CN104448324A - Grafted polysilane compound, preparation method and application of grafted polysilane compound in battery electrolyte - Google Patents
Grafted polysilane compound, preparation method and application of grafted polysilane compound in battery electrolyte Download PDFInfo
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Abstract
The invention discloses a grafted polysilane compound, a preparation method and an application of the grafted polysilane compound. A chemical structural formula of the grafted polysilane compound can be expressed with the following formula as shown in the specification, wherein the polymerization degree n is 18-23; the quantity m of -CH2- chain links is 0-6; and the grafted replacement rate x is 0-0.8. The invention also provides a preparation method of the grafted polysilane compound. The method comprises the following step: grafting a vinylene carbonate compound on a branch chain of poly-hydrogen methylsilane through hydrosilicenae addition reaction, so as to obtain grafted polysilane. The grafted polysilane compound provided by the invention can be applied to the battery electrolyte as a stabilizer, thus the charge and discharge cycling stability of the battery at a high temperature is improved.
Description
Technical field
The present invention relates to technical field of lithium ion, be specifically related to a kind of grafting polysilane-series compounds, also relate to the preparation method of this grafting polysilane-series compounds and the application in battery electrolyte.
Background technology
The use temperature scope of lithium ion battery depends primarily on the performance of electrolytic solution, requires that lithium-ion battery electrolytes has comparatively high ionic conductivity, comparatively low-freezing, higher boiling point and chemical and electrochemical stability.Current widely used liquid organic electrolyte is with its low cost, and the advantage of high ionic conductivity and more stable chemical property, still firmly in occupation of most of share of commercial li-ion Battery Market.
At present, in commercial lithium ion battery, most widely used electrolytic solution is by electric conducting lithium salt lithium hexafluoro phosphate (LiPF
6) be dissolved in the mixed solvent of binary based on NSC 11801 or ternary.Organic liquid lithium-ion battery electrolytes mainly comprises two kinds of carbonic ethers, and one is high polarity, full-bodied cyclic carbonate, as NSC 11801 (EC, 2,5-dioxolane-1-ketone); Another kind is low polarity, low viscous linear carbonate, as methylcarbonate (DMC), diethyl carbonate (DEC) and Methyl ethyl carbonate (EMC).Wherein, EC is the key ingredient in carbonate group electrolytic solution, because it can form the destruction that effective SEI film stops charge and discharge process graphite platelet structure on graphite cathode; Linear carbonate effectively can expand the liquid state range of electrolyte system.
But, improve the impossible realization often of low-temperature performance and high-temperature behavior by adding liquid component simultaneously.In order to improve electrolytic solution specific conductivity at low temperatures, usually add low-freezing, low viscous cosolvent to reduce the viscosity of whole ternary or quaternary electrolyte system.The cosolvent usually adopted at present has glycol dimethyl ether (DME), tetrahydrofuran (THF) (THF) is applied in low-temperature rate electrolytic solution.But these compounds often have higher vapour pressure and lower flash-point, may reduce the security that electrolytic solution is applied in environment more than 60 DEG C; Under high temperature, carbonic ether and lithium salts decompose themselves speed are accelerated, and the trend of the electrochemical oxidation/reduction reaction of electrolytic solution and positive and negative pole material obviously strengthens simultaneously, and the high temperature circulation stability of battery can be deteriorated.Usually can add lithium salts stablizer, anti-electuary, fire retardant etc. excessively, but the usual zero pour of these components is high, viscosity is large, brings disadvantageous effect to electrolytic solution low-temperature performance.Meanwhile, molecular structure is comparatively complicated, and synthesis technique difficulty is large; In new electrolyte system, the usage quantity of this solvent is large simultaneously, may cause the high of electrolytic solution cost.
Summary of the invention
The technical problem to be solved in the present invention overcomes the deficiencies in the prior art, the grafting polysilane-series compounds that a kind of impact on battery low-temperature performance is less, solvability is good is provided, additionally provides the preparation method of the grafting polysilane-series compounds that a kind of preparation technology is simple, product yield is high, purity is high.There is provided and additionally provide a kind of grafting polysilane-series compounds as the application of stablizer in battery electrolyte, addition is little, and application efficiency is high.
