetrafluoro (oxalate closes) lithium phosphate, three oxalic acid lithium phosphates, 1,8-naphthalene sulfonic acids lactone, 1, at least one in 3-propene sulfonic acid lactone, the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass.
Further, described additive is the three oxalic acid lithium phosphates that service quality is equivalent to described lithium salts and described organic solvent gross mass 1%.
Further, described additive is to be equivalent to 1 of described lithium salts and described organic solvent gross mass 2%, 8-naphthalene sulfonic acids lactone and 2% difluoro (two oxalates close) lithium phosphate.
Described lithium salts is lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), bis trifluoromethyl sulfimide lithium (LiN (CF
3sO
2)
2) in any one or several mixing wherein use, the concentration of described lithium salts is 0.5M-1.5M.
Described organic solvent is one or more of chain and cyclic carbonates, carboxylic acid esters, ethers and heterocyclic compound.
The technical scheme that a kind of lithium titanate battery of the present invention adopts is: lithium titanate battery of the present invention comprises positive electrode, negative material, electrolyte, and described negative material is lithium titanate (Li
4ti
5o
12), described electrolyte comprises lithium salts, organic solvent and additive, described additive is selected from difluoro (two oxalates close) lithium phosphate, tetrafluoro (oxalate closes) lithium phosphate, three oxalic acid lithium phosphates, 1,8-naphthalene sulfonic acids lactone, 1, one or more combinations in 3-propene sulfonic acid lactone, the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass.
The invention has the beneficial effects as follows: owing to having added difluoro (two oxalates close) lithium phosphate in electrolyte of the present invention, tetrafluoro (oxalate closes) lithium phosphate, three oxalic acid lithium phosphates, 1, 8-naphthalene sulfonic acids lactone, 1, one or more combinations in 3-propene sulfonic acid lactone, adding of above-mentioned substance can make the surface of lithium titanate battery form good SEI film, can stop direct contact that electrolyte is lithium titanate material with negative pole, the micro-molecular gas that electrolyte can effectively absorb the moisture in electrode and be produced by solvolysis in charge and discharge process with respect to conventional electrolysis liquid, therefore can effectively suppress the aerogenesis of lithium titanate battery, so the present invention can suppress lithium titanate battery aerogenesis to avoid battery flatulence when the high temperature.
Because the additive in the present invention is three oxalic acid lithium phosphates, on graphite cathode to Li+/Li reduction potential up to 2.1V, far away higher than conventional film for additive, thereby can mate high voltage system, the present invention meets positive electrode and adopts high voltage material, so can improve cell output voltage.
Embodiment
Below in conjunction with specific embodiment, the present invention and beneficial effect thereof are explained and illustrated, but are not as limitation of the present invention.
Embodiment mono-:
Lithium titanate battery of the present invention comprises positive electrode, negative material and electrolyte, and described negative material is lithium titanate, and described electrolyte comprises lithium salts, organic solvent and additive, and described lithium salts can be lithium hexafluoro phosphate (LiPF
6), LiBF4 (LiBF
4), bis trifluoromethyl sulfimide lithium (LiN (CF
3sO
2)
2) in any one or several mixing wherein use, its concentration range is 0.5M-1.5M, what in the present embodiment, adopt is that concentration is the lithium hexafluoro phosphate of 1M, selecting weight ratio is the ethylene carbonate (EC) of 1:1:1, the mixture of diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) is as organic solvent, described additive is selected from difluoro (two oxalates close) lithium phosphate, tetrafluoro (oxalate closes) lithium phosphate, three oxalic acid lithium phosphates, 1, 8-naphthalene sulfonic acids lactone, 1, at least one in 3-propene sulfonic acid lactone, the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass, in the present embodiment, add three oxalic acid lithium phosphates of 1 weight portion as described additive, adding of described three oxalic acid lithium phosphates not only makes the surface of lithium titanate battery form good SEI film, can stop direct contact that electrolyte is lithium titanate material with negative pole, the micro-molecular gas that electrolyte can effectively absorb the moisture in electrode and be produced by solvolysis in charge and discharge process with respect to conventional electrolysis liquid, and on graphite cathode to Li+/Li reduction potential up to 2.1V, far away higher than conventional film for additive, thereby can mate high voltage system, meet positive electrode and adopt high voltage material.
Embodiment bis-:
Other is identical with embodiment mono-, different, and described additive is difluoro (the two oxalates close) lithium phosphate of 1 weight portion.
Embodiment tri-:
Other is identical with embodiment mono-, different, and described additive is 1 of 1 weight portion, 8-naphthalene sulfonic acids lactone.
