CN102903956B - Lithium titanate battery and electrolyte thereof - Google Patents
Lithium titanate battery and electrolyte thereof Download PDFInfo
- Publication number
- CN102903956B CN102903956B CN201210397501.9A CN201210397501A CN102903956B CN 102903956 B CN102903956 B CN 102903956B CN 201210397501 A CN201210397501 A CN 201210397501A CN 102903956 B CN102903956 B CN 102903956B
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- CN
- China
- Prior art keywords
- lithium
- lithium titanate
- titanate battery
- electrolyte
- additive
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- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 48
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 239000003792 electrolyte Substances 0.000 title claims abstract description 20
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000000996 additive effect Effects 0.000 claims abstract description 28
- 239000000654 additive Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 17
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 16
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 claims abstract description 13
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229960002645 boric acid Drugs 0.000 claims abstract description 13
- 235000010338 boric acid Nutrition 0.000 claims abstract description 13
- 235000006408 oxalic acid Nutrition 0.000 claims abstract description 13
- DEUISMFZZMAAOJ-UHFFFAOYSA-N lithium dihydrogen borate oxalic acid Chemical compound B([O-])(O)O.C(C(=O)O)(=O)O.C(C(=O)O)(=O)O.[Li+] DEUISMFZZMAAOJ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910013188 LiBOB Inorganic materials 0.000 claims abstract description 5
- 239000006259 organic additive Substances 0.000 claims abstract description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 6
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 6
- QGHDLJAZIIFENW-UHFFFAOYSA-N 4-[1,1,1,3,3,3-hexafluoro-2-(4-hydroxy-3-prop-2-enylphenyl)propan-2-yl]-2-prop-2-enylphenol Chemical group C1=C(CC=C)C(O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(O)C(CC=C)=C1 QGHDLJAZIIFENW-UHFFFAOYSA-N 0.000 claims description 4
- 229910019142 PO4 Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000010452 phosphate Substances 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 4
- 229910013063 LiBF 4 Inorganic materials 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- MWQJGSUQGMJVCS-UHFFFAOYSA-N N=[S+]C(F)(F)F.[Li] Chemical compound N=[S+]C(F)(F)F.[Li] MWQJGSUQGMJVCS-UHFFFAOYSA-N 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 206010016766 flatulence Diseases 0.000 abstract description 4
- -1 lithium titanate Chemical class 0.000 abstract 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 229910052799 carbon Inorganic materials 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001733 carboxylic acid esters Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000005678 chain carbonates Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 150000005676 cyclic carbonates Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000003797 solvolysis reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
Classifications
-
- 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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- Secondary Cells (AREA)
Abstract
The invention discloses a kind of lithium titanate battery and electrolyte thereof, aim to provide a kind of lithium titanate battery aerogenesis that can suppress to avoid the lithium titanate battery of battery flatulence when high temperature.This lithium titanate battery comprises negative material and electrolyte, described negative material is lithium titanate, described electrolyte comprises lithium salts, organic solvent and additive, described additive comprises di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), 1, one or more combinations in 3-propane sultone (PS), the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass.The present invention can be widely used in lithium titanate battery field.
Description
Technical field
The present invention relates to a kind of lithium titanate battery and electrolyte thereof.
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 close, when over-charging of battery, the easy precipitating metal lithium of carbon electrodes, it and electrolyte react and produce combustible gas mixture, cause very large potential safety hazard thus 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.Therefore, find under slightly positive current potential, embed lithium than Carbon anode, cheap and easy to get, safe and reliable Novel anode material is necessary.Wherein electronegative potential transition metal oxide and composite oxides cause the extensive attention of people as the negative material of lithium ion battery, lithium titanate (Li
4ti
5o
12) be one of wherein extensively concerned material.Li
4ti
5o
12be 1.55V relative to the current potential of lithium electrode, theoretical specific capacity is 175mAh/g, actual specific capacity 150 ~ 160mAh/g.Embed at Li 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 causing structural damage due to the flexible back and forth of electrode material in charge and discharge cycles, thus improves cycle performance and the useful life of electrode, decrease and increase with cycle-index and bring specific capacity significantly to decay, make Li
4ti
5o
12there is the cycle performance more excellent than Carbon anode.At 25 DEG C, Li
4ti
5o
12electrochemical diffusion coefficient be 2 × 10
-8cm2/s, an order of magnitude larger than the diffusion coefficient in carbon negative pole material, high diffusion coefficient make this negative material can fast, multi cycle discharge and recharge.But find in actual applications, take lithium titanate as battery easy flatulence when high temperature of negative pole, this kind of phenomenon is particularly evident for flexible-packed battery.After deliberation, people generally believe that its reason is to contain trace impurity in lithium titanate, play the effect of catalysis solvolysis aerogenesis when high temperature.Research through us finds, can be addressed this problem by the improvement of electrolyte.