For solving the problems of the technologies described above, the invention provides a kind of grafting polysilane-series compounds, the chemical structural formula of foregoing graft polysilane-series compounds can represent with formula I:
Wherein, polymerization degree n is 18 ~ 23;
-CH
2-chain link number m is 0 ~ 6;
Grafting Replacement rate x is 0 ~ 0.8.
As a total technical conceive, present invention also offers a kind of preparation method of foregoing graft polysilane-series compounds, comprise the following steps: vinylene carbonate or its alkenyl substituted thing are grafted on the side chain of poly-hydrogen methyl-monosilane by addition reaction of silicon with hydrogen and obtain grafting polysilane.
Further, aforementioned preparation process also comprises post-processing step: foregoing graft polysilane is added normal hexane under an ar atmosphere successively, methyl alcohol carries out separating and extracting and obtain grafting polysilane solid.
Further, the concrete steps of aforementioned addition reaction of silicon with hydrogen are: vinylene carbonate or its alkenyl substituted thing and poly-hydrogen methyl-monosilane are dissolved in organic solvent and obtain mixing solutions, reflux aforementioned mixing solutions at 60 ~ 70 DEG C 12h.
Further, in aforementioned mixing solutions, add initiator, and then reflux.
Further, aforementioned organic solvents is tetrahydrofuran (THF); Foregoing initiators is Diisopropyl azodicarboxylate.
Further, the addition of foregoing initiators is 0.1wt% ~ 5wt%.
Further, the mass ratio of aforementioned vinylene carbonate or its alkenyl substituted thing and described poly-hydrogen methyl-monosilane is 1: 10 ~ 2.5: 1, and the alkenyl substituted thing of aforementioned vinylene carbonate is vinylethylene carbonate.
As a total skill design, present invention also offers a kind of aforesaid grafting polysilane-series compounds or the grafting polysilane-series compounds for preparing according to aforementioned preparation process as the application of stablizer in battery electrolyte.
Further, the addition of aforementioned stablizer is 0.1 ~ 2wt%.
Innovative point of the present invention is:
The invention discloses a kind of grafting polysilane-series compounds, obtain by the side chain that vinylene carbonate ester compound is grafted to poly-hydrogen methyl-monosilane by addition reaction of silicon with hydrogen, its reaction equation is:
Grafting polysilane-series compounds provided by the invention, Si-H on hydrogeneous polysilane is utilized to be easy to oxidation cross-linked characteristic in the layered cathode material surface of (>3.8V) under high potential, the ring-opening polymerization of cyclic carbonate grafted moiety generation simultaneously, at the protective layer of positive electrode surface stable performance; Utilize carbonate group (<0.5V) under comparatively low potential to generate stable SEI film at graphite cathode surface reduction, improve whole battery charge and discharge cycles stability at high temperature thus.Grafting polysilanes lithium-ion battery electrolytes additive is added in carbonate group electrolytic solution and effectively can improves layered cathode material-graphite cell charge and discharge cycles stability at high temperature, suppress the attenuation loss of capacity.
Meanwhile, because grafting polysilane-series compounds character is comparatively active, addition very little (<1wt%), can be exhausted, make whole battery system have higher high-temperature behavior in front several charge and discharge circulation.The impact of this mechanism on battery low-temperature performance is less.Therefore likely select the low temperature cosolvent be suitable for coordinate with grafting polysilane additive, make carbonate group electrolytic solution obtain wider use temperature scope.
Compared with prior art, the invention has the advantages that:
(1) principle is novel.Grafting polysilane-series compounds provided by the invention utilizes the ester groups of active Si-H and grafting on hydrogeneous polysilane; at the protective layer that positive/negative surface forming property is stable in front several circulation; improve whole battery charge and discharge cycles stability at high temperature thus, less on the impact of battery low-temperature performance.
(2) solvability is good.The present invention, by grafting ester class or carbonates group on hydrogeneous polysilane main chain, makes grafting polysilanes additive have good solubility in now widely used carbonate group electrolytic solution.
