CN102237551B - Non-aqueous electrolyte, preparation method thereof and battery adopting electrolyte - Google Patents
Non-aqueous electrolyte, preparation method thereof and battery adopting electrolyte Download PDFInfo
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- CN102237551B CN102237551B CN201010169632.2A CN201010169632A CN102237551B CN 102237551 B CN102237551 B CN 102237551B CN 201010169632 A CN201010169632 A CN 201010169632A CN 102237551 B CN102237551 B CN 102237551B
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- Y02E60/10—Energy storage using batteries
Abstract
The invention provides non-aqueous electrolyte, a preparation method thereof and a battery adopting the non-aqueous electrolyte. The electrolyte contains a lithium salt, an organic solvent and an additive. The additive has a structural formula, wherein R1 and R2 are one of alkylene, an aromatic group and alkyl with 1 to 12 carbon atoms respectively, or are one of F and/or N atom-containing alkylene, the aromatic group and the alkyl with the 1 to 12 carbon atoms respectively; and R3 and R4 are one of a hydrogen atom, a halogen atom, acetyl, trifluoromethyl, a carboxylic acid ester group, cyan and nitryl respectively.
Description
Technical field
The invention relates to a kind of nonaqueous electrolytic solution and preparation method thereof and the battery that adopts this electrolyte, relate in particular to a kind of non-aqueous electrolyte for lithium ion cell and preparation method thereof and the lithium ion battery that adopts this electrolyte.
Background technology
Lithium rechargeable battery application is extremely wide, but faces safety problem always, and overcharges and nonaqueous electrolytic solution inflammability is the key factor of bringing out safety problem.Electrolyte of lithium-ion secondary battery solvent is generally carbonates, as EC (ethylene carbonate), PC (propene carbonate), DMC (dimethyl carbonate), DEC (diethyl carbonate), EMC (methyl ethyl carbonate), these solvent compositions are all flammable.The lithium ion battery that contains above nonaqueous electrolytic solution is in the situation of overcharging, positive electrode active materials is due to excessively de-lithium recurring structure irreversible transformation, may discharge oxygen atom, there is oxidation Decomposition in electrolyte, send imflammable gas and a large amount of heat, once internal temperature of battery reaches the ignition point of electrolyte and catabolite, just can there is battery burning on fire, even explode etc.In other situation, as high temperature, shock etc., the lithium ion battery accident such as on fire of also can burning.Therefore, the behavior that overcharges of lithium ion battery and poor heat stability must be controlled, and its security performance just can get a promotion.
Improve at present lithium rechargeable battery anti-over-charging ability and thermal stability aspect; physical route has charging circuit, failure of current device (CID), dedicated diaphragm of having installed over-charge protective effect etc., and chemistry route is mainly aspect modified anode material and electrolyte two.Modification electrolyte aspect, is mainly in electrolyte, to add anti-overcharge additive and flame-retardant additive, plays anti-overcharge and effect Heat stability is good, thereby promotes the security performance of lithium rechargeable battery.
Conventional method, is in electrolyte the inside, to add more than a kind of functional additive, because additive addition is large, bring negative effect can to the combination property of lithium rechargeable battery, and such as the capacity of battery diminishes, cycle life shortens etc.
As CN101017919 discloses electrolyte, in this electrolyte, added a kind of phosphite ester: molecular structural formula is as follows, possess anti-overcharge and fire resistance simultaneously.Wherein, R1; R2; R3 is saturated/unsaturated alkyl or the substituted hydrocarbon radical that contains F, N, alkoxyl, R1 wherein, R2; in R3, the number of carbon atom is 1≤n≤12; although this electrolyte possesses fire-retardant and anti-overcharge performance simultaneously, the anti-overcharge performance that it provides is irreversible, belongs to disposable over-charge protective.
