CN103887563A - Lithium ion secondary battery electrolyte - Google Patents
Lithium ion secondary battery electrolyte Download PDFInfo
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- CN103887563A CN103887563A CN201410137879.4A CN201410137879A CN103887563A CN 103887563 A CN103887563 A CN 103887563A CN 201410137879 A CN201410137879 A CN 201410137879A CN 103887563 A CN103887563 A CN 103887563A
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- lithium
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- ion secondary
- secondary battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 40
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 39
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 13
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 13
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- -1 wherein Substances 0.000 claims description 19
- 239000000203 mixture Substances 0.000 claims description 15
- YACKEPLHDIMKIO-UHFFFAOYSA-L methylphosphonate(2-) Chemical compound CP([O-])([O-])=O YACKEPLHDIMKIO-UHFFFAOYSA-L 0.000 claims description 14
- 239000011356 non-aqueous organic solvent Substances 0.000 claims description 14
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 claims description 9
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 17
- 229910002804 graphite Inorganic materials 0.000 abstract description 17
- 239000010439 graphite Substances 0.000 abstract description 17
- 238000000034 method Methods 0.000 abstract description 13
- 125000004122 cyclic group Chemical group 0.000 abstract description 7
- 150000002148 esters Chemical class 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 abstract description 3
- 230000009467 reduction Effects 0.000 abstract description 3
- 239000007784 solid electrolyte Substances 0.000 abstract description 3
- 239000003125 aqueous solvent Substances 0.000 abstract 4
- 238000007599 discharging Methods 0.000 abstract 1
- 239000013538 functional additive Substances 0.000 abstract 1
- 238000009830 intercalation Methods 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 26
- 229910052744 lithium Inorganic materials 0.000 description 26
- 239000000654 additive Substances 0.000 description 8
- 230000000996 additive effect Effects 0.000 description 8
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- SIXOAUAWLZKQKX-UHFFFAOYSA-N carbonic acid;prop-1-ene Chemical compound CC=C.OC(O)=O SIXOAUAWLZKQKX-UHFFFAOYSA-N 0.000 description 5
- 230000014759 maintenance of location Effects 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- LGCNDZIFJKHQHB-UHFFFAOYSA-N 1,3-dioxacycloundecan-2-one Chemical compound O=C1OCCCCCCCCO1 LGCNDZIFJKHQHB-UHFFFAOYSA-N 0.000 description 2
- UXFQFBNBSPQBJW-UHFFFAOYSA-N 2-amino-2-methylpropane-1,3-diol Chemical compound OCC(N)(C)CO UXFQFBNBSPQBJW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910013872 LiPF Inorganic materials 0.000 description 2
- 101150058243 Lipf gene Proteins 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 239000007767 bonding agent Substances 0.000 description 2
- DLIJPAHLBJIQHE-UHFFFAOYSA-N butylphosphane Chemical compound CCCCP DLIJPAHLBJIQHE-UHFFFAOYSA-N 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 150000005676 cyclic carbonates Chemical class 0.000 description 2
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 2
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 2
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical group CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 2
- YYSONLHJONEUMT-UHFFFAOYSA-N pentan-3-yl hydrogen carbonate Chemical compound CCC(CC)OC(O)=O YYSONLHJONEUMT-UHFFFAOYSA-N 0.000 description 2
- 238000005476 soldering Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000009966 trimming Methods 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910015015 LiAsF 6 Inorganic materials 0.000 description 1
- 229910013063 LiBF 4 Inorganic materials 0.000 description 1
- 229910013188 LiBOB Inorganic materials 0.000 description 1
- 229910013684 LiClO 4 Inorganic materials 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000005030 aluminium foil Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- GATNOFPXSDHULC-UHFFFAOYSA-N ethylphosphonic acid Chemical compound CCP(O)(O)=O GATNOFPXSDHULC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000007614 solvation Methods 0.000 description 1
- 150000003871 sulfonates Chemical class 0.000 description 1
- 239000002562 thickening agent Substances 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic 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
Landscapes
- 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 lithium ion secondary battery electrolyte comprising a non-aqueous solvent and lithium salt dissolved into the non-aqueous solvent, wherein non-aqueous solvent contains cyclic phosphoric ester accounting for 0.5-15% of the total mass of non-aqueous solvent. Cyclic phosphoric ester has the structural formula as the specification, wherein n is an integer ranging from 0 to 2, and R is a straight-chain or branched-chain alkyl from C1 to C4. A functional additive used by the lithium ion secondary battery electrolyte has a relatively high reduction potential and can be used for forming a layer of compact and stable solid electrolyte passive film (SEI) in the first charging process, so that the co-intercalation of propylene carbonate (PC) to graphite can be effectively inhibited, the initial discharging capacity of a battery can be effectively increased, the cycle life of the battery can be effectively prolonged, and the high-and-low temperature performance of the battery can be effectively improved.