Embodiment tetra-:
Other is identical with embodiment mono-, different, described additive be 2 weight portions difluoro (two oxalates close) lithium phosphate, 2 weight portions 1,8-naphthalene sulfonic acids lactone.
Embodiment five:
Other is identical with embodiment mono-, different, and described additive is 1,3 propene sulfonic acid lactone of 1 weight portion,, 2 weight portions 1,8-naphthalene sulfonic acids lactone.
Embodiment six:
Other is identical with embodiment mono-, different, and described additive is 1 of 5 weight portions, 8-naphthalene sulfonic acids lactone.
Embodiment seven:
Other is identical with embodiment mono-, different, and described additive is 1,3 propene sulfonic acid lactone of 1 weight portion.
Embodiment eight:
Other is identical with embodiment mono-, different, and described additive is three oxalic acid lithium phosphates of 3 weight portions.
Embodiment nine:
Other is identical with embodiment mono-, different, and described additive is three oxalic acid lithium phosphates of 5 weight portions.
Embodiment ten:
Other is identical with embodiment mono-, different, and described additive is tetrafluoro (oxalate closes) lithium phosphate of 1 weight portion.
Embodiment 11:
Other is identical with embodiment mono-, different, and described additive is tetrafluoro (oxalate closes) lithium phosphate of 3 weight portions, difluoro (the two oxalates close) lithium phosphate of 2 weight portions.
Embodiment 12:
Other is identical with embodiment mono-, different, and described additive is tetrafluoro (oxalate closes) lithium phosphate of 5 weight portions.
Comparative example:
Electrolyte select weight ratio be the mixture of ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) of 1:1:1 as organic solvent, LiPF6 is 1.0M.
Electrolyte in above-described embodiment, after making battery, is measured storge quality at high temperature of battery and normal-temperature circulating performance etc., and result is as shown in the table:
Result of the test by table one can be found out, with respect to comparative example, has used after additive of the present invention, and the high-temperature storage performance of battery and the cycle life of battery obviously improve.
Claims (6)
1. a lithium titanate battery nonaqueous electrolytic solution, it comprises lithium salts, organic solvent and additive, it is characterized in that: described additive is selected from difluoro (two oxalates close) lithium phosphate, tetrafluoro (oxalate closes) lithium phosphate, three oxalic acid lithium phosphates, 1,8-naphthalene sulfonic acids lactone, 1, at least one in 3-propene sulfonic acid lactone, the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass.
2. lithium titanate battery nonaqueous electrolytic solution according to claim 1, is characterized in that: described additive is the three oxalic acid lithium phosphates that service quality is equivalent to described lithium salts and described organic solvent gross mass 1%.
3. lithium titanate battery nonaqueous electrolytic solution according to claim 1, is characterized in that: described additive is to be equivalent to 1 of described lithium salts and described organic solvent gross mass 2%, 8-naphthalene sulfonic acids lactone and 2% difluoro (two oxalates close) lithium phosphate.
4. lithium titanate battery nonaqueous electrolytic solution according to claim 1, it is characterized in that: described lithium salts is that any one or several mixing wherein in lithium hexafluoro phosphate or LiBF4 or bis trifluoromethyl sulfimide lithium are used, and the concentration of described lithium salts is 0.5M-1.5M.
5. lithium titanate battery nonaqueous electrolytic solution according to claim 1, is characterized in that: described organic solvent is one or more of chain and cyclic carbonates, carboxylic acid esters, ethers and heterocyclic compound.