Also have other one piece of patent CN1518155A to mention, added a kind of phosphate in a kind of electrolyte, this molecular formula has following structure:
Wherein, R1 and R2 independently selected from: replace or unsubstituted C
1-C
20alkyl, replaces or unsubstituted C
1-C
20alkoxyl, replaces or unsubstituted C
2-C
20alkenyl, replaces or unsubstituted C
6-C
30aryl, replace or unsubstituted C
7-C
30aralkyl, replaces or unsubstituted aryloxy group, replaces or unsubstituted heteroaryloxy, replaces or unsubstituted C
5-C
20cycloalkyl, and replacement or unsubstituted C
2-C
20heterocyclylalkyl; And R3 and R4 are independently selected from hydrogen atom and replacement or unsubstituted C
2-C
20heterocyclylalkyl; And R3-R4 is independently selected from hydrogen atom and replacement or unsubstituted C
1-C
20alkyl.This kind of electrolyte can make battery first irreversible capacity decline, and efficiency for charge-discharge and cycle performance be improved, but this kind of additive just improved above performance, can not improve the anti-overcharge and fire resistance of battery simultaneously.
Summary of the invention
The present invention is for solving in prior art, and electrolyte cannot obtain the technical problem of reversible over-charge protective and fire-retardant two performances simultaneously.
For this reason, the invention provides a kind of nonaqueous electrolytic solution, this electrolyte contains lithium salts, organic solvent and additive, and described additive is the additive with following structural formula:
Wherein, R1, R2 is independently selected from respectively alkylene, aryl and C
1-C
12alkyl in a kind of, or the alkylene that contains F and/or N atom, the aryl that contains F and/or N atom and contain F and/or the C of N atom
1-C
12alkyl in a kind of; R3, R4 is independently selected from respectively a kind of in hydrogen atom, halogen atom, acetyl group, trifluoromethyl, carboxylic acid ester groups, cyano group, nitro.
The present invention provides a kind of preparation method of nonaqueous electrolytic solution simultaneously, and the method comprises:
1) by C
1-C
4alcohol and phosphorus oxychloride mix, under the condition of 15 ℃, generate a chlorine phosphate;
2), after chlorine phosphate step (1) being generated mixes with substituted phenothiazine, successively by stirring at room and backflow, obtain having the additive of structure below
Wherein, R1, R2 is independently selected from respectively alkylene, aryl and C
1-C
12alkyl in a kind of, or the alkylene that contains F and/or N atom, the aryl that contains F and/or N atom and contain F and/or the C of N atom
1-C
12alkyl in a kind of; R3, R4 is independently selected from respectively a kind of in hydrogen atom, halogen atom, acetyl group, trifluoromethyl, carboxylic acid ester groups, cyano group, nitro;
3) lithium salts and organic solvent are mixed, then add after the additive mixing of preparation in step 2, obtain nonaqueous electrolytic solution.
And a kind of battery is provided, and this battery comprises battery core and nonaqueous electrolytic solution, and described battery core comprises positive pole, negative pole and the barrier film between positive pole and negative pole, and described nonaqueous electrolytic solution is nonaqueous electrolytic solution provided by the present invention.
Nonaqueous electrolytic solution provided by the present invention possesses anti-overcharge and fire resistance simultaneously, and the over-charge protective providing is reversible.
Embodiment
The present inventor finds by great many of experiments; if adopt the phosphite ester that contains unsaturated alkyl adopting in the prior art; although possess fire-retardant and anti-overcharge performance simultaneously; but the anti-overcharge genus being to provide is irreversible; over-charge protective can only be provided one time; although can there is not security incident once battery overcharges, can not continue to use.And in nonaqueous electrolytic solution provided by the present invention by adding special additive; added the electrolyte of additive, not only possess fire-retardant and anti-overcharge performance, and the over-charge protective providing has been reversible simultaneously; even if overcharge conditions occurs battery, also can continue to use.Reason is that in over-charge protective process, additive molecule serves as shuttling agent, overcharging current drain, becomes dissipation of heat and goes out.There is not any variation in battery material itself, has stopped the basic reason of the security incidents such as battery explosion.