(3) prepare easy.The preparation method of the grafting polysilanes that the present invention also provides, preparation technology is simple, be applicable to suitability for industrialized production, significantly improves product yield and purity, be conducive to as the addO-on therapy of lithium-ion battery electrolytes.
(4) addition is few.The present invention adopts grafting polysilane-series compounds to add in battery electrolyte as stablizer, in carbonate group electrolytic solution, only add the grafting polysilane-series compounds of 0.1 ~ 2wt%, effectively can improve layered cathode material-graphite cell charge and discharge cycles stability at high temperature, the attenuation loss of suppression capacity, Be very effective.
Accompanying drawing explanation
For making the object of the embodiment of the present invention, technical scheme and advantage clearly, below in conjunction with the accompanying drawing in the embodiment of the present invention, clear, complete description is carried out to the technical scheme in the embodiment of the present invention.
Fig. 1 is the FTIR spectrogram of the grafting polysilane additive of the embodiment of the present invention 1.
Fig. 2 is the grafting polysilane additive of the embodiment of the present invention 1
1h-NMR spectrogram.
Fig. 3 is the FTIR spectrogram of the grafting polysilane additive of the embodiment of the present invention 2.
Fig. 4 is the grafting polysilane additive of the embodiment of the present invention 2
1h-NMR spectrogram.
Fig. 5 is the FTIR spectrogram of the grafting polysilane additive of the embodiment of the present invention 3.
Fig. 6 is the grafting polysilane additive of the embodiment of the present invention 3
1h-NMR spectrogram.
Fig. 7 is the FTIR spectrogram of the grafting polysilane additive of the embodiment of the present invention 4.
Fig. 8 is the grafting polysilane additive of the embodiment of the present invention 4
1h-NMR spectrogram.
Fig. 9 is the FTIR spectrogram of the grafting polysilane additive of the embodiment of the present invention 5.
Figure 10 is the grafting polysilane additive of the embodiment of the present invention 5
1h-NMR spectrogram.
Figure 11 is LiCoO
2high temperature cyclic performance in the electrolytic solution of-graphite cell in the embodiment of the present invention 6 and comparative example 1.
Figure 12 is LiCoO
2specific storage-the voltage curve of the 2nd circulation in the electrolytic solution of-graphite cell in the embodiment of the present invention 6 and comparative example 1.
Figure 13 is LiCoO
2high temperature cyclic performance in the electrolytic solution of-graphite cell in the embodiment of the present invention 9 and comparative example 1.
Figure 14 is LiCoO
2high temperature cyclic performance in the electrolytic solution of-graphite cell in the embodiment of the present invention 10 and comparative example 2.
Embodiment
Below in conjunction with Figure of description and concrete preferred embodiment, the invention will be further described, but protection domain not thereby limiting the invention.
The material adopted in following examples and instrument are commercially available.
Embodiment 1:
A kind of grafting polysilane-series compounds PMSVC, its structural formula is as follows:
Wherein, polymerization degree n is 21;-CH on grafted moiety
2-chain link number m is 0; Grafting Replacement rate x is 8%.
The synthetic method of grafting polysilane-series compounds PMSVC, specifically comprises the following steps:
(1) get 0.88g vinylene carbonate (VC) and 4.40g and gather hydrogen methyl-monosilane (PMS) (mass ratio of VC and PMS be all can implement at 1: 10 ~ 2: 1), be dissolved in tetrahydrofuran (THF) (THF), add 0.01g Diisopropyl azodicarboxylate (AIBN), reflux 12h at 60 ~ 70 DEG C, and underpressure distillation removes desolventizing and obtains grafting polysilane-series compounds PMSVC.
(2) grafting polysilane-series compounds PMSVC is added normal hexane under Ar atmosphere protection, stirring makes reaction product fully dissolve and obtains mixed solution.In mixed solution, add equivalent methyl alcohol carry out sedimentation, discard supernatant liquid after centrifugal and obtain PMSVC precipitation.
