CN107154511A - For the electrolyte of lithium titanate anode battery and the secondary cell including it - Google Patents
For the electrolyte of lithium titanate anode battery and the secondary cell including it Download PDFInfo
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- CN107154511A CN107154511A CN201610118265.0A CN201610118265A CN107154511A CN 107154511 A CN107154511 A CN 107154511A CN 201610118265 A CN201610118265 A CN 201610118265A CN 107154511 A CN107154511 A CN 107154511A
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- electrolyte
- aqueous solvent
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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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- 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)
- Inorganic Chemistry (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)
- Secondary Cells (AREA)
Abstract
The invention provides a kind of electrolyte for lithium titanate anode battery and the secondary cell including it, the electrolyte includes non-aqueous solvent and the LiPF being dissolved in the non-aqueous solvent6, non-aqueous solvent contains：The PC or EC of 20%~60% (weight), the linear carbonates of 44%~74% (weight), the PEC of the FEC of 1%~5% (weight) and 1%~5% (weight).The secondary cell including above-mentioned electrolyte of present invention cubical expansivity after charge and discharge cycles is small.
Description
Technical field
The present invention relates to rechargeable battery field, and in particular to chargeable lithium titanate battery.
Background technology
Lithium titanate (Li4Ti5O12) there is spinel structure, when it is used as the negative material of lithium ion battery, specific capacity
Theoretical value 175mAh/g.Do not changed during embedding de- lithium additionally, due to its lattice constant, be a kind of " zero strain " material
Material.Lithium titanate has excellent electrochemical properties and a structural stability, therefore is a kind of lithium ion very with application prospect
The negative material of battery.
Be presently used for lithium battery electrolyte include non-aqueous solvent and be dissolved in solute salt therein (such as 0.9~
1.3mol/L lithium hexafluoro phosphate (LiPF6)).Non-aqueous solvent is made up of high dielectric solvent and low viscosity solvent, wherein Gao Jie
Electric solvent selects (ring-type) carbonic ester such as propylene carbonate (PC) and vinyl carbonate (EC), and high dielectric solvent has higher Jie
Electric constant, is conducive to the diffusion of lithium ion.Low viscosity solvent selects (linear) carbonic ester such as dimethyl carbonate (DMC), carbonic acid
Diethylester (DEC) and methyl ethyl carbonate (EMC).DMC, DEC or EMC can with propylene carbonate (PC) or vinyl carbonate (EC) with
Arbitrary proportion dissolves each other, and obtained non-aqueous solvent has high lithium salts dissociation capability, high inoxidizability, low viscosity and high led
Electrically.
Although being prepared for the Li of excellent performance at present4Ti5O12Material, the lithium titanate battery prepared using above-mentioned electrolyte is existed
In charge and discharge process, side reaction can occur in electrolyte, cause electrode surface passivation and electrolyte volatilization.Therefore lithium titanate battery
After up to a hundred charge and discharge cycles, the volume of battery can expand, and then cause the problems such as burning or even blast.
The content of the invention
The above-mentioned technical problem existed for prior art, is used for lithium titanate anode The embodiment provides one kind
The electrolyte of battery, including：
Non-aqueous solvent, it contains：
The PC or EC of 20%~60% (weight)；
The linear carbonates of 44%~74% (weight)；
The FEC of 1%~5% (weight)；
The PEC of 1%~5% (weight)；And
It is dissolved in the LiPF in the non-aqueous solvent6。
It is preferred that, the mass ratio of the FEC and PEC are 1：2~2：1.
It is preferred that, the content of the FEC is the 2%~4% of the non-aqueous solvent quality, and the content of the PEC is institute
State the 2%~4% of non-aqueous solvent quality.
It is preferred that, the content of the FEC is the 2%~3% of the non-aqueous solvent quality, and the content of the PEC is institute
State the 2% of non-aqueous solvent quality.
It is preferred that, the LiPF6Concentration be 0.9~1.3mol/L.
It is preferred that, the linear carbonates contain the DMC of 24%~40% (weight) and the EMC of 15%~40% (weight).
Embodiments of the invention additionally provide a kind of secondary cell, including：
Negative pole and positive pole；And
Electrolyte as described above.
It is preferred that, the negative material is Li4Ti5O12。
It is preferred that, the positive electrode is Li [Ni1/3Co1/3Mn1/3] O or LiCoO2。
Fluorinated ethylene carbonate (FEC) and the alkene -1,3- propane sultones (PES) of pillar 1 add non-aqueous as additive
In electrolyte, the volumetric expansion of lithium titanate battery (after up to a hundred times of charge and discharge cycles) is reduced, metatitanic acid is additionally improves
The capability retention of lithium battery.
