CN105552438A - Lithium ion battery electrolyte and preparation method - Google Patents
Lithium ion battery electrolyte and preparation method Download PDFInfo
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- CN105552438A CN105552438A CN201510947000.7A CN201510947000A CN105552438A CN 105552438 A CN105552438 A CN 105552438A CN 201510947000 A CN201510947000 A CN 201510947000A CN 105552438 A CN105552438 A CN 105552438A
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
The invention relates to the technical field of a lithium ion battery, in particular to a lithium ion battery electrolyte and a preparation method thereof. The lithium ion battery electrolyte comprises a non-aqueous solvent, a lithium salt and an additive, wherein the additive comprises a first type of additive capable of water removal and acid reduction and a second type of additive capable of stabilizing color change of the electrolyte, the first type of additive is a silazane compound or a carbodiimide compound, and the second type of additive is a benzothiodiazole compound or a phosphite ester compound. Compared with the prior art, the lithium ion battery electrolyte has the advantages that by controlling an environmental temperature for configuring the electrolyte and with the first type of additive capable of water removal and acid reduction and the second type of additive capable of stabilizing the color change of the electrolyte, long-term control on moisture, acidity and chromaticity of the electrolyte can be simultaneously achieved, the storage time of the electrolyte is substantially prolonged, and the electrolyte quality is ensured. The lithium ion battery electrode is particularly and suitably used for an additive system which easily causes the chromaticity and the acidity of the electrolyte to change.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of lithium-ion battery electrolytes and preparation method thereof.
Background technology
Lithium-ion battery electrolytes is as one of large critical material of lithium battery four, and the performance of its product confrontation lithium battery is most important.Wherein moisture, acidity, colourity are evaluate the most basic physical index of electrolyte quality, but inevitably bring portion of water in process of production.Current commodity electrolyte lithium salts mainly LiPF
6, it is very responsive to water, LiPF
6be dissolved in dissolving agent process and release heat, and the PF with catalytic polymerization effect may be produced
5, FOF
3, make electrolyte acidity and colourity increase gradually.The moisture later stage in electrolyte gradates as acid, and the change of increase to electrolyte colourity of acidity plays catalytic action again, and electrolyte also has important impact in the temperature of preparation process and storage process to the acidity of electrolyte and colourity in addition.
Along with the abundant and development of lithium battery product category, quantity, higher requirement be it is also proposed to electrolyte property.For improving the performance of electrolyte, a series of functional form additive often adds and is incorporated in electrolyte system, additive types and quantity abundant, solve the problem of electrolyte property on the one hand, what find some additives in testing but then and producing adds the change easily accelerating electrolyte acidity, colourity.Such as the compound such as sulfuric acid vinyl ester, 4-methylsulfuric acid vinyl acetate has excellent chemical property, have a better role, but this additive very easily causes the rising of electrolyte acidity and colourity to battery properties tool.So realizing the long-term stability of electrolyte moisture, acidity, colourity is the technological difficulties that many electrolyte manufacturing enterprises face simultaneously.
Summary of the invention
An object of the present invention is for the deficiencies in the prior art, provides a kind of lithium-ion battery electrolytes, and this electrolyte realizes the long-term control to moisture, acidity, colourity simultaneously, significantly extends the storage time of electrolyte, ensures the quality of electrolyte.
Two of object of the present invention is for the deficiencies in the prior art, a kind of preparation method of lithium-ion battery electrolytes is provided, the electrolyte of employing obtained by the method realizes the long-term control to moisture, acidity, colourity simultaneously, significantly extends the storage time of electrolyte, ensures the quality of electrolyte.
To achieve these goals, the present invention adopts following technical scheme:
There is provided a kind of lithium-ion battery electrolytes, be made up of electrolyte lithium salt, nonaqueous solvents and additive, described additive comprises the first kind additive with the deacidification that dewaters and the Equations of The Second Kind additive with the change of stable electrolyte colourity; Described first kind additive is silazane compounds or carbodiimide compound, and described Equations of The Second Kind additive is thiocarboxylic acid ester type compound or phosphite ester compound.Wherein, silazane compounds or carbodiimide compound can form hydrogen bond with the micro-moisture effect in electrolyte, with HF effect in conjunction with salify or amine, thus realize the object reducing moisture and acidity; S containing the valence state that mediates in thiocarboxylic acid ester type compound or phosphite ester compound or P element, there is non-oxidizability, organic substance can be blocked under HF, PF5 or PFO3 catalytic action, form copolymer, oligomer, thus suppress the change of electrolyte colourity.