(3), add the abundant stirring of methylcarbonate DMC (10 ~ 50mL all can implement) of 20mL in PMSVC precipitation after, leaching solution is crossed.Add in the solution
after molecular sieve makes moisture be down to below 10ppm, pressure reducing and steaming solvent, obtains pale yellow transparent thick liquid, can directly add in battery electrolyte.
Synthesize THF realization sodium Metal 99.5 backflow used except Water warfare, methyl alcohol, normal hexane and DMC adopt analytical reagent, and re-distillation gets middle runnings, use
molecular sieve dewaters.
In the building-up process of grafting polysilane-series compounds PMSVC, organic solvent is not limited in tetrahydrofuran (THF); Initiator is not limited in Diisopropyl azodicarboxylate; any can reach phase same-action organic solvent and initiator all belong to protection scope of the present invention; meanwhile, the addition of initiator is that 0.1wt% ~ 5wt% all can implement, and reaches same or analogous technique effect.
Structural characterization is carried out to the grafting polysilane-series compounds PMSVC of embodiment 1:
See Fig. 1, the FTIR spectrogram of the grafting polysilane PMSVC of embodiment 1, wave number is at 2950 ~ 2850cm
-1between peak belong to the stretching vibration peak of C-H, 2150cm
-1peak belong to the stretching vibration peak of Si-H, 1800cm
-1peak belong to the stretching vibration peak of C=O in grafted moiety, 1250cm
-1peak belong to Si-CH
3formation vibration peak, 870cm
-1peak belong to the formation vibration peak of Si-H.The spectrogram of contrast PMSVC and raw material PMS is known, and after grafting replaces, Si-H peak intensity reduces, and accordingly, has occurred C=O peak, illustrates that the raw material PMS occurred Si-H addition reaction occurs and carried out grafting.
See Fig. 2, the grafting polysilane PMSVC's of embodiment 1
1h-NMR spectrogram, chemical shift is returned in the ebb of 4.7 ~ 4.5ppm and 4.3 ~ 4.1ppm and is belonged to methylene radical (-CH on grafted moiety respectively
2-) and the proton peak of methyne (-CH<); Chemical shift belongs to the proton peak of Si-H at the broad peak at 3.8 ~ 3.6ppm place, and chemical shift belongs at the strong peak of 1.2 ~ 1.0ppm and 1.0 ~ 0.8ppm to be affected and not by the-Si-CH that grafting affects by grafted moiety
2-proton peak.Chemical shift belongs to-Si-CH at the strong broad peak of 0.6 ~ 0.1ppm
3proton peak, after with this peak area, to be interior mark be normalized full spectrum, the grafting Replacement rate that can be calculated grafting polysilane by the integral area of the proton peak of Si-H is further 5%.
Embodiment 2:
A kind of grafting polysilane-series compounds PMSVEC10, its structural formula is as follows:
Wherein, polymerization degree n is 20;-CH
2-chain link number m is 2; Grafting Replacement rate x is 0.10.
The synthetic method of grafting polysilane-series compounds PMSVEC10, specifically comprises the following steps:
(1) 1.14g vinylethylene carbonate (VEC) and 4.40g PMS (mass ratio of VEC and PMS be all can implement at 1: 10 ~ 2.5: 1) is got, be dissolved in THF, add 0.01g AIBN, reflux 12h at 60 ~ 70 DEG C, and underpressure distillation is except desolventizing.
(2) under Ar atmosphere protection, add normal hexane, stir and make it fully dissolve.Add equivalent methyl alcohol and carry out sedimentation, discard supernatant liquid after centrifugal and be precipitated.
(3) add the abundant stirring of methylcarbonate DMC (10 ~ 50mL all can implement) of 20mL to precipitation after, leaching solution.Add
after molecular sieve makes moisture be down to below 10ppm, pressure reducing and steaming solvent, obtains pale yellow transparent thick liquid.
Synthesize THF realization sodium Metal 99.5 backflow used except Water warfare, methyl alcohol, normal hexane and DMC adopt analytical reagent, and re-distillation gets middle runnings, use
molecular sieve dewaters.