Brief description of the drawings
Embodiments of the present invention is further illustrated referring to the drawings, wherein：
Fig. 1 is the lithium titanate battery charge and discharge cycles capacity curve at room temperature of embodiment 1.
Fig. 2 be embodiment 1 lithium titanate battery at 55 DEG C charge and discharge cycles capacity curve.
Fig. 3 be comparative example 1 lithium titanate battery at 55 DEG C charge and discharge cycles capacity curve.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, pass through below in conjunction with accompanying drawing specific real
Applying example, the present invention is described in more detail.Describe for convenience, below with PC, DMC, EMC, FEC, PES, LiPF6Difference table
Show propylene carbonate, dimethyl carbonate, methyl ethyl carbonate, fluorinated ethylene carbonate, the alkene -1,3- propane sultones of pillar 1 and
Lithium hexafluoro phosphate.
Embodiment 1
Prepare secondary cell
PC is prepared first：DMC：EMC：FEC：PES mass percent=32%：32%：32%：1%：3% it is non-aqueous
Property solvent, by electrolyte LiPF6It is 1mol/L to be dissolved in wherein to concentration, so as to prepare electrolyte.From Li4Ti5O12It is used as negative pole
Material, Li [Ni1/3Co1/3Mn1/3] O is as positive electrode, aluminium foil is as the collector of both positive and negative polarity, and aluminium flake presses as battery pole ear
Aluminum plastic film soft-package battery is prepared according to method of the prior art.
Aluminum plastic film soft-package battery prepared by embodiment 1 carries out charge and discharge cycles 300 times at room temperature.Fig. 1 shows it
Charge and discharge cycles capacity curve at room temperature, from Fig. 1 it can be calculated that capacity is kept after charge and discharge cycles 300 times at room temperature
Rate is 97%, therefore its low temperature performance excellent.In addition, entering under the conditions of 55 DEG C to aluminum plastic film soft-package battery prepared by embodiment 1
Row charge and discharge cycles 400 times.Fig. 2 shows its charge and discharge cycles capacity curve at 55 DEG C, from Fig. 2 it can be calculated that 55
Capability retention at DEG C after charge and discharge cycles 400 times is about 60%, and its high-temperature behavior is good.Aluminium prepared by embodiment 1
Plastic film soft-package battery is at room temperature after charge and discharge cycles 500 times, and it is only 0.1% to measure its cubical expansivity.Prepared by embodiment 1
The cubical expansivity of aluminum plastic film soft-package battery is shown in Table 1.
Embodiment 2~19：
Electrolyte and aluminum plastic film soft-package battery are prepared using technique same as Example 1, difference is, using table
The constituting of listed different non-aqueous solvents in 1, different additive levels, positive electrode replace corresponding used in embodiment 1
Non-aqueous solvent, additive level and positive electrode.And the cubical expansivity after 500 charge and discharge cycles is measured, battery
The cubical expansivity of manufacture material and battery is also depicted in table 1.
Comparative example 1：
Prepare PC：DMC：EMC mass percent=34%：33%：33% non-aqueous solvent, by electrolyte LiPF6
It is 1mol/L to be dissolved in wherein to concentration, so as to prepare electrolyte.From Li4Ti5O12It is used as negative material, Li [Ni1/3Co1/3Mn1/3]
O is as positive electrode, and aluminium foil is as the collector of both positive and negative polarity, and aluminium flake is as battery pole ear, so as to be prepared for aluminum plastic film soft-package battery.
The aluminum plastic film soft-package battery for preparing comparative example 1 under the conditions of 55 DEG C carries out charge and discharge cycles 350 times, and Fig. 3 is shown
Its charge and discharge cycles capacity curve at 55 DEG C, from Fig. 3 it can be calculated that appearance at 55 DEG C after charge and discharge cycles 350 times
It is only 36% to measure conservation rate.In addition, aluminum plastic film soft-package battery prepared by comparative example 1 is at room temperature after charge and discharge cycles 500 times,
It is 5% to measure its cubical expansivity.The cubical expansivity of aluminum plastic film soft-package battery is also depicted in table 1.
Table 1
Understood based on table 1, the DMC that the PC for being 20%~60% in mass percent, mass percent are 24%~40%
The FEC and 1% that mass percent is 1%~5% is added in the non-aqueous solvent for the EMC for being 15%~40% with mass percent
~5% PEC, reduces cubical expansivity of the metatitanic acid lithium secondary battery after 500 discharge cycles.Wherein, in electrolyte
FEC and PEC mass ratio is preferably 1：2~2：1, more preferably FEC and PEC mass percent are all 2%~4%.