The invention provides a kind of nonaqueous electrolytic solution, this electrolyte contains lithium salts, organic solvent and additive, it is characterized in that, described additive is the additive with following structural formula:
Wherein, R1, R2 is independently selected from respectively alkylene, aryl and C
1-C
12alkyl in a kind of, or the alkylene that contains F and/or N atom, the aryl that contains F and/or N atom and contain F and/or the C of N atom
1-C
12alkyl in a kind of; R3, R4 is independently selected from respectively a kind of in hydrogen atom, halogen atom, acetyl group, trifluoromethyl, carboxylic acid ester groups, cyano group, nitro.
In preferred situation, R1 is CH
3, R2 is CH
3, R3 is COCH
3, R4 is COCH
3.
Take nonaqueous electrolytic solution total weight as benchmark, and the weight ratio of wherein said lithium salts, organic solvent and additive is 12.7:86.8-56.3:0.5-30.
Lithium salts is LiPF
6, LiBF
4, LiClO
4, LiBOB, LiCF
3sO
3, LiN (CF
3sO
2)
2, LiAsF
6, LiN (C
2f
5sO
2)
2in one or more; Organic solvent is selected from one or more in propene carbonate (PC), dimethyl carbonate (DMC), ethylene carbonate (EC), diethyl carbonate (DEC).Described lithium salts and organic solvent can obtain by outsourcing.
The present invention also provides a kind of preparation method of nonaqueous electrolytic solution, and the method comprises:
1) by C
1-C
4alcohol and phosphorus oxychloride mix, under the condition of 15 ℃, generate a chlorine phosphate;
2), after chlorine phosphate step (1) being generated mixes with substituted phenothiazine and hydrogen sulfate tetra-n-butyl ammonium, successively by stirring at room and backflow, obtain having the additive of structure below
Wherein, R1, R2 is independently selected from respectively alkylene, aryl and C
1-C
12alkyl in a kind of, or contain F and/or N atom alkylene, aryl and C
1-C
12alkyl in a kind of; R3, R4 is independently selected from respectively a kind of in hydrogen atom, halogen atom, acetyl group, trifluoromethyl, carboxylic acid ester groups, cyano group, nitro;
3) lithium salts and organic solvent are mixed, then add after the additive mixing of preparation in step 2, obtain nonaqueous electrolytic solution.
C
1-C
4alcohol and the weight ratio of phosphorus oxychloride be 2:1, if this ratio surpasses 2:1, three of part phosphorus oxychloride chlorine atoms are all by methoxy substitution, target product productive rate is low; If this ratio is lower than 2:1, portion of product only has a chlorine atom by methoxy substitution, product that neither target.
In step 1, esterification reaction temperature is 15 ℃, and the rate of addition of absolute methanol is 0.5g/min, after absolute methanol dropwises, and insulation 1h.
In step 2, the weight ratio of a chlorine phosphate and substituted phenothiazine and hydrogen sulfate tetra-n-butyl ammonium is 8.3-11:11-13:0.169.
The speed of the stirring in step 2 is 80r/min, and the time of stirring is 24h, and the time of backflow is 24h, and the temperature of backflow is 100-120 ℃.
Described substituted phenothiazine is 2-acetyl phenthazine, 2-first cyanogen phenthazine, 2, a kind of in 7-diacetyl phenthazine.
The mode of mixing in step 3 is hybrid mode known in those skilled in the art, first lithium salts is added in organic solvent, stirs (mixing speed 80r/min) and dissolve under normal temperature, then adds additive, with the mixing speed of 120r/min, dissolves.
The present invention also provides a kind of lithium ion battery, this battery comprises battery core, housing and nonaqueous electrolytic solution, described battery core comprises positive pole, negative pole and the barrier film between positive pole and negative pole, in described housing, accommodate battery core and nonaqueous electrolytic solution, described electrolyte is nonaqueous electrolytic solution provided by the present invention.
