CN106920992A - A kind of high magnification capacity type power battery electrolyte - Google Patents
A kind of high magnification capacity type power battery electrolyte Download PDFInfo
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- CN106920992A CN106920992A CN201510992123.2A CN201510992123A CN106920992A CN 106920992 A CN106920992 A CN 106920992A CN 201510992123 A CN201510992123 A CN 201510992123A CN 106920992 A CN106920992 A CN 106920992A
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- additive
- power battery
- type power
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- battery electrolyte
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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
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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- 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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- 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 present invention provides a kind of high magnification high capacity type power battery electrolyte, includes lithium salts, non-aqueous organic solvent, functional additive and film for additive, and the film for additive is the double fluorine phosphorous acid lithiums of lithium salts.The present invention adds a kind of new lithium salts additive LiDFP on the basis of existing capability the additive such as electrolyte comprising VC, optimizes SEI film chemical compositions, and lifting negative pole/electrolyte interface Li+ transmission dynamics improves electrokinetic cell high-multiplying power discharge specific capacity.
Description
【Technical field】
The present invention relates to technical field of lithium batteries, more particularly to a kind of high magnification capacity type power battery electrolyte.
【Background technology】
At present, lithium battery is applied to electric automobile field more and more widely.Existing commercial electrolyte liquid is born
Functional additive such as vinylene carbonate VC in pole forms polymer SEI films (solid electrolyte
Interface, solid electrolyte interface film) although film forming efficiency is high, good cycling stability, it is high into membrane impedance,
The migration of lithium ion during battery high power charging-discharging is further hindered in the case of the negative pole high-pressure solid,
The requirement of electrokinetic cell high magnification high power capacity can not be met.Existing electrolyte improves high rate performance and can pass through
Solvent complex reduction electrolysis fluid viscosity, the solubility (increase amount of ions), the improvement that improve electrolyte lithium salt
Electrolyte and both positive and negative polarity interface and increase electrolyte to wellability of positive and negative pole material etc. and realize.Publication number
CN1925207A patents are added crown ether and improve electrolytic conductivity to a certain extent in the electrolytic solution, but forthright again
Negative pole/electrolyte interface ionic conduction can be still limited by, and crown ether toxicity is high, it is expensive, and do not apply to
In high volume applications；CN 102496739A patents reduce electrolyte by the introducing containing fluorous solvent FEC
The degree of dissociation of viscosity and lithium salts, improves the diffusion speed of electrolyte ion electrical conductivity and ion in electrode material
Rate, effectively reduces SEI membrane impedances, but FEC amounts are excessively easy to produce HF in negative terminal surface reduction, trigger not
Good side reaction；Same CN103715457A patents use dimethylacetylamide as additive, are only to carry
Nonaqueous electrolytic solution electrical conductivity high, it is impossible to fundamentally meet the requirement of battery high magnification high power capacity.
【The content of the invention】
The technical problems to be solved by the invention are to provide a kind of high magnification capacity type power battery electrolyte,
To improve electrokinetic cell rate charge-discharge characteristic.
To achieve these goals, the present invention provides a kind of high magnification high capacity type power battery electrolyte, bag
Containing lithium salts, non-aqueous organic solvent, functional additive and film for additive, the film for additive is lithium salts
Double fluorine phosphorous acid lithiums.
The beneficial effects of the invention are as follows：Base of the present invention in the existing capability additive such as electrolyte comprising VC
On plinth, a kind of new lithium salts additive LiDFP is added, optimize SEI film chemical compositions, lift negative pole/electrolysis
Liquid interface Li+ transmits dynamics, improves electrokinetic cell high-multiplying power discharge specific capacity.
【Brief description of the drawings】
Fig. 1 is the film for additive fluorine phosphorous acid lithium of high magnification high capacity type power battery electrolyte of the present invention
Chemical constitution.
Fig. 2 is the negative pole SEI membrane modles of invention high magnification high capacity type power battery electrolyte.
Fig. 3 is that high magnification high capacity type power battery electrolyte of the present invention is electrolysed with the electrokinetic cell of prior art
The battery that liquid is respectively prepared circulates 200 weeks performance charts in normal temperature 6C.
Fig. 4 is invention high magnification high capacity type power battery electrolyte and other existing power battery electrolytes
The impedance spectra at the negative pole SEI interfaces of formation.