See Fig. 3, the FTIR spectrogram of the grafting polysilane PMSVEC10 of embodiment 2, wave number is at 2950 ~ 2850cm
-1between peak belong to the stretching vibration peak of C-H, 2150cm
-1peak belong to the stretching vibration peak of Si-H, 1800cm
-1peak belong to the stretching vibration peak of C=O in grafted moiety, 1400cm
-1peak belong to methylene radical (-CH in grafting group
2-) formation vibration peak, 1250cm
-1peak belong to Si-CH
3formation vibration peak, 870cm
-1peak belong to the formation vibration peak of Si-H.The spectrogram of contrast PMSVEC10 and raw material PMS is known, and after grafting replaces, Si-H peak intensity reduces, and accordingly, has occurred C=O peak, illustrates that the raw material PMS occurred Si-H addition reaction occurs and carried out grafting.
See Fig. 4, the grafting polysilane PMSVEC10's of embodiment 2
1h-NMR spectrogram, chemical shift is returned in the ebb of 4.6 ~ 4.5ppm and 4.1 ~ 4.0ppm and is belonged to methylene radical (-CH on grafted moiety five-ring respectively
2-) and the proton peak of methyne (-CH<); Chemical shift belongs to the proton peak of the Si-H of grafting and non-grafting on adjacent S i chain link at the broad peak at 4.8 ~ 4.6ppm and 3.8 ~ 3.6ppm place, and chemical shift belongs to-CH on grafted moiety at the broad peak at 2.0 ~ 1.5ppm place
2-CH
2-proton peak, chemical shift belongs at the strong peak of 1.2 ~ 1.0ppm and 1.0 ~ 0.8ppm to be affected and not by the-Si-CH that grafting affects by grafted moiety
2-proton peak.Chemical shift belongs to-Si-CH at the strong broad peak of 0.6 ~ 0.1ppm
3proton peak, after with this peak area, to be interior mark be normalized full spectrum, the grafting Replacement rate being calculated grafting polysilane by the integral area of the proton peak of Si-H is further 10%.
Embodiment 3:
A kind of grafting polysilane-series compounds PMSVEC40, its structural formula is as follows:
Wherein, polymerization degree n is 20;-CH
2-chain link number m is 2; Grafting Replacement rate x is 0.37.
The synthetic method of grafting polysilane-series compounds PMSVEC40, specifically comprises the following steps:
(1) get 4.56g VEC and 4.40g PMS (mass ratio of VEC and PMS be all can implement at 1: 10 ~ 2.5: 1), be dissolved in THF, add the AIBN of 0.01g, reflux 12h at 60 ~ 70 DEG C, and underpressure distillation is except desolventizing.
(2) under Ar atmosphere protection, add normal hexane, stir and make it fully dissolve.Add equivalent methyl alcohol and carry out sedimentation, discard supernatant liquid after centrifugal and be precipitated.
(3) add the abundant stirring of methylcarbonate DMC (10 ~ 50mL all can implement) of 20mL to precipitation after, leaching solution.Add
after molecular sieve makes moisture be down to below 10ppm, pressure reducing and steaming solvent, obtains pale yellow transparent thick liquid.
Synthesize THF realization sodium Metal 99.5 backflow used except Water warfare, methyl alcohol, normal hexane and DMC adopt analytical reagent, and re-distillation gets middle runnings, use
molecular sieve dewaters.
See Fig. 5, the FTIR spectrogram of the grafting polysilane PMSVEC40 of embodiment 3, wave number is at 2950 ~ 2850cm
-1between peak belong to the stretching vibration peak of C-H, 2150cm
-1peak belong to the stretching vibration peak of Si-H, 1800cm
-1peak belong to the stretching vibration peak of C=O in grafted moiety, 1400cm
-1peak belong to methylene radical (-CH in grafting group
2-) formation vibration peak, 1250cm
-1peak belong to Si-CH
3formation vibration peak, 870cm
-1peak belong to the formation vibration peak of Si-H.The spectrogram of contrast PMSVEC40 and raw material PMS is known, and after grafting replaces, Si-H peak intensity reduces, and accordingly, has occurred C=O peak, illustrates that the raw material PMS occurred Si-H addition reaction occurs and carried out grafting.