Because the preparation technology of negative plate, positive plate, barrier film is technology known in the field, and the assembling of battery is also technology known in the field, at this, just repeats no more.
Below, in connection with embodiment, the execution mode of this patent is described herein, but is not limited to following examples:
Embodiment 1
The present embodiment is used for illustrating additive provided by the present invention, electrolyte, positive/negative plate and preparation method thereof.
(1) additive and added the preparation of the electrolyte of this kind of additive:
In 500ml twoport flask, add 7.75g phosphorus oxychloride, with 0.5g/min speed, add 3.2g absolute methanol, magnetic agitation 80r/min, with brine ice, regulating temperature is 15 ℃.After absolute methanol dropwises, insulation 1h.
Above-mentioned reactant liquor is poured in cucurbit, carry out decompression distillation (55 ℃), collect cut, obtain a chlorine phosphate, and a chlorine phosphate of 8.375g is dissolved in 100mL methyl isopropyl Ketone together with the 2-of 12.07g acetyl phenthazine, 0.169g hydrogen sulfate tetra-n-butyl ammonium, under stirring, add 50mL50% sodium hydrate aqueous solution, under room temperature, stir the 24h 24h that refluxes again.
Reactant liquor is poured in 1000mL separatory funnel, adds 100mL deionized water and 50mL methyl iso-butyl ketone (MIBK), collects organic phase, and water is washed with methyl iso-butyl ketone (MIBK), merges organic phase, uses anhydrous Mg
2sO
4dry, be spin-dried for rear with column chromatography (solvent is benzinum, 230-400 silicagel column, eluant, eluent is n-hexane: benzinum=15:1) separation, obtains molecular structural formula and be:
By LiPF
6join the propene carbonate that volume ratio is 1:2:1:2: dimethyl carbonate: ethylene carbonate: wiring solution-forming in diethyl carbonate mixed solution, and then add the additive that mass fraction is more than 5% preparation.LiPF wherein
6, organic solvent, above-mentioned additive mass ratio be 12.7:86.8:0.5, finally obtains electrolyte A1.
(2) preparation of negative plate
100 weight portion MCMB, 3 weight portion adhesive SBR, 3 weight portion CMC are joined in 50 weight parts waters, then in de-airing mixer, stir 2h, make cathode size, this slurry is coated on Copper Foil equably, through 120 ℃ of oven dry, rollings, obtain negative plate.
(3) preparation of positive plate
By 90 weight portion LiFePO4,10 weight portion 3M company carbon blacks, 9 weight portion binding agent PVDF, appropriate solvent, then in de-airing mixer, stir 2h, make anode sizing agent, this slurry is coated on aluminium foil equably, through 120 ℃ of oven dry, rollings, obtain positive plate.
(4) assembling of battery
The polypropylene film of above-mentioned positive and negative electrode and 25 micron thickness is wound into the electrode group of square lithium ion secondary battery, pack in battery container, and inject the nonaqueous electrolytic solution A1 making above, and make the lithium rechargeable battery sample T1 of 053450A, design capacity is 650mAh.
Embodiment 2
The present embodiment is used for illustrating additive provided by the present invention, electrolyte, positive/negative plate and preparation method thereof.
In 500ml twoport flask, add 7.75g phosphorus oxychloride, with 0.5g/min speed, add 4.6g absolute ethyl alcohol, magnetic agitation 80r/min, with brine ice, regulating temperature is 15 ℃.After absolute ethyl alcohol dropwises, insulation 1h.
Above-mentioned reactant liquor is poured in cucurbit, carry out decompression distillation (55 ℃), collect cut, obtain a chlorine phosphate, and a chlorine phosphate of 10.75g is dissolved in 100mL methyl isopropyl Ketone together with the 2-of 11.22g first cyanogen phenthazine, 0.169g hydrogen sulfate tetra-n-butyl ammonium, under stirring, add 50mL50% sodium hydrate aqueous solution, under room temperature, stir the 24h 24h that refluxes again.