6. comprise described in claim 1 lithium titanate battery for electrolyte for lithium titanate battery, it is characterized in that: it also comprises negative material, described negative material is lithium titanate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310649658.0A CN103633370A (en) | 2013-12-06 | 2013-12-06 | Lithium titanate battery non-water electrolyte and lithium titanate battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310649658.0A CN103633370A (en) | 2013-12-06 | 2013-12-06 | Lithium titanate battery non-water electrolyte and lithium titanate battery |
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| Publication Number | Publication Date |
|---|---|
| CN103633370A true CN103633370A (en) | 2014-03-12 |
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ID=50214152
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|---|---|---|---|
| CN201310649658.0A Pending CN103633370A (en) | 2013-12-06 | 2013-12-06 | Lithium titanate battery non-water electrolyte and lithium titanate battery |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810997A (en) * | 2014-12-31 | 2016-07-27 | 龙能科技（苏州）有限公司 | Lithium ion battery electrolyte solution and preparation method thereof, and lithium ion battery |
| CN106299473A (en) * | 2016-08-29 | 2017-01-04 | 宁德市凯欣电池材料有限公司 | A kind of oxalic acid lithium phosphate and preparation method thereof |
| CN106450427A (en) * | 2016-08-29 | 2017-02-22 | 宁德市凯欣电池材料有限公司 | Electrolyte containing oxalic acid lithium phosphate and lithium ion battery adopting electrolyte |
| CN106450457A (en) * | 2016-10-26 | 2017-02-22 | 东莞市凯欣电池材料有限公司 | Lithium titanate secondary battery |
| CN107887648A (en) * | 2017-11-09 | 2018-04-06 | 安徽智森电子科技有限公司 | A kind of lithium titanate battery of not flatulence |
| CN108923067A (en) * | 2018-09-06 | 2018-11-30 | 桑德集团有限公司 | A kind of electrolysis additive and electrolyte, lithium ion battery and equipment containing it |
| CN109273763A (en) * | 2018-09-06 | 2019-01-25 | 贵州兴锂新能源科技有限公司 | It is a kind of using lithium titanate as the lithium-ion battery electrolytes of cathode |
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| US20110195316A1 (en) * | 2009-09-11 | 2011-08-11 | Kenichi Morigaki | Lithium battery |
| CN102544584A (en) * | 2010-12-31 | 2012-07-04 | 张家港市国泰华荣化工新材料有限公司 | Energy storage battery with non-aqueous electrolyte solution of lithium perfluoro-alkoxy (-phenoxy) sulfonylimide |
| WO2013141165A1 (en) * | 2012-03-19 | 2013-09-26 | 三菱化学株式会社 | Nonaqueous electrolyte and nonaqueous electrolyte cell |
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Patent Citations (4)
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| CN101427416A (en) * | 2006-08-04 | 2009-05-06 | 株式会社东芝 | Nonaqueous electrolyte battery, battery pack and vehicle |
| US20110195316A1 (en) * | 2009-09-11 | 2011-08-11 | Kenichi Morigaki | Lithium battery |
| CN102544584A (en) * | 2010-12-31 | 2012-07-04 | 张家港市国泰华荣化工新材料有限公司 | Energy storage battery with non-aqueous electrolyte solution of lithium perfluoro-alkoxy (-phenoxy) sulfonylimide |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105810997A (en) * | 2014-12-31 | 2016-07-27 | 龙能科技（苏州）有限公司 | Lithium ion battery electrolyte solution and preparation method thereof, and lithium ion battery |
| CN106299473A (en) * | 2016-08-29 | 2017-01-04 | 宁德市凯欣电池材料有限公司 | A kind of oxalic acid lithium phosphate and preparation method thereof |
| CN106450427A (en) * | 2016-08-29 | 2017-02-22 | 宁德市凯欣电池材料有限公司 | Electrolyte containing oxalic acid lithium phosphate and lithium ion battery adopting electrolyte |
| CN106299473B (en) * | 2016-08-29 | 2019-01-11 | 宁德市凯欣电池材料有限公司 | A kind of oxalic acid lithium phosphate and preparation method thereof |
| CN106450427B (en) * | 2016-08-29 | 2019-01-15 | 宁德市凯欣电池材料有限公司 | A kind of electrolyte containing oxalic acid lithium phosphate and the lithium ion battery using the electrolyte |
| CN106450457A (en) * | 2016-10-26 | 2017-02-22 | 东莞市凯欣电池材料有限公司 | Lithium titanate secondary battery |
| CN106450457B (en) * | 2016-10-26 | 2019-04-23 | 广州天赐高新材料股份有限公司 | A kind of metatitanic acid lithium secondary battery |
| CN107887648A (en) * | 2017-11-09 | 2018-04-06 | 安徽智森电子科技有限公司 | A kind of lithium titanate battery of not flatulence |
| CN108923067A (en) * | 2018-09-06 | 2018-11-30 | 桑德集团有限公司 | A kind of electrolysis additive and electrolyte, lithium ion battery and equipment containing it |
| CN109273763A (en) * | 2018-09-06 | 2019-01-25 | 贵州兴锂新能源科技有限公司 | It is a kind of using lithium titanate as the lithium-ion battery electrolytes of cathode |
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Address after: South Bay Area South Town Guangdong city Zhuhai province 519000 two Road No. 2 Applicant after: ZHUHAI SMOOTHWAY ELECTRONIC MATERIALS CO., LTD. Address before: 1 workshop No. four, No. three, Village Road, Toyama Industrial Park, Doumen District, Zhuhai, Guangdong, 519000 Applicant before: Zhuhai Smoothway Electronic Materials Co., Ltd. |
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Application publication date: 20140312 |