Preferably, the content of described first kind additive accounts for the 0.01%-1.5% of lithium-ion battery electrolytes gross mass, and the content of described Equations of The Second Kind additive accounts for the 0.005%-1.5% of lithium-ion battery electrolytes gross mass.
Preferably, described silazane compounds is at least one in hexamethyldisiloxane, heptamethyldisilazane (HMDS), hexamethyl cyclotrisiloxane, pregnancy basic ring three silazane, nine methyl three silazane;
Preferably, described carbodiimide compound is dicyclohexylcarbodiimide, N, at least one in N'-DIC, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide, 1-(3-dimethylamino-propyl)-3-cyclohexyl, N, N-di-t-butyl carbodiimide.
Preferably, described carbothioic acid ester is at least one in dilauryl thiodipropionate (DLTP), pentaerythrite four (3-lauryl thiopropionate), thio-2 acid two (18) ester (DSTP).
Preferably, described phosphite ester compound is triphenyl phosphite (TPPi), tri iso octyl phosphorite, diphenylisodecyl base ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,4,6-tri-tert phenyl) pentaerythritol diphosphites, four (2,4-di-tert-butylphenol)-4, at least one in 4'-xenyl diphosphites, three (2,4-di-tert-butyl-phenyl) phosphite ester.
Preferably, described nonaqueous solvents is the two or more mixture in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, ethylene carbonate, methyl propyl carbonate, ethyl propionate, ethyl acetate, Ethyl formate, propyl butyrate, oxolane, dioxy cycloalkanes, diethanol diethyl ether, gamma-butyrolacton; The content of described nonaqueous solvents accounts for the 75.0%-88.0% of lithium-ion battery electrolytes gross mass.
Preferably, described electrolyte lithium salt is at least one in lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two fluorine sulfimide lithium, and the content of described lithium salts accounts for the 10.0%-18.0% of lithium-ion battery electrolytes gross mass.
Preferably, described additive also comprises vinylethylene carbonate (VC), fluorinated ethylene carbonate, 1, at least one in 3-propane sultone, sulfuric acid vinyl ester (DTD), 4-methylsulfuric acid vinyl acetate, its content accounts for the 0.1%-5.0% of lithium-ion battery electrolytes gross mass.
The present invention also provides the preparation method of above-mentioned lithium-ion battery electrolytes: the liquid nitrogen passing into flowing in the chuck of stainless steel cauldron cools, then in stainless steel cauldron, add the nonaqueous solvents of formula ratio, when the temperature of nonaqueous solvents is reduced to-15 DEG C ~ 0 DEG C, in stainless steel cauldron, slowly add the electrolyte lithium salt of formula ratio and fully stir, matter lithium salts to be electrolysed dissolves the additive adding formula ratio in backward reactor completely, obtains described lithium-ion battery electrolytes after stirring.
The invention has the beneficial effects as follows:
Compared with prior art, a kind of lithium-ion battery electrolytes of the present invention and preparation method thereof has the following advantages:
(1) the present invention adopts the silazane compounds or carbodiimide compound with the deacidification function that dewaters as first kind additive, silazane compounds or carbodiimide compound can form hydrogen bond with the micro-moisture effect in electrolyte, with HF effect in conjunction with salify or amine, thus realize the object reducing moisture and acidity;
(2) the present invention adopts the thiocarboxylic acid ester type compound or phosphite ester compound with the change of stable electrolyte colourity as Equations of The Second Kind additive, S containing the valence state that mediates in thiocarboxylic acid ester type compound or phosphite ester compound or P element, it has non-oxidizability, organic substance can be blocked under HF, PF5 or PFO3 catalytic action, form copolymer, oligomer, thus suppress the change of electrolyte colourity.
(3) the present invention is by controlling the ambient temperature of electrolyte configuration phase at-15 DEG C ~ 0 DEG C, at such a low temperature, the Equations of The Second Kind additive of the first kind additive and the change of stable electrolyte colourity that simultaneously add the above-mentioned deacidification that dewaters can reach optimum efficiency, synergy is produced by the conbined usage of first kind additive and Equations of The Second Kind additive, realize the moisture to electrolyte simultaneously, acidity, the long-term control of colourity, significantly extend the storage time of electrolyte, ensure the quality of electrolyte, the present invention is particularly useful for containing easily causing electrolyte colourity, the additive of acidity change is (as sulfuric acid vinyl ester, 4-methylsulfuric acid vinyl acetate etc.) system, the present invention has obvious advantage and has higher commercial value.