Description
Technical field
The present invention relates to a kind of lithium rechargeable battery, especially improve lithium rechargeable battery and the electrolyte thereof of cycle performance of battery.
Background technology
Lithium ion battery is the green high-capacity environment-protecting battery occurring the nineties in 20th century, there is the advantages such as voltage is high, volume is little, quality is light, specific energy is high, memory-less effect, pollution-free, self discharge is little, the life-span is long due to it, emphasize in compact, multi-functional portable type electronic product application universal rapidly at mobile phone, notebook computer, video camera, digital camera etc.
Graphite is the most frequently used negative material of lithium ion battery, is also current application electrode material the most widely.Battery is in initial charge process, the lithium ion being discharged by the anodal lithium-transition metal oxide of battery, through electrolyte, sees through barrier film and arrives graphite cathode, and generate half lithium carbonate in graphite cathode generation reduction reaction, the lithium salts such as Sulfonic Lithium, form film in negative terminal surface thus.The film of this type is called as organic solid electrolyte interface (SEI) film.Peeling off of the graphite that the effect that this passivating film not only plays lithium ion passage also can stop solvent to be embedded into cause in graphite.Propene carbonate is as one of conventional electrolyte solvent, and it has wide liquid scope, and its fusing point is low, and boiling point is high, is conventional electrolyte solvent.In the time of propene carbonate and graphite collocation use, propylene carbonate solvent molecule can not form stable SEI film at graphite electrode surface, it together embeds graphite layers in company with solvation lithium ion, cause peeling off of graphite, and then destroy the lamellar structure of graphite, performance to graphite causes adverse influence, makes the degradation such as battery capacity, circulation.In view of this, be necessary to provide a kind of additive that can promote graphite cathode film forming, effectively improve initial discharge capacity, cycle life and the high temperature performance of lithium ion battery.
Summary of the invention
The problem existing for prior art, the invention provides a kind of electrolyte of lithium-ion secondary battery.This electrolyte solves battery in charging process, the reduction decomposition of organic solvent in electrolyte, the problem that causes graphite to be peeled off.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of electrolyte of lithium-ion secondary battery, it comprises non-aqueous organic solvent and is dissolved in the lithium salts in non-aqueous organic solvent, wherein, non-aqueous organic solvent contains quality and accounts for the annular phosphonate of non-aqueous organic solvent gross mass 0.5%～15%; The structural formula of described annular phosphonate is as follows:
Wherein, the positive integer that n is 0～2, R is C1～C4 straight or branched alkyl.
Foregoing a kind of electrolyte of lithium-ion secondary battery, described annular phosphonate is preferably 1,3-PD methyl phosphonate, 1,2-ethylene glycol ethyl phosphonate ester or BDO methyl phosphonate.
Foregoing a kind of electrolyte of lithium-ion secondary battery, the quality percentage composition of described annular phosphonate in non-aqueous organic solvent is 5%～10%.
Foregoing a kind of electrolyte of lithium-ion secondary battery, described lithium salts is LiPF
6, described lithium salt is 1M.
The present invention has added after the cyclic phosphonic acid ester additive that contains molecular structural formula of the present invention in electrolyte of lithium-ion secondary battery, because this cyclic phosphonic acid ester additive has higher reduction potential, in initial charge process, can form one deck densification, stable solid electrolyte passivating film (SEI), can effectively suppress the common embedding of propene carbonate (PC) to graphite, the initial discharge capacity, cycle life and the high temperature performance that effectively improve battery, effectively solve the battery problem that graphite is peeled off in charging process.