【Specific embodiment】
In order that the purpose of the present invention, technical scheme and Advantageous Effects become apparent from understanding, below in conjunction with
The drawings and specific embodiments, the present invention will be described in further detail.It should be appreciated that this explanation
Specific embodiment described in book is not intended to limit the present invention just for the sake of explaining the present invention.
The present invention provides a kind of high magnification high capacity type power battery electrolyte, includes lithium salts, non-aqueous organic
Solvent, functional additive and film for additive, the film for additive are the double fluorine phosphorous acid lithiums of lithium salts.
In present embodiment, the lithium salts is lithium salts lithium hexafluoro phosphate.
The non-aqueous organic solvent contains cyclic carbonate and linear carbonates.In the present embodiment, it is described
Cyclic carbonate and linear carbonates are selected from ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid first
One or more in ethyl ester, diethyl carbonate, gamma-butyrolacton, ethyl acetate, propyl acetate, ethyl propionate
Combination.
The functional additive is selected from vinylene carbonate, 1,3- propane sultones, fluorinated ethylene carbonate, carbon
Sour ethene vinylene, sulfuric acid vinyl ester, sulfuric acid propylene, 1,3- propene sultones, methane-disulfonic acid are sub-
Methyl esters, 1,4- butyl sultones, biphenyl, fluorobenzene, cyclohexyl benzene, tert-butyl benzene, hmds, seven
The combination of one or more in the silicon amine of methyl two, succinonitrile, adiponitrile.Described functional additive is in electricity
Weight/mass percentage composition in solution liquid is 0.5-10%.
The structural formula of the double fluorine phosphorous acid lithium LiDFP of lithium salts is as shown in Figure 1.The film for additive has non-aqueous
Weight/mass percentage composition in machine solvent is 0.5-2%.The double fluorine phosphorous acid lithium LiDFP of lithium salts are used as film for additive
SEI film chemical compositions can be improved with VC collective effects, negative pole/electrolyte interface impedance is reduced, lithium is lifted
Ion interface transmits dynamics.Active lithium-ion can be supplemented simultaneously, it is ensured that high rate cyclic process lithium ion
Consumption.Because LiDFP anion structures have high symmetry, electric negative center P atoms are strong with having
- F the functional groups of strong electron-withdrawing power are connected, and make the distribution of charges of anion more dispersed, and ionic radius is big,
Therefore there is degree of dissociation very high, its electrolytic conductivity is high.From electrochemical reaction, P element film forming
Agent contains more Li in the chemical composition of cathodic reductionXPFyAnd LiXPOFy, above material and VC are also originated in
The SEI films that thing builds jointly have more preferable lithium ion conduction performance and stability (SEI membrane modles such as Fig. 2).
To sum up, double fluorine phosphorous acid lithium LiDFP are a kind of very promising electrolyte film for additive.
Embodiment 1：At room temperature, by ethylene carbonate (EC), dimethyl carbonate in the glove box full of argon gas
(DMC), ethyl acetate (EA) is according to mass ratio 1:2:1 is mixed, and is added to weight/mass percentage composition and is
2% vinylene carbonate (VC) and 1% pair of fluorine phosphorous acid lithium (LiDFP), add lithium salts lithium hexafluoro phosphate
LiPF6 is dissolved to concentration for 1.1mol/L, is prepared into electrolyte 1.
Embodiment 2：At room temperature, by ethylene carbonate (EC), dimethyl carbonate in the glove box full of argon gas
(DMC), ethyl acetate (EA) is according to mass ratio 1:2:1 is mixed, and is added to weight/mass percentage composition and is
2% vinylene carbonate (VC), adds lithium salts lithium hexafluoro phosphate LiPF6 and is dissolved to concentration for 1.1mol/L,
It is prepared into electrolyte 2.
Using iron lithium as positive pole, graphite as negative pole, negative pole compacting >=1.60g/cm3, while using embodiment
1 and 2 electrolyte are assembled into the full battery of cylinder, and capacity 5.8Ah carries out rate charge-discharge circulation with 6C electric currents,
Measurement result is as shown in Figure 3.