Reactant liquor is poured in 1000mL separatory funnel, adds 100mL deionized water and 50mL methyl iso-butyl ketone (MIBK), collects organic phase, and water is washed with methyl iso-butyl ketone (MIBK), merges organic phase, uses anhydrous Mg
2sO
4dry, be spin-dried for rear with column chromatography (solvent is benzinum, 230-400 silicagel column, eluant, eluent is n-hexane: benzinum=15:1) separation, molecular structural formula is:
By LiCF
3sO
3join in propene carbonate and mix, and then add the additive of above preparation, obtain electrolyte A2, wherein LiCF
3sO
3, organic solvent, additive weight ratio be that 12.7:86.8:0.5 finally obtains nonaqueous electrolytic solution sample A2 and battery sample T2.
Embodiment 3
The present embodiment is used for illustrating additive provided by the present invention, electrolyte, positive/negative plate and preparation method thereof.
In 500ml twoport flask, add 7.75g phosphorus oxychloride, with 0.5g/min speed, add 10.0g anhydrous 2,2,2-trifluoroethanol, magnetic agitation 80r/min, with brine ice, regulating temperature is 15 ℃.After 2,2,2-trifluoroethanol dropwises, insulation 1h.
Above-mentioned reactant liquor is poured in cucurbit; carry out decompression distillation (55 ℃); collect cut; obtain a chlorine phosphate; and by 2 of a chlorine phosphate of 11g and 14.21g; 7-diacetyl phenthazine, 0.169g hydrogen sulfate tetra-n-butyl ammonium are dissolved in 100mL methyl isopropyl Ketone together, add 50mL50% sodium hydrate aqueous solution under stirring, stir the 24h 24h that refluxes again under room temperature.
Reactant liquor is poured in 1000mL separatory funnel, adds 100mL deionized water and 50mL methyl iso-butyl ketone (MIBK), collects organic phase, and water is washed with methyl iso-butyl ketone (MIBK), merges organic phase, uses anhydrous Mg
2sO
4dry, be spin-dried for rear with column chromatography (solvent is benzinum, 230-400 silicagel column, eluant, eluent is n-hexane: benzinum=15:1) separation, obtains molecular structural formula and be:
By LiAsF
6joining volume ratio is to mix in the propene carbonate of 1:2 and the mixed solvent of dimethyl carbonate, and then adds the additive of above preparation, obtains electrolyte A3, wherein LiAsF
6, organic solvent, additive weight ratio be 12.7:86.8:0.5, according to method identical in embodiment 1, prepare negative pole and positive pole, and the electrolyte of positive pole, negative pole and preparation is assembled into battery according to method identical in embodiment 1, finally obtain sample battery sample T3.
Comparative example 1
According to the scheme described in embodiment in CN101017919 2, prepare electrolyte sample B1, and according to preparing positive plate, negative plate and will prepare positive plate, negative plate with embodiment 1 same procedure, and be assembled into battery sample CT1 according to method described in embodiment 1.
Comparative example 2
According to the scheme of embodiment in CN1518155A 2, prepare electrolyte sample B2, and according to preparing positive plate, negative plate and will prepare positive plate, negative plate and be assembled into battery sample CT2 according to method described in embodiment 1 with embodiment 1 same procedure
Embodiment 4-6
The present embodiment is used for the properties of the prepared electrolyte sample of test implementation example 1-3 A1-A3, battery sample T1-T3, comprising:
1) electrolyte self-extinguishing time (SET) test
To in the glass fibre cotton balls of diameter 6mm, immerse 0.3g electrolyte, then light this glass fibre cotton balls, record t burning time, according to formula S ET (s/g)=t/0.3, adopt identical method to survey 10 times, average, obtain the self-extinguishing time (SET) of this electrolyte, test result is in Table 1.