Embodiment
Below in conjunction with embodiment and comparative example, the invention will be further elaborated.
Lithium rechargeable battery of the present invention, comprises positive plate, negative plate, is interval in barrier film and electrolyte between adjacent positive/negative plate.
The preparation method of described positive plate is: by cobalt acid lithium, conductive agent SuperP, bonding agent PVDF in mass ratio 96:2.0:2.0 mix the anode paste of Li-ion secondary battery of making certain viscosity, be coated on collector aluminium foil, its coating weight is 0.0194g/cm
2, after drying at 85 DEG C, cold pressing; Then carry out after trimming, cut-parts, itemize, after itemize under vacuum condition 85 DEG C dry 4 hours, soldering polar ear, makes the lithium ion secondary battery positive electrode meeting the demands.
The preparation method of described negative plate is: by graphite and conductive agent SuperP, thickener CMC, bonding agent SBR in mass ratio 96.5:1.0:1.0:1.5 make slurry, be coated on copper foil of affluxion body and at 85 DEG C and dry, coating weight is 0.0089g/cm
2; Carry out after trimming, cut-parts, itemize, after itemize under vacuum condition 110 DEG C dry 4 hours, soldering polar ear, makes the lithium ion secondary battery negative pole meeting the demands.
Described barrier film adopts Celgard2400.
Electrolyte of lithium-ion secondary battery of the present invention contains wherein one or more the mixture in organic sulfoxide compounds, sulfonates compounds, halogenated cyclic carbonats compound, the sub-alkylene compound of carbonic acid, cyano compound.Described non-aqueous organic solvent contains cyclic carbonate and linear carbonate, can be selected from wherein one or more mixture of ethylene carbonate, propene carbonate, dimethyl carbonate, butyl lactone, butylene, diethyl carbonate, dipropyl carbonic ester, methyl ethyl carbonate, methyl propyl carbonate, diethyl carbonate or ethyl propyl carbonic acid ester.
The concrete preparation method of electrolyte of lithium-ion secondary battery of the present invention is:
Embodiment 1
By ethylene carbonate (EC), propene carbonate (PC), diethyl carbonate (DEC), fluorinated ethylene carbonate (FEC) (fluorinated ethylene carbonate is the one of halogenated cyclic carbonates) and annular phosphonate, mass ratio according to table 1 is mixed to get electrolyte solvent, dissolves in the LiPF of 1M in this electrolyte solvent
6obtain nonaqueous electrolytic solution.
The preparation of lithium rechargeable battery: it is 4.2mm that the lithium-ion secondary battery positive plate of preparing according to aforementioned technique, negative plate and barrier film are made into thickness through winding process, width is 34mm, length is the lithium rechargeable battery of 82mm, vacuum bakeout 10 hours at 75 DEG C, inject above-mentioned nonaqueous electrolytic solution, leave standstill after 24 hours, with 0.1C(160mA) constant current charge to 4.2V, then drop to 0.05C(80mA with 4.2V constant voltage charge to electric current); Then with 0.1C(160mA) be discharged to 3.0V, repeat to discharge and recharge for 2 times, finally again with 0.1C(160mA) battery is charged to 3.8V, complete battery and make.
Embodiment 2
Method with reference to embodiment 1 is prepared lithium rechargeable battery, just, in the time preparing electrolyte of lithium-ion secondary battery, uses 1,2-ethylene glycol ethyl phosphonate ester to replace the 1,3-PD methyl phosphonate in embodiment 1.
Embodiment 3
Method with reference to embodiment 1 is prepared lithium rechargeable battery, just, in the time preparing electrolyte of lithium-ion secondary battery, uses BDO methyl phosphonate to replace the 1,3-PD methyl phosphonate in embodiment 1.
Embodiment 4
Method with reference to embodiment 1 is prepared lithium rechargeable battery, just in the time preparing electrolyte of lithium-ion secondary battery, service quality percentage composition is that 0.5% 1,3-PD methyl phosphonate replaces the 1,3-PD methyl phosphonate that the quality percentage composition in embodiment 1 is 5%.