As can be seen from Figure 3：Electrolyte 1, the normal temperature 6C of electrolyte 2 circulate 200 weeks capability retention difference
For the addition of 96%, 88%, LiDFP additives can be effectively improved the circulation performance of high power capacity electrokinetic cell,
Because pure VC is as film forming agent, and the interface impedance in the case of negative pole high compacted density is big, hinder lithium from
The fast transferring of son, causes polarize big negative pole analysis lithium, circulation diving.
In addition, be can be seen that from Fig. 4 AC impedance spectroscopies：The addition of LiDFP can effectively reduce negative pole/electrolysis
The impedance of liquid interface SEI films, lifting lithium ion interface transmission dynamics, meets under negative pole high compacted density
High-multiplying power discharge specific capacity.
The new lithium salts additive LiDFP of addition of the invention, electrolyte conventional additives VC collective effects,
The SEI films that stability is high and interface impedance is low are formed in negative terminal surface, improves high power capacity electrokinetic cell in high power
Cycle performance under rate charge status.LiDFP anion structures have high symmetry, electric negative center P
Atom is connected with-F the functional groups with strong electron-withdrawing power, makes the distribution of charges of anion more dispersed,
Ionic radius is big, therefore with degree of dissociation very high, its electrolytic conductivity is high.From electrochemical reaction
See, P element film forming agent contains more Li in the chemical composition of cathodic reductionXPFyAnd LiXPOFy, above thing
The SEI films that matter builds jointly with VC reduzates have more preferable lithium ion conduction performance and stability.
The present invention is not restricted to described in specification and implementation method, therefore for the people of familiar field
Additional advantage and modification are easily achieved for member, therefore are limited without departing substantially from claim and equivalency range
In the case of the spirit and scope of fixed universal, the present invention is not limited to specific details, representational
Equipment and shown here as with description examples shown.
Claims (8)
1. a kind of high magnification high capacity type power battery electrolyte, includes lithium salts, non-aqueous organic solvent, work(
Energy additive and film for additive, it is characterised in that：The film for additive is the double fluorine phosphorous acid lithiums of lithium salts.
2. high magnification high capacity type power battery electrolyte as claimed in claim 1, it is characterised in that：Institute
The structural formula for stating the double fluorine phosphorous acid lithiums of lithium salts is as follows：
3. high magnification high capacity type power battery electrolyte as claimed in claim 2, it is characterised in that：Institute
Weight/mass percentage composition of the film for additive in non-aqueous organic solvent is stated for 0.5-2%.
4. high magnification high capacity type power battery electrolyte as claimed in claim 1, it is characterised in that：Lithium
Salt is lithium salts lithium hexafluoro phosphate.
5. high magnification high capacity type power battery electrolyte as claimed in claim 1, it is characterised in that：Institute
State non-aqueous organic solvent and contain cyclic carbonate and linear carbonates.
6. high magnification high capacity type power battery electrolyte as claimed in claim 5, it is characterised in that：Institute
State cyclic carbonate and linear carbonates are selected from ethylene carbonate, propene carbonate, dimethyl carbonate, carbonic acid
One kind or several in methyl ethyl ester, diethyl carbonate, gamma-butyrolacton, ethyl acetate, propyl acetate, ethyl propionate
The combination planted.
7. high magnification high capacity type power battery electrolyte as claimed in claim 1, it is characterised in that：Institute
State functional additive and be selected from vinylene carbonate, 1,3- propane sultones, fluorinated ethylene carbonate, ethylene carbonate
Vinylene, sulfuric acid vinyl ester, sulfuric acid propylene, 1,3- propene sultones, methane-disulfonic acid methylene ester,
1,4- butyl sultones, biphenyl, fluorobenzene, cyclohexyl benzene, tert-butyl benzene, hmds, seven methyl two
The combination of one or more in silicon amine, succinonitrile, adiponitrile.