See Fig. 6, the grafting polysilane PMSVEC40's of embodiment 3
1h-NMR spectrogram, chemical shift is returned in the ebb of 4.6 ~ 4.5ppm and 4.1 ~ 4.0ppm and is belonged to methylene radical (-CH on grafted moiety five-ring respectively
2-) and the proton peak of methyne (-CH<); Chemical shift belongs to the proton peak of the Si-H of grafting and non-grafting on adjacent S i chain link at the broad peak at 4.8 ~ 4.6ppm and 3.8 ~ 3.6ppm place, and chemical shift belongs to-CH on grafted moiety at the broad peak at 2.0 ~ 1.5ppm place
2-CH
2-proton peak, chemical shift belongs at the strong peak of 1.2 ~ 1.0ppm and 1.0 ~ 0.8ppm to be affected and not by the-Si-CH that grafting affects by grafted moiety
2-proton peak.Chemical shift belongs to-Si-CH at the strong broad peak of 0.6 ~ 0.1ppm
3proton peak, after with this peak area, to be interior mark be normalized full spectrum, the grafting Replacement rate being calculated grafting polysilane by the integral area of the proton peak of Si-H is further 37%.
Embodiment 4:
A kind of grafting polysilane-series compounds PMSVEC70, its structural formula is as follows:
Wherein, polymerization degree n is 20;-CH
2-chain link number m is 2; Grafting Replacement rate x is 0.50.
The synthetic method of grafting polysilane-series compounds PMSVEC70, specifically comprises the following steps:
(1) get 7.98g VEC and 4.40g PMS (mass ratio of VEC and PMS be all can implement at 1: 10 ~ 2.5: 1), be dissolved in THF, add 0.01g AIBN, reflux 12h at 60 ~ 70 DEG C, and underpressure distillation is except desolventizing.
(2) under Ar atmosphere protection, add normal hexane, stir and make it fully dissolve.Add equivalent methyl alcohol and carry out sedimentation, discard supernatant liquid after centrifugal and be precipitated.
(3) add the abundant stirring of methylcarbonate DMC (10 ~ 50mL all can implement) of 20mL to precipitation after, leaching solution.Add
after molecular sieve makes moisture be down to below 10ppm, pressure reducing and steaming solvent, obtains pale yellow transparent thick liquid.
Synthesize THF realization sodium Metal 99.5 backflow used except Water warfare, methyl alcohol, normal hexane and DMC adopt analytical reagent, and re-distillation gets middle runnings, use
molecular sieve dewaters.
See Fig. 7, the FTIR spectrogram of the grafting polysilane PMSVEC70 of embodiment 4, wave number is at 2950 ~ 2850cm
-1between peak belong to the stretching vibration peak of C-H, 2150cm
-1peak belong to the stretching vibration peak of Si-H, 1800cm
-1peak belong to the stretching vibration peak of C=O in grafted moiety, 1400cm
-1peak belong to methylene radical (-CH in grafting group
2-) formation vibration peak, 1250cm
-1peak belong to Si-CH
3formation vibration peak, 870cm
-1peak belong to the formation vibration peak of Si-H.The spectrogram of contrast PMSVEC70 and raw material PMS is known, and after grafting replaces, Si-H peak intensity reduces, and accordingly, has occurred C=O peak, illustrates that the raw material PMS occurred Si-H addition reaction occurs and carried out grafting.