Summary of the invention
Technical problem to be solved by this invention overcomes the deficiencies in the prior art, provides a kind of lithium titanate battery aerogenesis that can suppress to avoid lithium titanate battery and the electrolyte thereof of battery flatulence when high temperature.
The technical scheme that a kind of lithium titanate battery electrolyte of the present invention adopts is: the present invention includes lithium salts, organic solvent and additive, described additive comprises di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), 1, one or more combinations in 3-propane sultone (PS), the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass.
The service quality of described additive is equivalent to described lithium salts and described organic solvent gross mass 2%-3%.
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 wherein several used in combination, 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 the present invention includes negative material, electrolyte lithium salts, organic solvent and additive, described additive comprises di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), 1, one or more combinations in 3-propane sultone (PS), the service quality of described additive is equivalent to 1% ~ 5% of described lithium salts and described organic solvent gross mass, it also comprises negative material, and described negative material is lithium titanate (Li
4ti
5o
12).
The invention has the beneficial effects as follows: owing to adding di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), 1 in electrolyte of the present invention, one or more combined additives in 3-propane sultone (PS), adding of above-mentioned substance can make the surface of lithium titanate battery form excellent SEI film, electrolyte and negative pole can be stoped to be that the direct of lithium titanate material contacts, therefore the present invention the aerogenesis of lithium titanate battery can effectively be suppressed, so can suppress lithium titanate battery aerogenesis to avoid battery flatulence when high temperature.
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 one:
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 wherein several used in combination, its concentration can be 0.5M-1.5M, the lithium hexafluoro phosphate of to be concentration the be 1M adopted in the present embodiment, weight ratio is selected to be that the mixture of the ethylene carbonate (EC) of 1:1:1, diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) is as organic solvent, and by the described lithium salts of 100 weight portions and described organic solvent, add the di-oxalate lithium borate of 1 weight portion as described additive.
Embodiment two:
Other is identical with embodiment one, and described additive is difluorine oxalic acid boracic acid lithium, the di-oxalate lithium borate of 1 weight portion, the PS of 3 weight portions of 1 weight portion.
Embodiment three:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 2 weight portions, the PS of 0.5 weight portion.
Embodiment four:
Other is identical with embodiment one, and described additive is the di-oxalate lithium borate of 1 weight portion, the PS of 3 weight portions.
Embodiment five:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 0.5 weight portion, the di-oxalate lithium borate of 0.5 weight portion.
Embodiment six:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 1 weight portion.
Embodiment seven:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 2.5 weight portions.
Embodiment eight:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 5 weight portions.
Embodiment nine:
Other is identical with embodiment one, and described additive is the PS of 1 weight portion.
Embodiment ten:
Other is identical with embodiment one, and described additive is the PS of 2.5 weight portions.
Embodiment 11:
Other is identical with embodiment one, and described additive is the PS of 5 weight portions.
Embodiment 12:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 0.5 weight portion, the PS of 2 weight portions.
Embodiment 13:
Other is identical with embodiment one, and described additive is the difluorine oxalic acid boracic acid lithium of 2.5 weight portions, the PS of 2.5 weight portions.
Comparative example:
Electrolyte select weight ratio be the mixture of the ethylene carbonate (EC) of 1:1:1, diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) as organic solvent, LiPF6 is 1.0M.
Electrolyte in above-described embodiment is after making battery, and measure battery storge quality at high temperature and normal-temperature circulating performance etc., result is as shown in the table:
Table one
As can be seen from the result of the test of table one, relative to comparative example, after employing additive of the present invention, the high-temperature storage performance of battery and the cycle life of battery significantly improve.