8. high magnification high capacity type power battery electrolyte as claimed in claim 7, it is characterised in that：Institute
The functional additive stated weight/mass percentage composition in the electrolytic solution is 0.5-10%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510992123.2A CN106920992A (en) | 2015-12-27 | 2015-12-27 | A kind of high magnification capacity type power battery electrolyte |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510992123.2A CN106920992A (en) | 2015-12-27 | 2015-12-27 | A kind of high magnification capacity type power battery electrolyte |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107681191A (en) * | 2017-08-29 | 2018-02-09 | 江苏楚汉新能源科技有限公司 | A kind of high-voltage lithium ion batteries |
| CN108767318A (en) * | 2018-05-24 | 2018-11-06 | 国联汽车动力电池研究院有限责任公司 | A kind of lithium salt electrolyte containing additive |
| WO2019025980A1 (en) * | 2017-07-31 | 2019-02-07 | Tesla Motors Canada ULC | Novel battery systems based on lithium difluorophosphate |
| CN109428118A (en) * | 2017-08-23 | 2019-03-05 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN110233291A (en) * | 2019-05-31 | 2019-09-13 | 骆驼集团新能源电池有限公司 | A kind of wide temperate zone lithium battery electrolytes of 12V start and stop balancing high/low temperature |
| CN113270643A (en) * | 2017-08-28 | 2021-08-17 | 朝阳光达化工有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
| CN116190777A (en) * | 2022-12-20 | 2023-05-30 | 重庆太蓝新能源有限公司 | Cellulose-based eutectic gel electrolyte, preparation method and application thereof |
| US11961959B2 (en) | 2017-07-31 | 2024-04-16 | Tesla, Inc. | Battery systems based on lithium difluorophosphate |
| US12100812B2 (en) | 2020-10-16 | 2024-09-24 | Tesla, Inc. | Battery systems based on two-additive electrolyte system |
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| CN104781976A (en) * | 2013-02-20 | 2015-07-15 | 株式会社Lg化学 | Electrolyte additive for lithium secondary battery, non-aqueous electrolyte containing said electrolyte additive, and lithium secondary battery |
| KR20150095248A (en) * | 2014-02-13 | 2015-08-21 | 파낙스 이텍(주) | Electrolyte with additive for lithium secondary battery and lithium secondary battery |
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Patent Citations (3)
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| CN104781976A (en) * | 2013-02-20 | 2015-07-15 | 株式会社Lg化学 | Electrolyte additive for lithium secondary battery, non-aqueous electrolyte containing said electrolyte additive, and lithium secondary battery |
| KR20150095248A (en) * | 2014-02-13 | 2015-08-21 | 파낙스 이텍(주) | Electrolyte with additive for lithium secondary battery and lithium secondary battery |
| US20150288033A1 (en) * | 2014-04-07 | 2015-10-08 | Samsung Sdi Co., Ltd. | Rechargeable lithium battery |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019025980A1 (en) * | 2017-07-31 | 2019-02-07 | Tesla Motors Canada ULC | Novel battery systems based on lithium difluorophosphate |
| CN111149247A (en) * | 2017-07-31 | 2020-05-12 | 特斯拉汽车加拿大无限责任公司 | Novel battery system based on lithium difluorophosphate |
| US11961959B2 (en) | 2017-07-31 | 2024-04-16 | Tesla, Inc. | Battery systems based on lithium difluorophosphate |
| CN109428118A (en) * | 2017-08-23 | 2019-03-05 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN109428118B (en) * | 2017-08-23 | 2021-04-30 | 宁德时代新能源科技股份有限公司 | Lithium ion battery and electrolyte thereof |
| CN113270643A (en) * | 2017-08-28 | 2021-08-17 | 朝阳光达化工有限公司 | Lithium ion battery electrolyte and lithium ion battery containing same |
| CN107681191A (en) * | 2017-08-29 | 2018-02-09 | 江苏楚汉新能源科技有限公司 | A kind of high-voltage lithium ion batteries |
| CN108767318A (en) * | 2018-05-24 | 2018-11-06 | 国联汽车动力电池研究院有限责任公司 | A kind of lithium salt electrolyte containing additive |
| CN110233291A (en) * | 2019-05-31 | 2019-09-13 | 骆驼集团新能源电池有限公司 | A kind of wide temperate zone lithium battery electrolytes of 12V start and stop balancing high/low temperature |
| US12100812B2 (en) | 2020-10-16 | 2024-09-24 | Tesla, Inc. | Battery systems based on two-additive electrolyte system |
| CN116190777A (en) * | 2022-12-20 | 2023-05-30 | 重庆太蓝新能源有限公司 | Cellulose-based eutectic gel electrolyte, preparation method and application thereof |
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Application publication date: 20170704 |