Embodiment 5
Method with reference to embodiment 1 is prepared lithium rechargeable battery, just in the time preparing electrolyte of lithium-ion secondary battery, service quality percentage composition is that 10% 1,3-PD methyl phosphonate replaces the 1,3-PD methyl phosphonate that the quality percentage composition in embodiment 1 is 5%.
Embodiment 6
Method with reference to embodiment 1 is prepared lithium rechargeable battery, just in the time preparing electrolyte of lithium-ion secondary battery, service quality percentage composition is that 15% 1,3-PD methyl phosphonate replaces the 1,3-PD methyl phosphonate that the quality percentage composition in embodiment 1 is 5%.
Comparative example 1
Method with reference to embodiment 1 is prepared lithium rechargeable battery, is in the time preparing electrolyte of lithium-ion secondary battery, the fluorinated ethylene carbonate (FEC) that additive is only 5% for quality percentage composition.
For the lithium rechargeable battery of embodiment 1～6 and comparative example 1, carry out following high-temperature cycle test.The result of the capability retention (%) of reaction cell cycle performance is asked for an interview table 1.
High temperature cyclic performance test
For the lithium rechargeable battery of embodiment 1～6 and comparative example 1, under 45 DEG C of conditions first with 0.7C(1120mA) constant current lithium rechargeable battery is charged to 4.2V, further be less than 0.05C(80mA at 4.2V constant-potential charge to electric current), then with 0.5C(800mA) constant current lithium rechargeable battery is discharged to 3.0V.Current discharge capacity is cyclic discharge capacity for the first time.Battery carries out cycle charge discharge electrical testing in a manner described, gets the discharge capacity of the 500th circulation.
Carry out par high temperature cyclic performance by the capability retention of lithium rechargeable battery, capability retention is calculated as follows, and the result of gained is listed table 1 in.
Capability retention (%)=[discharge capacity/discharge capacity of circulation for the first time of the 500th circulation] * 100%.
The configuration of table 1 electrolyte (each component in non-aqueous organic solvent comprises mass percent and the capability retention (%) of the additive in non-aqueous organic solvent)
Table 1 is depicted as lithium rechargeable battery embodiment 1～6 lithium rechargeable battery of the present invention and comparative example 1 lithium rechargeable battery cycle performance under 45 DEG C, 0.7C charging/0.5C electric discharge, 3.0-4.2V condition.Can find out from embodiment 1～6 and comparative example 1: the lithium rechargeable battery that has added the cyclic phosphonic acid ester additive that contains molecular structural formula of the present invention electrolyte of lithium-ion secondary battery can effectively improve the high temperature cyclic performance of lithium rechargeable battery.
Although it is pointed out that in the embodiment of this specification only with 1,3-PD methyl phosphonate
, 1, 2-ethylene glycol ethyl phosphonate ester and 1, 4-butanediol methyl phosphonate is that example is illustrated the additive of electrolyte of lithium-ion secondary battery of the present invention, but, other execution mode of lithium rechargeable battery according to the present invention, electrolyte of lithium-ion secondary battery additive can be also 1, ammediol ethyl phosphonate, 1, ammediol propyl phosphonous acid ester, 1, ammediol butyl phosphine acid esters, 1, 2-ethylene glycol propyl phosphonous acid, 1, 4-butanediol ethyl phosphonate, 1, 4-butanediol propyl phosphonous acid ester and 1, wherein one or more the mixture such as 4-butanediol butyl phosphine acid esters.
Although it is pointed out that in the embodiment of this specification only with LiPF
6for example is illustrated electrolyte of lithium-ion secondary battery of the present invention, still, other execution mode of lithium rechargeable battery according to the present invention, in electrolyte, lithium salts can be also LiN (C
xf2
x+1sO
2) (C
yf
2y+1sO
2), LiPF
6, LiBF
4, LiBOB, LiAsF
6, Li (CF
3sO
2)
2n, LiCF
3sO
3, LiClO
4wherein one or more mixture; 1M is to be only also lithium salts LiPF in lithium rechargeable battery
6typical concentrations, the concentration of lithium salts can be the arbitrary value between 0.5M～1.5M; In addition, non-aqueous organic solvent can be selected from wherein one or more mixture of ethylene carbonate, propene carbonate, dimethyl carbonate, butyl lactone, butylene, diethyl carbonate, dipropyl carbonic ester, methyl ethyl carbonate, methyl propyl carbonate, ethyl propyl carbonic acid ester.。
According to announcement and the instruction of above-mentioned specification, those skilled in the art in the invention can also change and revise above-mentioned execution mode.Therefore, the present invention is not limited to embodiment disclosed and described above, also should fall in the protection range of claim of the present invention modifications and changes more of the present invention.In addition,, although used some specific terms in this specification, these terms just for convenience of description, do not form any restriction to the present invention.
