CN103346351A - Novel borate solvent for lithium-ion secondary battery - Google Patents
Novel borate solvent for lithium-ion secondary battery Download PDFInfo
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- CN103346351A CN103346351A CN201310267745XA CN201310267745A CN103346351A CN 103346351 A CN103346351 A CN 103346351A CN 201310267745X A CN201310267745X A CN 201310267745XA CN 201310267745 A CN201310267745 A CN 201310267745A CN 103346351 A CN103346351 A CN 103346351A
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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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention discloses a novel solvent for electrolyte of a lithium secondary battery. The structural characteristic of the solvent is that for an ether-group-substitution borate compound, the condensed structural formula is R1OB(OR2)OR3, wherein R1, R2 and R3 in the formula can be single-ether-group substitution and also can be double or tri-ether-group substitution. The ether chain of the substitution group R1, R2 or R3 can comprise an aryl group, a haloalkane group and a halogenated aromatic group, the halogen is F, Cl or Br, and the halogenate is partially or completely substituted. By adopting the borate solvent, the moisture in the electrolyte can be automatically eliminated, and the influence of the moisture on the performance of the battery can be reduced; in addition, the burned product diboron trioxide can be attached on the surface of the electrode and has a solid flame-retardant capacity; and the influence of the solvent on the performance of the lithium-ion battery such as capacity and cycling property is small.
Description
Technical field
The present invention relates to a kind of secondary lithium batteries novel dissolvent.Relating to a kind of boric acid ester compound that contains the ether chain particularly is the electrolyte of solvent, belongs to the technical field of electrochemistry and chemical power source product.
Background technology
Lithium ion battery has the advantage of high-energy-density, long-life and environmental protection, plays important effect as the energy storage system in alleviating energy problem and environmental problem.At present, lithium ion battery mainly adopts liquid electrolyte as electrolyte.Wherein, solvent is the important component part of electrolyte.Solvent mainly adopts the mixed solvent of the cyclic carbonate (ethylene carbonate, propene carbonate) of low melting point, low viscous linear carbonate (dimethyl carbonate, diethyl carbonate and methyl ethyl carbonate) and high-k.Carbonic ester electrolyte has wideer operating temperature range, high conductivity and to the excellent electrochemical compatibility of electrode material.But the organic carbonate solvents flash-point is low, has the very easily safety issue of burning, is limiting the large-scale application of lithium ion battery.Therefore, seek the important directions that fail safe electrolyte is the development lithium ion battery.
Boric acid ester compound has the characteristic that self eliminates moisture, can reduce moisture to the influence of battery performance; And the product diboron trioxide after the boric acid ester compound burning can be attached to electrode material surface, and isolation contacts with air, has solid-state fire-retardant ability.Therefore, boric acid ester compound can improve the fail safe of electrolyte to a certain extent as the solvent of electrolyte.
Summary of the invention
Technical problem to be solved by this invention provides a kind of novel secondary lithium batteries solvent.
Purpose of the present invention is achieved through the following technical solutions: a kind of secondary lithium batteries solvent, and it is the boric acid ester compound that contains the ether chain, structural formula is:
R in the formula
1, R
2And R
3Can be that the monoether chain replaces, also can be two or the replacement of three ether chains.Wherein, substituent R
1, R
2Or R
3The ether chain in can contain aryl, haloalkyl, halogenated aryl, wherein: halogen is F, Cl or Br, halo is partly or entirely to replace.
Solvent form of the present invention is liquid.
The boric acid ester compound that contains the ether chain that the present invention is above-mentioned separately or mix as the solvent in the electrolyte of lithium-ion secondary battery.If mix use in the electrolyte other solvents can select in linear carbonate (dimethyl carbonate DMC, diethyl carbonate DEC, methyl ethyl carbonate EMC etc.) and the cyclic carbonate (ethylene carbonate EC, propene carbonate PC, gamma-butyrolacton GBL etc.) one or more for use.Solvent can also extend to ether solvent such as glycol dimethyl ether DME, 1,3-dioxolane DOL and tetrahydrofuran THF etc.Available lithium salts is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, at least a among LiBOB and the LiTFSI, the concentration of lithium salts is 0.5-2M.
The present invention is to the evaluation of lithium secondary battery charge-discharge performance: use the electrolyte of solvent preparation as mentioned above to assemble 2016 button cells: MCMB/Li, LiFePO respectively
4/ Li, LiMn
2O
4/ Li.
Beneficial effect of the present invention is: the electrolyte that contains solvent of the present invention has the character that self dewaters, and reduces moisture to the influence of battery performance; In addition, the product diboron trioxide of burning can be attached to electrode surface, has solid-state fire-retardant ability; And this solvent is less to performance such as the influences such as specific capacity, cyclicity of lithium ion battery.