(4) the present invention adopts stainless steel cauldron, the cooling effectiveness of electrolyte significantly can be improved using the liquid nitrogen of flowing as coolant, the preparation environment that the dry liquid nitrogen adopted is built is good, do not bring moisture into, and continuous print cooling can be realized in layoutprocedure, without the need to repeatedly changing coolant.
Embodiment
The invention will be further described with the following Examples.
Comparative example 1:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, state that the temperature remains within the normal range, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, obtain the lithium-ion battery electrolytes of comparative example 1.
Comparative example 2:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, state that the temperature remains within the normal range, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, obtain the lithium-ion battery electrolytes of comparative example 2.
Comparative example 3:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, obtain the lithium-ion battery electrolytes of comparative example 3.
Comparative example 4:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.02% heptamethyldisilazane, obtain the lithium-ion battery electrolytes of comparative example 4.
Comparative example 5:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% triphenyl phosphite, obtain the lithium-ion battery electrolytes of comparative example 5.
Comparative example 6:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, state that the temperature remains within the normal range, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% triphenyl phosphite, 0.02% heptamethyldisilazane, obtain the lithium-ion battery electrolytes of comparative example 6.
Embodiment 1:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.01% triphenyl phosphite, 0.01% heptamethyldisilazane, obtain the lithium-ion battery electrolytes of embodiment 1.
Embodiment 2:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% triphenyl phosphite, 0.02% heptamethyldisilazane, obtain the lithium-ion battery electrolytes of embodiment 2.
Embodiment 3:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% triphenyl phosphite, 0.02%N, N'-DIC, obtain the lithium-ion battery electrolytes of embodiment 3.
Embodiment 4:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6be stirred to it to dissolve completely, the vinylene carbonate that mass fraction is 1.0% is added in mixed solution, 1% sulfuric acid vinyl ester, 0.03% 3 (2,4-2 tert-butyl-phenyl) phosphite ester, 0.02%N, N'-DIC, obtains the lithium-ion battery electrolytes of embodiment 4.
Embodiment 5:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% 3 (2,4-2 tert-butyl-phenyl) phosphite ester, 0.02% heptamethyldisilazane, obtains the lithium-ion battery electrolytes of embodiment 5.
Embodiment 6:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% dilauryl thiodipropionate, 0.02% heptamethyldisilazane, obtain the lithium-ion battery electrolytes of embodiment 6.
Embodiment 7:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.03% dilauryl thiodipropionate, 0.02%N, N'-DIC, obtains the lithium-ion battery electrolytes of embodiment 7.
Embodiment 8:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.1% 3 (2,4-2 tert-butyl-phenyl) phosphite ester, 0.05%N, N'-DIC obtains the lithium-ion battery electrolytes of embodiment 8.
Embodiment 9:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 0.1% dilauryl thiodipropionate, 0.05%N, N'-DIC obtains the lithium-ion battery electrolytes of embodiment 9.
Embodiment 10:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 1.0% dilauryl thiodipropionate, 1.0%N, N'-DIC obtains the lithium-ion battery electrolytes of embodiment 10.
Embodiment 11:
Be full of glove box (the moisture < 10ppm of argon gas, oxygen divides < 1ppm) in, dimethyl carbonate, methyl ethyl carbonate, ethylene carbonate, ethyl propionate are mixed with 1:1:1:1 mass ratio in the stainless steel cauldron joined using liquid nitrogen as coolant, control temperature, at-15 DEG C ~ 0 DEG C, slowly adds the LiPF that mass fraction is 12.0% in mixed solution
6, be stirred to it and dissolve completely, in mixed solution, add the vinylene carbonate that mass fraction is 1.0%, 1% sulfuric acid vinyl ester, 1.0% 3 (2,4-2 tert-butyl-phenyl) phosphite ester, 1.0%N, N'-DIC obtains the lithium-ion battery electrolytes of embodiment 11.
The lithium-ion battery electrolytes of the above-mentioned comparative example 1-6 that configures and embodiment 1-11 is transferred in water white reagent bottle respectively, store under being placed on 30 DEG C of environment, observe the color situation of change of electrolyte, its moisture, acidity and colourity is tested respectively the 0th day, the 5th day, 10 days, 20 days, 30 days, 45 days time, moisture measurement adopts Karl_Fischer method, acidity test adopts NaOH titration, colourity records employing platinum-cobalt method, and the lithium-ion battery electrolytes of comparative example 1-6 and embodiment 1-11 moisture, acidity changing value in storage process is as shown in table 1.Lithium-ion battery electrolytes colourity changing value in storage process of comparative example 1-6 and embodiment 1-11 is as shown in table 2.
