CN103872376A - Lithium titanate battery and electrolyte thereof - Google Patents
Lithium titanate battery and electrolyte thereof Download PDFInfo
- Publication number
- CN103872376A CN103872376A CN201410057460.8A CN201410057460A CN103872376A CN 103872376 A CN103872376 A CN 103872376A CN 201410057460 A CN201410057460 A CN 201410057460A CN 103872376 A CN103872376 A CN 103872376A
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- CN
- China
- Prior art keywords
- lithium
- lithium titanate
- titanate battery
- electrolyte
- additive
- 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.)
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Classifications
-
- 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
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses a lithium titanate battery and an electrolyte thereof, and aims at providing the lithium titanate battery and the electrolyte thereof capable of preventing the lithium titanate battery from producing a gas to avoid flatulence of the battery at high temperature. The lithium titanate battery comprises a cathode material and an electrolyte, wherein the cathode material is lithium titanate; the electrolyte comprises a lithium salt, an organic solvent and an additive; the additive comprises one or more of lithium bis(oxalato) borate (LiBOB), lithium oxalyldifluoroborate (LiODFB) and 1,3-propane sultone (PS). The quality of the additive in use is equal to 1-5% of total mass of the lithium salt and the organic solvent. The electrolyte can be widely applied to the field of the lithium titanate battery.
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 approaching, in the time of 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.Therefore, searching embeds lithium than carbon negative pole under slightly positive current potential, cheap and easy to get, safe and reliable Novel anode material is necessary.Wherein electronegative potential transition metal oxide and composite oxides have caused people's extensive attention, lithium titanate (Li as the negative material of lithium ion battery
4ti
5o
12) be one of wide concerned material wherein.Li
4ti
5o
12be 1.55V with respect to the current potential of lithium electrode, theoretical specific capacity is 175mAh/g, actual specific capacity 150～160mAh/g.Embed or deviate from process at Li, 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, thus cycle performance and the useful life of improving electrode, reduce with cycle-index and increased and bring specific capacity significantly to decay, made Li
4ti
5o
12there is the cycle performance better than carbon negative pole.At 25 DEG C, 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, to find in actual applications, the battery taking lithium titanate as negative pole is easy flatulence in the time of high temperature, and 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 in the time of high temperature.Research through us is found, can address this problem by the improvement of electrolyte.
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 and the electrolyte thereof of battery flatulence when the high temperature.
The technical scheme that a kind of lithium titanate battery of the present invention adopts with electrolyte 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 (LiPF6), LiBF4 (LiBF4), bis trifluoromethyl sulfimide lithium
Any one in (LiN (CF3SO2) 2) or several mixing uses wherein, 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 to 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 having added 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 good SEI film, and can stop electrolyte and negative pole is directly connecing of lithium titanate material
The present invention touches, therefore can effectively suppress the aerogenesis of lithium titanate battery, so can suppress lithium titanate battery aerogenesis to avoid battery flatulence when the 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 mono-:
Lithium titanate battery of the present invention comprises positive electrode, negative material and electrolyte, described negative material is lithium titanate, described electrolyte comprises lithium salts, organic solvent and additive, and described lithium salts can be lithium hexafluoro phosphate (LiPF6), tetrafluoro boron
Any one in acid lithium (LiBF4), bis trifluoromethyl sulfimide lithium (LiN (CF3SO2) 2) or several mixing uses wherein, its concentration can be 0.5M-1.5M, what in the present embodiment, adopt is that concentration is the lithium hexafluoro phosphate of 1M, selecting weight ratio is that the mixture of ethylene carbonate (EC), diethyl carbonate (DEC) and methyl ethyl carbonate (EMC) of 1:1:1 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 bis-:
Other is identical with embodiment mono-, described additive be difluorine oxalic acid boracic acid lithium, 1 weight portion of 1 weight portion di-oxalate lithium borate, 3 weight portions 1,3-propane sultone.
Embodiment tri-:
Other is identical with embodiment mono-, described additive be 2 weight portions difluorine oxalic acid boracic acid lithium, 0.5 weight portion 1,3-third
Alkane sultone.