Description of drawings
Accompanying drawing 1: the structure chart of the used boric acid ester compound of the present invention.
Accompanying drawing 2: embodiment of the invention 2-4 and comparative example 1---use contains the electrolyte of described three (ethyoxyl ethylene) borate solvent and the charge-discharge performance figure of the button cell that blank electrolysis liquid is assembled.
The cyclic voltammetry curve of accompanying drawing 3: the embodiment of the invention 2---MCMB electrode in the electrolyte of three (ethyoxyl ethylene) the borate solvent that contains film for additive.
Embodiment
The invention will be further described below in conjunction with embodiment and accompanying drawing, but these embodiment do not constitute any limitation of the invention.
Embodiment 1
In being full of the glove box of argon gas, use borate ester solvent preparation electrolyte of the present invention, employed lithium salts is LiTFSI, the concentration of LiTFSI in electrolyte is 1M, and employed boric acid ester compound is three (ethyoxyl ethylene) borate, and concrete structure is as follows:
Embodiment 2
Assembling MCMB/Li 2016 button cells in being full of the glove box of argon gas, the electrolyte that uses embodiment 1 described novel dissolvent to prepare, the charging/discharging voltage interval is 0～3 V, current density is 40 mA/g.Test result by accompanying drawing 2 as seen, for the MCMB negative pole, first all charge ratio capacity are that the first all coulombic efficiencies of 296 mAh/g(are 63%), 100 week of circulation back charge ratio capacity be 181 mAh/g, capability retention is 61%.The performance of MCMB electrode in the electrolyte of employed novel dissolvent preparation coexists comparative example 1 blank electrolysis liquid compared, and differs bigger, and electrolyte anticathode compatible relatively poor of the described novel dissolvent of use be described.But can see that from accompanying drawing 3 the cyclic voltammetric stability of MCMB electrode in containing the described borate electrolyte of film for additive better illustrates the performance of MCMB electrode in the described novel dissolvent electrolyte space that has greatly improved.
Embodiment 3
In being full of the glove box of argon gas, assemble LiFePO
4/ Li 2016 button cells, the electrolyte that uses embodiment 1 described novel dissolvent to prepare, the charging/discharging voltage interval is 3～4 V, current density is 40 mA/g.Test result by accompanying drawing 3 as seen, for LiFePO
4Positive pole, first all specific discharge capacities are that the first all coulombic efficiencies of 103 mAh/g(are 74%), specific discharge capacity is 107 mAh/g after 100 weeks of circulation, capacity does not have decay substantially, but capacity is on the low side relatively, illustrates that the electrolyte that uses described novel dissolvent preparation is to LiFePO
4Anodal performance has certain influence.
Embodiment 4
In being full of the glove box of argon gas, assemble LiMn
2O
4/ Li 2016 button cells, the electrolyte that uses embodiment 1 described novel dissolvent to prepare, the charging/discharging voltage interval is 3～4.3 V, current density is 40 mA/g.From Fig. 2 as seen, for LiMn
2O
4Positive pole, first all specific discharge capacities are that the first all coulombic efficiencies of 109 mAh/g(are 95%), capability retention is 86% after 100 weeks of circulation, illustrates that the electrolyte that uses described novel dissolvent preparation is to LiMn
2O
4Anodal performance impact is less.
Embodiment 5
Selected novel dissolvent is R in the structure shown in the accompanying drawing 1
1, R
2And R
3Be ethyoxyl ethylene group (EtOCH
2CH
2-) boric acid ester compound that replaces, i.e. three (ethyoxyl ethylene) borate, as follows:
The synthetic route of three (ethyoxyl ethylene) borate is as follows:
Adopt the method for classical borate preparation, boric acid and corresponding alcohol reaction are removed the water that generates in the course of reaction with toluene for the solvent azeotropic, extent of reaction height.
Experimental procedure: in 250 mL single port flasks, add 24.7 g (0.4 mol) boric acid, 126 g (1.4 mol) ethylene glycol monoethyl ether and 150 mL toluene, place oil bath pan, oil water separator is installed successively, spherical condensating tube and oily bubbler are installed on the oil water separator, are poured into part toluene in the oil water separator.Be heated to 120 ℃ be back to no longer include in the oil water separator stop when the globule drips the reaction, steam toluene, the decompression distillation of remaining liq oil pump obtains 74-80 ℃ of (＜3.5 mmHg) cut 93.9 g, yield is 84.4%.The product warp
1H NMR nuclear-magnetism is identified.