Lithium-ion battery electrolytes moisture, acidity changing value in storage process of table 1 comparative example 1-6 and embodiment 1-11
From the results shown in Table 1, the moisture of all lithium-ion battery electrolytes presents the trend first increasing and reduce afterwards, and acidity presents the trend increased gradually along with the increase in storage time, and this is moisture due to electrolyte in storage process and LiPF
6reaction causes moisture to be consumed, and is converted into HF.Do not add the sulfuric acid vinyl ester additive easily causing electrolyte acidity and colourity to increase in the electrolyte of comparative example 1, moisture change first increases and reduces afterwards comparatively slowly, and acidity growth trend is slower relative to comparative example 2.Sulfuric acid vinyl ester is added in comparative example 2, moisture first increases rear quick reduction, and significantly rises along with the storage time increases the acidity of electrolyte, and this itself has certain acidity due to this additive, generate sulfuric acid with water slow reaction, thus electrolyte acidity is increased fast.Comparative example 3 owing to being configure at low ambient temperatures, LiPF in electrolyte layoutprocedure
6heat release is less, and initial period acidity is lower, and in post storage process, acidity increases quite slower.Because adding of heptamethyldisilazane makes electrolyte moisture reduce in comparative example 4, acidity change is comparatively slow, and this compound has certain alkalescent, can with H
+in conjunction with and can with HF and H
2o forms hydrogen bond, thus reduces acidity.The growth that cannot suppress electrolyte acidity is added due to triphenyl phosphite in comparative example 5.Because electrolyte is that its acidity is higher, and later stage acidity is appointed bigger than normal in normal temperature configuration in comparative example 6.Can find out the increase along with the first kind additive level with the deacidification that dewaters from embodiment 1,2,5 contrast, the acidity of electrolyte has the trend of reduction; Comparative example 2,3 can find that the speed of initial period embodiment 2 pairs of controlling pH is faster than embodiment 3, this is because heptamethyldisilazane not only can form hydrogen bond with acidic materials effect, and self there is certain alkalescent, and N, N DIC is substantially without alkalescence, but can form hydrogen bond with HF or addition reaction occur, reaction speed be comparatively slow, but the ability that this compound later stage reduces acidity is still better.
Lithium-ion battery electrolytes colourity changing value in storage process of table 2. comparative example 1-6 and embodiment 1-11
Table 2 is lithium-ion battery electrolytes colourity delta data in storage process of comparative example 1-6 and embodiment 1-11, as can be seen from comparative example 1,2, sulfuric acid vinyl ester very easily causes the change of electrolyte colourity, stores the 5th day electrolyte colourity and rises to 30-40Hazen.The change of electrolyte colourity can be improved by reducing electrolyte configuration temperature, but still object steady in a long-term cannot be reached, phosphite ester or adding of carbothioic acid ester can significantly suppress electrolyte colourity to change, as can be seen from embodiment 1, electrolyte colourity still increases phase after storage, illustrate that colourity inhibitor is less and be not enough to electrolyte colourity steady in a long-term change, when the content of phosphite ester or carbothioic acid ester be promoted to 0.03% and above time, the basic nondiscolouring of electrolyte colourity can be ensured for a long time; From embodiment 4,5 and embodiment 6,7 relatively, carbothioic acid ester suppresses the effect of electrolyte colourity poorer than phosphite ester, and this may be because sulfuric acid carboxylate antioxygenic property is lower than phosphite ester chemical combination.
Can obviously be found out by moisture, acidity, colourity delta data in above lithium-ion battery electrolytes storage process, when control well electrolyte configuration temperature at-15 DEG C ~ 0 DEG C time, add the above-mentioned additive with the deacidification that dewaters and the additive with the change of stable electrolyte colourity simultaneously, significantly can improve the quality of electrolyte.Especially, in the electrolyte preparation process containing the additive system easily causing electrolyte acidity and colourity to change, the present invention has obvious advantage and has higher commercial value.
Finally should be noted that; above embodiment is only for illustration of technical scheme of the present invention but not limiting the scope of the invention; although be explained in detail the present invention with reference to preferred embodiment; those of ordinary skill in the art is to be understood that; can modify to technical scheme of the present invention or equivalent replacement, and not depart from essence and the scope of technical solution of the present invention.