Claims (1)
1. a lithium titanate battery, it comprises lithium titanate battery electrolyte and negative material, and described lithium titanate battery electrolyte comprises lithium salts, organic solvent and additive, and described negative material is lithium titanate (Li
4ti
5o
12), it is characterized in that: described additive comprises di-oxalate lithium borate (LiBOB), difluorine oxalic acid boracic acid lithium (LiODFB), 1, one or more combinations in 3-propane sultone (PS), the service quality of described additive is equivalent to 2% ~ 3% of described lithium salts and described organic solvent gross mass; Described organic solvent selects weight ratio to be the mixture of the ethylene carbonate (EC) of 1:1:1, diethyl carbonate (DEC) and methyl ethyl carbonate (EMC); 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 wherein several used in combination, the concentration of described lithium salts is 0.5M-1.5M.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210397501.9A CN102903956B (en) | 2012-10-19 | 2012-10-19 | Lithium titanate battery and electrolyte thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210397501.9A CN102903956B (en) | 2012-10-19 | 2012-10-19 | Lithium titanate battery and electrolyte thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102903956A CN102903956A (en) | 2013-01-30 |
| CN102903956B true CN102903956B (en) | 2015-09-16 |
Family
ID=47576095
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210397501.9A Active CN102903956B (en) | 2012-10-19 | 2012-10-19 | Lithium titanate battery and electrolyte thereof |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103117414B (en) * | 2013-01-31 | 2016-03-23 | 中航锂电（洛阳）有限公司 | A kind of negative pole lithium titanate battery electrolyte, lithium ion battery and preparation method thereof |
| EP3041078A4 (en) * | 2013-08-30 | 2017-03-08 | UBE Industries, Ltd. | Nonaqueous electrolyte solution for electricity storage devices |
| CN103618110B (en) * | 2013-12-12 | 2015-12-02 | 宁德新能源科技有限公司 | Lithium rechargeable battery and electrolyte thereof |
| CN103840191A (en) * | 2014-03-24 | 2014-06-04 | 四川兴能新材料有限公司 | Lithium titanate battery electrolyte film-forming additive doped with zirconium by gradients |
| KR20160055083A (en) * | 2014-11-07 | 2016-05-17 | 에이일이삼 시스템즈, 엘엘씨 | Electrolyte formulation for reduced gassing wide temperature range cycling |
| CN104600363B (en) * | 2015-02-05 | 2018-02-02 | 中国科学院过程工程研究所 | Electrolyte solution for preventing flatulence of spinel lithium titanate-based lithium-ion secondary battery |
| CN104752768B (en) * | 2015-04-21 | 2018-01-09 | 叶利萍 | A kind of lithium titanate battery electrolyte and its lithium titanate battery |
| CN104979589A (en) * | 2015-07-23 | 2015-10-14 | 东莞市凯欣电池材料有限公司 | High-voltage electrolyte and lithium ion battery using electrolyte |
| CN107305963A (en) * | 2016-04-25 | 2017-10-31 | 上海交通大学 | Electrolyte for lithium-sulfur cell and preparation method thereof |
| 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 |
| CN111540951A (en) * | 2020-05-12 | 2020-08-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Lithium ion battery high-voltage electrolyte for lithium titanate negative electrode material |
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| CN102867990A (en) * | 2011-07-08 | 2013-01-09 | 中国科学院物理研究所 | Electrolyte system for preventing spinel lithium titanate radical lithium ion secondary battery from flatulence |
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|---|---|---|---|---|
| KR100424644B1 (en) * | 2002-03-06 | 2004-03-25 | 삼성에스디아이 주식회사 | Negative active material slurry composition for rechargeable lithium battery and method of preparing negative electrode for rechargeable lithium battery prepared using same |
-
2012
- 2012-10-19 CN CN201210397501.9A patent/CN102903956B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101847750A (en) * | 2009-02-17 | 2010-09-29 | 三星Sdi株式会社 | Flame retardant electrolyte for rechargeable lithium battery and rechargeable lithium battery including the same |
| CN101572331A (en) * | 2009-06-09 | 2009-11-04 | 东莞市杉杉电池材料有限公司 | Lithium ion battery electrolyte suitable for high-temperature environment and preparation method thereof |
| CN102867990A (en) * | 2011-07-08 | 2013-01-09 | 中国科学院物理研究所 | Electrolyte system for preventing spinel lithium titanate radical lithium ion secondary battery from flatulence |
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|---|---|
| CN102903956A (en) | 2013-01-30 |
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Address after: South Bay Area South Town Guangdong city Zhuhai province 519000 two Road No. 2 Patentee 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 Patentee before: Zhuhai Smoothway Electronic Materials Co., Ltd. |