1H?NMR?(300?MHz,?CDCl
3)?δ/ppm:?3.94?(t,?6H,?-O
CH 2 CH
2O-),?3.49-3.55?(m,?12H,?-
CH 2 OCH 2 -),?1.20?(t,?9H,?-CH
2 CH 3 )。
The comparative example 1
Assembling MCMB/Li 2016 button cells use 1mol/L LiPF in being full of the glove box of argon gas
6DMC/EC/EMC 1:1:1(volume ratio) be blank electrolysis liquid, the charging/discharging voltage interval is 0～3 V, and current density is 40 mA/g.
Claims (3)
1. a lithium rechargeable battery is characterized in that with novel borate solvent, and described solvent is boric acid ester compound, and structural formula is:
R in the formula
1, R
2And R
3Can be that the monoether chain replaces, also can be two or the replacement of three ether chains, wherein, and substituent R
1, R
2Or R
3The ether chain in can contain aryl, haloalkyl, halogenated aryl, wherein: halogen is F, Cl or Br, halo is partly or entirely to replace.
2. a kind of lithium rechargeable battery is characterized in that with novel borate solvent described solvent is used alone as the solvent of lithium-ion battery electrolytes according to claim 1, but does not get rid of as cosolvent or additive.
3. a kind of lithium rechargeable battery is characterized in that with novel borate solvent according to claim 1, and the lithium salts of selecting for use in the electrolyte is LiClO
4, LiBF
4, LiPF
6, LiAsF
6, at least a among LiBOB or the LiTFSI, the concentration of lithium salts is 0.5-2M.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310267745.XA CN103346351B (en) | 2013-06-28 | 2013-06-28 | A kind of Novel borate solvent for lithium-ion secondary battery |
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| CN201310267745.XA CN103346351B (en) | 2013-06-28 | 2013-06-28 | A kind of Novel borate solvent for lithium-ion secondary battery |
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| CN103346351B CN103346351B (en) | 2016-12-28 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655633A (en) * | 2016-03-30 | 2016-06-08 | 龙能科技（苏州）有限责任公司 | Lithium ion battery electrolyte suitable for lithium titanate battery |
| CN108822172A (en) * | 2018-08-29 | 2018-11-16 | 上海兆维科技发展有限公司 | The novel processing step of 5 '-DMTr-2 '-EOE- thymus gland pyridine nucleosides of nucleosides modifier |
| CN109980287A (en) * | 2019-04-04 | 2019-07-05 | 常州创标新能源科技有限公司 | A kind of electrolyte and preparation method thereof for lithium battery |
| CN111883845A (en) * | 2020-08-27 | 2020-11-03 | 湖北亿纬动力有限公司 | Electrolyte for lithium battery, lithium battery and application of bisborate solvent |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW432733B (en) * | 1997-10-02 | 2001-05-01 | Basf Ag | Esters as solvents in electrolyte systems for Li-ion storage cells |
| WO2009153052A1 (en) * | 2008-06-20 | 2009-12-23 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | A non-aqueous electrolyte containing as a solvent a borate ester and/or an aluminate ester |
-
2013
- 2013-06-28 CN CN201310267745.XA patent/CN103346351B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| TW432733B (en) * | 1997-10-02 | 2001-05-01 | Basf Ag | Esters as solvents in electrolyte systems for Li-ion storage cells |
| WO2009153052A1 (en) * | 2008-06-20 | 2009-12-23 | MAX-PLANCK-Gesellschaft zur Förderung der Wissenschaften e.V. | A non-aqueous electrolyte containing as a solvent a borate ester and/or an aluminate ester |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105655633A (en) * | 2016-03-30 | 2016-06-08 | 龙能科技（苏州）有限责任公司 | Lithium ion battery electrolyte suitable for lithium titanate battery |
| CN108822172A (en) * | 2018-08-29 | 2018-11-16 | 上海兆维科技发展有限公司 | The novel processing step of 5 '-DMTr-2 '-EOE- thymus gland pyridine nucleosides of nucleosides modifier |
| CN109980287A (en) * | 2019-04-04 | 2019-07-05 | 常州创标新能源科技有限公司 | A kind of electrolyte and preparation method thereof for lithium battery |
| CN109980287B (en) * | 2019-04-04 | 2021-10-19 | 常州创标新能源科技有限公司 | Electrolyte for lithium battery and preparation method thereof |
| CN111883845A (en) * | 2020-08-27 | 2020-11-03 | 湖北亿纬动力有限公司 | Electrolyte for lithium battery, lithium battery and application of bisborate solvent |
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| Publication number | Publication date |
|---|---|
| CN103346351B (en) | 2016-12-28 |
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