Claims (7)
1. an electrolyte of lithium-ion secondary battery, it comprises non-aqueous organic solvent and be dissolved in the lithium salts in non-aqueous organic solvent, wherein, non-aqueous organic solvent contains quality and accounts for the annular phosphonate of non-aqueous organic solvent gross mass 0.5%～15%; The structural formula of described annular phosphonate is as follows:
Wherein, the positive integer that n is 0～2, R is C1～C4 straight or branched alkyl.
2. a kind of electrolyte of lithium-ion secondary battery according to claim 1, is characterized in that: described annular phosphonate is preferably 1,3-PD methyl phosphonate, 1,2-ethylene glycol ethyl phosphonate ester or BDO methyl phosphonate.
3. a kind of electrolyte of lithium-ion secondary battery according to claim 1 and 2, is characterized in that: the quality percentage composition of described annular phosphonate in non-aqueous organic solvent is 5%～10%.
4. a kind of electrolyte of lithium-ion secondary battery according to claim 1 and 2, is characterized in that: described lithium salts is LiPF
6.
5. a kind of electrolyte of lithium-ion secondary battery according to claim 3, is characterized in that: described lithium salts is LiPF
6.
6. electrolyte of lithium-ion secondary battery according to claim 4, is characterized in that: described lithium salt is 1M.
7. a kind of electrolyte of lithium-ion secondary battery according to claim 5, is characterized in that: described lithium salt is 1M.
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| CN201410137879.4A CN103887563A (en) | 2014-04-08 | 2014-04-08 | Lithium ion secondary battery electrolyte |
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Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105789698A (en) * | 2016-03-04 | 2016-07-20 | 深圳新宙邦科技股份有限公司 | Non-aqueous electrolyte of lithium ion battery and lithium ion battery |
| CN106920988A (en) * | 2017-04-01 | 2017-07-04 | 上海中聚佳华电池科技有限公司 | A kind of sodium-ion battery electrolyte, its preparation method and application |
| CN110299561A (en) * | 2018-03-21 | 2019-10-01 | 比亚迪股份有限公司 | Nonaqueous electrolytic solution, the lithium ion battery containing the nonaqueous electrolytic solution |
| CN111430800A (en) * | 2020-05-20 | 2020-07-17 | 天津市捷威动力工业有限公司 | Electrolyte additive, application thereof, non-aqueous electrolyte containing electrolyte additive and battery |
| CN112531210A (en) * | 2020-12-03 | 2021-03-19 | 天津市捷威动力工业有限公司 | Electrolyte additive, application and non-aqueous electrolyte comprising electrolyte additive |
| CN112751082A (en) * | 2020-12-30 | 2021-05-04 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
| CN112803070A (en) * | 2020-12-30 | 2021-05-14 | 珠海冠宇电池股份有限公司 | Non-aqueous electrolyte for lithium ion battery and lithium ion battery comprising same |
| WO2021179300A1 (en) * | 2020-03-13 | 2021-09-16 | 宁德新能源科技有限公司 | Electrochemical device and electronic device comprising same |
| CN114094182A (en) * | 2021-11-03 | 2022-02-25 | 珠海冠宇电池股份有限公司 | Secondary battery |
| CN114243089A (en) * | 2021-12-13 | 2022-03-25 | 上海瑞浦青创新能源有限公司 | Lithium iron phosphate secondary battery |
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| CN114243089A (en) * | 2021-12-13 | 2022-03-25 | 上海瑞浦青创新能源有限公司 | Lithium iron phosphate secondary battery |
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