2) overcharge test:
With 0.1C, carry out charge and discharge cycles, the charging interval is 20h, and be 10h discharge time, and battery 100% overcharges.Whether observing battery does not have sharply and raises overcharging stage voltage, be on specific voltage platform, i.e. over-charge protective voltage platform.The results are shown in Table 2.
Comparative example 3-4
This comparative example is used for electrolyte sample B1-B2 prepared by test comparison example 1-2 and the properties of battery sample CT1-CT2, and it is identical that described properties test and the properties of describing in embodiment 4-6 are tested, test result respectively in Table 1, table 2.
Table 1
| Numbering | Additive addition (mass fraction) | Self-extinguishing time SET (S) |
| A1 | 5% | 44 |
| A2 | 5% | 46 |
| A3 | 5% | 39 |
| B1 | 5% | 46 |
| B2 | 5% | 63 |
Table 2
| Numbering | Over-charge protective platform voltage (V) | Whether reversible protection |
| T1 | 3.57 | Reversible |
| T2 | 3.53 | Reversible |
| T3 | 3.77 | Reversible |
| CT1 | 4.22 | Irreversible |
| CT2 | Without over-charge protective platform | / |
By table 1, can find out, the self-extinguishing time of the shortest sample B1 for 1 preparation of 39s comparative example of self-extinguishing time of embodiment of the present invention electrolyte sample A1-A3 is 46s, the self-extinguishing time of the sample B2 of embodiment 2 preparations is 63 self-extinguishing times much larger than electrolyte provided by the present invention, this shows that electrolyte provided by the present invention has good fire resistance, the battery sample CT2 of embodiment 2 preparations does not have additives for overcharge protection platform as can be seen from Table 2, and although its over-charge protective platform voltage of sample CT1 of embodiment 1 preparation is 4.22V, but its over-charge protective is irreversible protection, be that over-charge protective can only be used once, and battery sample provided by the present invention not only possesses reversible protection, over-charge protective platform voltage is also less than the over-charge protective platform voltage of the battery sample CT1 of embodiment 1 preparation simultaneously, this shows that electrolyte provided by the present invention has good fire resistance, adopt the battery of the prepared electrolyte of the present invention to possess good reversible over-charge protective performance simultaneously.
Claims (11)
1. a nonaqueous electrolytic solution, this electrolyte contains lithium salts, organic solvent and additive, it is characterized in that, and described additive is the additive with following structural formula:
Wherein, R1, R2 is independently selected from respectively alkylene, aryl and C
1-C
12alkyl in a kind of, or the alkylene that contains F and/or N atom, the aryl that contains F and/or N atom and contain F and/or the C of N atom
1-C
12alkyl in a kind of; R3, R4 is independently selected from respectively a kind of in hydrogen atom, halogen atom, acetyl group, trifluoromethyl, carboxylic acid ester groups, cyano group, nitro.
2. nonaqueous electrolytic solution according to claim 1, in the structure of described additive, R1 is CH
3, R2 is CH
3, R3 is COCH
3, R4 is COCH
3.
3. nonaqueous electrolytic solution according to claim 1, take nonaqueous electrolytic solution total weight as benchmark, and the weight ratio of wherein said lithium salts, organic solvent and additive is 12.7:56.3-86.8:0.5-30.
4. nonaqueous electrolytic solution according to claim 1, described lithium salts is LiPF
6, LiBF
4, LiClO
4, LiBOB, LiCF
3sO
3, LiN (CF3SO2)
2, LiAsF
6, LiN (C
2f
5sO
2)
2in a kind of; Organic solvent is selected from one or more in propene carbonate, dimethyl carbonate, ethylene carbonate, diethyl carbonate.