The mass percent of linear carbonates in the non-aqueous solvent of above-described embodiment is 44%~74%, but the present invention
Non-aqueous solvent in linear carbonates be not limited to DMC and EMC.In the other embodiment of the present invention, linear carbonates
The group constituted selected from DMC, EMC and DEC.
In other embodiments of the invention, metatitanic acid lithium secondary battery can also be reduced in up to a hundred electric discharges by PC being replaced with into EC
Cubical expansivity after circulation.
LiPF in the electrolyte of the present invention6Concentration be not limited to 1mol/L, add in other embodiments of the invention
0.9~1.3mol/L LiPF6Also the cubical expansivity after battery charging and discharging can be substantially reduced.
Although the present invention be described by means of preferred embodiments, but the present invention be not limited to it is described here
Embodiment, without departing from the present invention also include made various changes and change.
Claims (9)
1. a kind of electrolyte for lithium titanate anode battery, it is characterised in that the electrolyte includes：
Non-aqueous solvent, it contains：
The PC or EC of 20%~60% (weight)；
The linear carbonates of 44%~74% (weight)；
The FEC of 1%~5% (weight)；
The PEC of 1%~5% (weight)；And
It is dissolved in the LiPF in the non-aqueous solvent6。
2. electrolyte according to claim 1, it is characterised in that the mass ratio of the FEC and PEC are 1：2~2：1.
3. electrolyte according to claim 2, it is characterised in that the content of the FEC is the non-aqueous solvent quality
2%~4%, the content of the PEC is the 2%~4% of the non-aqueous solvent quality.
4. electrolyte according to claim 3, it is characterised in that the content of the FEC is the non-aqueous solvent quality
2%~3%, the content of the PEC is the 2% of the non-aqueous solvent quality.
5. the electrolyte according to any one of claim 1-4, it is characterised in that the LiPF6Concentration be 0.9~
1.3mol/L。
6. the electrolyte according to any one of claim 1-4, it is characterised in that the linear carbonates contain 24%~
The DMC of 40% (weight) and 15%~40% (weight) EMC.
7. a kind of secondary cell, it is characterised in that including：
Negative pole and positive pole；And
Electrolyte as any one of claim 1-6.
8. secondary cell according to claim 7, it is characterised in that the negative material is Li4Ti5O12。
9. secondary cell according to claim 7, it is characterised in that the positive electrode is Li [Ni1/3Co1/3Mn1/3]O
Or LiCoO2。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118265.0A CN107154511A (en) | 2016-03-02 | 2016-03-02 | For the electrolyte of lithium titanate anode battery and the secondary cell including it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610118265.0A CN107154511A (en) | 2016-03-02 | 2016-03-02 | For the electrolyte of lithium titanate anode battery and the secondary cell including it |
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| Publication Number | Publication Date |
|---|---|
| CN107154511A true CN107154511A (en) | 2017-09-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610118265.0A Pending CN107154511A (en) | 2016-03-02 | 2016-03-02 | For the electrolyte of lithium titanate anode battery and the secondary cell including it |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101453006A (en) * | 2007-12-03 | 2009-06-10 | 中国科学院成都有机化学有限公司 | Lithium ionic cell electrode material with micro hole construction and manufacturing method thereof |
| CN102082300A (en) * | 2009-11-27 | 2011-06-01 | 三星Sdi株式会社 | Method of manufacturing lithium secondary battery |
| CN105322227A (en) * | 2014-07-09 | 2016-02-10 | 惠州Tcl金能电池有限公司 | Lithium ion battery electrolyte, preparation method thereof, and lithium ion battery |
| CN105359326A (en) * | 2013-12-19 | 2016-02-24 | Sk新技术株式会社 | Lithium secondary battery electrolyte and lithium secondary battery including same |
-
2016
- 2016-03-02 CN CN201610118265.0A patent/CN107154511A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101453006A (en) * | 2007-12-03 | 2009-06-10 | 中国科学院成都有机化学有限公司 | Lithium ionic cell electrode material with micro hole construction and manufacturing method thereof |
| CN102082300A (en) * | 2009-11-27 | 2011-06-01 | 三星Sdi株式会社 | Method of manufacturing lithium secondary battery |
| CN105359326A (en) * | 2013-12-19 | 2016-02-24 | Sk新技术株式会社 | Lithium secondary battery electrolyte and lithium secondary battery including same |
| CN105322227A (en) * | 2014-07-09 | 2016-02-10 | 惠州Tcl金能电池有限公司 | Lithium ion battery electrolyte, preparation method thereof, and lithium ion battery |
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Application publication date: 20170912 |