Embodiment tetra-:
Other is identical with embodiment mono-, 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 mono-, 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 mono-, and described additive is the difluorine oxalic acid boracic acid lithium of 1 weight portion.
Embodiment seven:
Other is identical with embodiment mono-, and described additive is the difluorine oxalic acid boracic acid lithium of 2.5 weight portions.
Embodiment eight:
Other is identical with embodiment mono-, and described additive is the difluorine oxalic acid boracic acid lithium of 5 weight portions.
Embodiment nine:
Other is identical with embodiment mono-, and described additive is 1 of 1 weight portion, 3-propane sultone.
Embodiment ten:
Other is identical with embodiment mono-, and described additive is 1 of 2.5 weight portions, 3-propane sultone.
Embodiment 11:
Other is identical with embodiment mono-, and described additive is 1 of 5 weight portions, 3-propane sultone.
Embodiment 12:
Other is identical with embodiment mono-, 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 mono-, described additive be 2.5 weight portions difluorine oxalic acid boracic acid lithium, 2.5 weight portions 1,3-propane sultone.
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 is after making battery, measure battery storge quality and normal-temperature circulating performance etc. at high temperature, with respect to comparative example, use after additive of the present invention, the high-temperature storage performance of battery and the cycle life of battery obviously improve.
The foregoing is only preferred embodiment of the present invention, not in order to limit the present invention, all any amendments of doing within the spirit and principles in the present invention, replace and improvement etc. on an equal basis, within all should dropping on protection scope of the present invention.
Claims (5)
1. a lithium titanate battery electrolyte, it comprises lithium salts, organic solvent and additive, 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 1% ~ 5% of described lithium salts and described organic solvent gross mass.
2. according to the lithium titanate battery electrolyte described in claim 1, it is characterized in that: the service quality of described additive is equivalent to the 2%-3% of described lithium salts and described organic solvent gross mass.
3. according to the lithium titanate battery electrolyte described in claim 1, it is characterized in that: 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 are wherein used, the concentration of described lithium salts is 0.5M-1.5M.
4. according to the lithium titanate battery electrolyte described in claim 1, it is characterized in that: described organic solvent is one or more of chain and cyclic carbonates, carboxylic acid esters, ethers and heterocyclic compound.
5. a lithium titanate battery that comprises lithium titanate battery electrolyte described in claim 1, is characterized in that: it also comprises negative material, described negative material is lithium titanate (Li
4ti
5o
12).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410057460.8A CN103872376A (en) | 2014-02-20 | 2014-02-20 | Lithium titanate battery and electrolyte thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410057460.8A CN103872376A (en) | 2014-02-20 | 2014-02-20 | Lithium titanate battery and electrolyte thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN103872376A true CN103872376A (en) | 2014-06-18 |
Family
ID=50910669
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410057460.8A Pending CN103872376A (en) | 2014-02-20 | 2014-02-20 | Lithium titanate battery and electrolyte thereof |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600363A (en) * | 2015-02-05 | 2015-05-06 | 中国科学院过程工程研究所 | Electrolyte for preventing spinel lithium titanate-based lithium ion secondary battery from flatulence |
| CN104900917A (en) * | 2015-07-09 | 2015-09-09 | 上海动力储能电池系统工程技术有限公司 | Electrolyte for lithium titanate lithium ion 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 |
| CN111987358A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Titanium-containing lithium ion battery electrolyte additive and preparation method and application thereof |
-
2014
- 2014-02-20 CN CN201410057460.8A patent/CN103872376A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104600363A (en) * | 2015-02-05 | 2015-05-06 | 中国科学院过程工程研究所 | Electrolyte for preventing spinel lithium titanate-based lithium ion secondary battery from flatulence |
| CN104900917A (en) * | 2015-07-09 | 2015-09-09 | 上海动力储能电池系统工程技术有限公司 | Electrolyte for lithium titanate lithium ion 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 |
| CN111987358A (en) * | 2019-11-27 | 2020-11-24 | 中节能万润股份有限公司 | Titanium-containing lithium ion battery electrolyte additive and preparation method and application thereof |
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| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20140618 |
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| WD01 | Invention patent application deemed withdrawn after publication |