Claims (10)
1. a lithium-ion battery electrolytes, is made up of electrolyte lithium salt, nonaqueous solvents and additive, it is characterized in that: described additive comprises the first kind additive with the deacidification that dewaters and the Equations of The Second Kind additive with the change of stable electrolyte colourity; Described first kind additive is silazane compounds or carbodiimide compound, and described Equations of The Second Kind additive is thiocarboxylic acid ester type compound or phosphite ester compound.
2. a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: the content of described first kind additive accounts for the 0.01%-1.5% of lithium-ion battery electrolytes gross mass, the content of described Equations of The Second Kind additive accounts for the 0.005%-1.5% of lithium-ion battery electrolytes gross mass.
3. a kind of lithium-ion battery electrolytes according to claim 1, is characterized in that: described silazane compounds is at least one in hexamethyldisiloxane, heptamethyldisilazane, hexamethyl cyclotrisiloxane, pregnancy basic ring three silazane, nine methyl three silazane.
4. a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: described carbodiimide compound is dicyclohexylcarbodiimide, N, at least one in N'-DIC, 1-(3-dimethylaminopropyl)-3-ethyl carbodiimide, 1-(3-dimethylamino-propyl)-3-cyclohexyl, N, N-di-t-butyl carbodiimide.
5. a kind of lithium-ion battery electrolytes according to claim 1, is characterized in that: described thiocarboxylic acid ester type compound is at least one in dilauryl thiodipropionate, pentaerythrite four (3-lauryl thiopropionate), thio-2 acid two (18) ester.
6. a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: described phosphite ester compound is triphenyl phosphite, tri iso octyl phosphorite, diphenylisodecyl base ester, two (2,4-di-tert-butyl-phenyl) pentaerythritol diphosphites, two (2,4,6-tri-tert phenyl) pentaerythritol diphosphites, four (2,4-di-tert-butylphenol)-4, at least one in 4'-xenyl diphosphites, three (2,4-di-tert-butyl-phenyl) phosphite ester.
7. a kind of lithium-ion battery electrolytes according to claim 1, is characterized in that: described nonaqueous solvents is the two or more mixture in dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, propene carbonate, ethylene carbonate, methyl propyl carbonate, ethyl propionate, ethyl acetate, Ethyl formate, propyl butyrate, oxolane, dioxy cycloalkanes, diethanol diethyl ether, gamma-butyrolacton; The content of described nonaqueous solvents accounts for the 75.0%-88.0% of lithium-ion battery electrolytes gross mass.
8. a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: described electrolyte lithium salt is at least one in lithium hexafluoro phosphate, di-oxalate lithium borate, difluorine oxalic acid boracic acid lithium, two fluorine sulfimide lithium, and the content of described lithium salts accounts for the 10.0%-18.0% of lithium-ion battery electrolytes gross mass.
9. a kind of lithium-ion battery electrolytes according to claim 1, it is characterized in that: described additive also comprises vinylethylene carbonate, fluorinated ethylene carbonate, 1, at least one in 3-propane sultone, sulfuric acid vinyl ester, 4-methylsulfuric acid vinyl acetate, its content accounts for the 0.1%-5.0% of lithium-ion battery electrolytes gross mass.
10. the preparation method of a kind of lithium-ion battery electrolytes described in claim 1-9 any one, it is characterized in that: the liquid nitrogen passing into flowing in the chuck of stainless steel cauldron cools, then in stainless steel cauldron, add the nonaqueous solvents of formula ratio, when the temperature of nonaqueous solvents is reduced to-15 DEG C ~ 0 DEG C, in stainless steel cauldron, slowly add the electrolyte lithium salt of formula ratio and fully stir, matter lithium salts to be electrolysed dissolves the additive adding formula ratio in backward reactor completely, obtains described lithium-ion battery electrolytes after stirring.
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Effective date of registration: 20230921 Address after: No.62 Huayin North Road, Kecheng District, Quzhou City, Zhejiang Province Patentee after: New Asia Shanshan New Material Technology (Quzhou) Co.,Ltd. Address before: 523085 Dongguan Shanshan Battery Materials Co., Ltd., Plant Area 5, Shuilian Pengdong Industrial Zone, Nancheng District, Dongguan City, Guangdong Province Patentee before: DONGGUAN SHANSHAN BATTERY MATERIALS Co.,Ltd. |