5. a preparation method for nonaqueous electrolytic solution, the method comprises:
(1) by C
1-C
4alcohol and phosphorus oxychloride mix, under the condition of 15 ℃, generate a chlorine phosphate;
(2), after chlorine phosphate step (1) being generated mixes with substituted phenothiazine and hydrogen sulfate tetra-n-butyl ammonium, successively by stirring at room and backflow, obtain having the additive of structure below:
Wherein, R1, R2 is independently selected from respectively alkylene, aryl and C
1-C
12alkyl in a kind of, or the alkylene that contains F and/or N atom, the aryl that contains F and/or N atom and contain F and/or the C of N atom
1-C
12alkyl in a kind of; R3, R4 is independently selected from respectively a kind of in hydrogen atom, halogen atom, acetyl group, trifluoromethyl, carboxylic acid ester groups, cyano group, nitro;
(3) lithium salts and organic solvent are mixed, then add after the additive mixing of preparation in step (2), obtain nonaqueous electrolytic solution.
6. the preparation method of nonaqueous electrolytic solution according to claim 5, C in step (1)
1-C
4alcohol and the weight ratio of phosphorus oxychloride be 2:1.
7. the preparation method of nonaqueous electrolytic solution according to claim 6, in step (2), the weight ratio of a chlorine phosphate and substituted phenothiazine and hydrogen sulfate tetra-n-butyl ammonium is 8.3-11:11-13:0.169.
8. the preparation method of nonaqueous electrolytic solution according to claim 6, the weight ratio of described lithium salts, organic solvent and additive is 12.7:56.3-86.8:0.5-30.
9. the preparation method of nonaqueous electrolytic solution according to claim 6, described substituted phenothiazine is 2-acetyl phenthazine, 2-first cyanogen phenthazine, 2, a kind of in 7-diacetyl phenthazine.
10. the preparation method of nonaqueous electrolytic solution according to claim 6, the speed of the stirring in step (2) is 80r/min, and the time of stirring is 24h, and the time of backflow is 24h, and the temperature of backflow is 100-120 ℃.
11. 1 kinds of lithium ion batteries, this battery comprises battery core, housing and nonaqueous electrolytic solution, described battery core comprises positive pole, negative pole and the barrier film between positive pole and negative pole, in described housing, accommodate battery core and nonaqueous electrolytic solution, it is characterized in that, described electrolyte is the nonaqueous electrolytic solution described in any one in claim 1-5.
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| WO2013145669A1 (en) * | 2012-03-30 | 2013-10-03 | 東ソー・エフテック株式会社 | Fluorine-containing phosphate ester-amide, and flame retardant resin, flame retardant liquid and flame retardant solvent for oranic synthesis containing same |
| JP6435235B2 (en) * | 2015-05-25 | 2018-12-05 | 東ソー・ファインケム株式会社 | Fluorine-containing phosphate ester cyanoalkylamide, nonaqueous electrolyte containing the same, and nonaqueous secondary battery |
| JP6439645B2 (en) * | 2015-10-08 | 2018-12-19 | 株式会社村田製作所 | Batteries, battery packs, electronic devices, electric vehicles, power storage devices, and power systems |
| CN107026284B (en) * | 2016-01-29 | 2019-10-11 | 比亚迪股份有限公司 | A kind of electrolyte and the lithium ion battery containing the electrolyte and/or anode |
| DE102017203164A1 (en) | 2017-02-27 | 2018-08-30 | Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. | Efficient phosphorus-containing stabilizers based on diphenylamine and heterocyclic diphenylamine derivatives |
| CN107959054A (en) * | 2017-12-25 | 2018-04-24 | 湖北环天高科新能源有限公司 | A kind of power battery electrolyte |
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| CN101017917A (en) * | 2007-02-26 | 2007-08-15 | 中国科学技术大学 | Electrolyte for the lithium ion battery |
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| CN1925206A (en) * | 2006-09-20 | 2007-03-07 | 广州市天赐高新材料科技有限公司 | Dynamic electrolyte for lithium ion battery |
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