See Fig. 8, the grafting polysilane PMSVEC70's of embodiment 4
1h-NMR spectrogram, chemical shift is returned in the ebb of 4.6 ~ 4.5ppm and 4.1 ~ 4.0ppm and is belonged to methylene radical (-CH on grafted moiety five-ring respectively
2-) and the proton peak of methyne (-CH<); Chemical shift belongs to the proton peak of the Si-H of grafting and non-grafting on adjacent S i chain link at the broad peak at 4.8 ~ 4.6ppm and 3.8 ~ 3.6ppm place, and chemical shift belongs to-CH on grafted moiety at the broad peak at 2.0 ~ 1.5ppm place
2-CH
2-proton peak, chemical shift belongs at the strong peak of 1.2 ~ 1.0ppm and 1.0 ~ 0.8ppm to be affected and not by the-Si-CH that grafting affects by grafted moiety
2-proton peak.Chemical shift belongs to-Si-CH at the strong broad peak of 0.6 ~ 0.1ppm
3proton peak, after with this peak area, to be interior mark be normalized full spectrum, the grafting Replacement rate that can be calculated grafting polysilane by the integral area of the proton peak of Si-H is further 50%.
Embodiment 5:
A kind of grafting polysilane-series compounds PMSVEC100, its structural formula is as follows:
Wherein, polymerization degree n is 20;-CH
2-chain link number m is 2; Grafting Replacement rate x is 0.61.
The synthetic method of grafting polysilane-series compounds PMSVEC100, specifically comprises the following steps:
(1) get 11.4g VEC and 4.40g PMS (mass ratio of VEC and PMS be all can implement at 1: 10 ~ 2.5: 1), be dissolved in THF, add 0.01g AIBN, reflux 12h at 60 ~ 70 DEG C, and underpressure distillation is except desolventizing.
(2) under Ar atmosphere protection, add normal hexane, stir and make it fully dissolve.Add equivalent methyl alcohol and carry out sedimentation, discard supernatant liquid after centrifugal and be precipitated.
(3) after the methylcarbonate DMC adding 20mL (10 ~ 50mL all can implement) to precipitation fully stirs, leaching solution.Add
after molecular sieve makes moisture be down to below 10ppm, pressure reducing and steaming solvent, obtains pale yellow transparent thick liquid.Synthesize THF realization sodium Metal 99.5 backflow used except Water warfare, methyl alcohol, normal hexane and DMC adopt analytical reagent, and re-distillation gets middle runnings, use
molecular sieve dewaters.
See Fig. 9, the FTIR spectrogram of the grafting polysilane PMSVEC100 of embodiment 5, wave number is at 2950 ~ 2850cm
-1between peak belong to the stretching vibration peak of C-H, 2150cm
-1peak belong to the stretching vibration peak of Si-H, 1800cm
-1peak belong to the stretching vibration peak of C=O in grafted moiety, 1400cm
-1peak belong to methylene radical (-CH in grafting group
2-) formation vibration peak, 1250cm
-1peak belong to Si-CH
3formation vibration peak, 870cm
-1peak belong to the formation vibration peak of Si-H.The spectrogram of contrast PMSVEC100 and raw material PMS is known, and after grafting replaces, Si-H peak intensity reduces, and accordingly, has occurred C=O peak, illustrates that the raw material PMS occurred Si-H addition reaction occurs and carried out grafting.
See Figure 10, the grafting polysilane PMSVEC100's of embodiment 5
1h-NMR spectrogram, chemical shift is returned in the ebb of 4.6 ~ 4.5ppm and 4.1 ~ 4.0ppm and is belonged to methylene radical (-CH on grafted moiety five-ring respectively
2-) and the proton peak of methyne (-CH<); Chemical shift belongs to the proton peak of the Si-H of grafting and non-grafting on adjacent S i chain link at the broad peak at 4.8 ~ 4.6ppm and 3.8 ~ 3.6ppm place, and chemical shift belongs to-CH on grafted moiety at the broad peak at 2.0 ~ 1.5ppm place
2-CH
2-proton peak, chemical shift belongs at the strong peak of 1.2 ~ 1.0ppm and 1.0 ~ 0.8ppm to be affected and not by the-Si-CH that grafting affects by grafted moiety
2-proton peak.Chemical shift belongs to-Si-CH at the strong broad peak of 0.6 ~ 0.1ppm
3proton peak, after with this peak area, to be interior mark be normalized full spectrum, the grafting Replacement rate that can be calculated grafting polysilane by the integral area of the proton peak of Si-H is further 61%.
Embodiment 1 to 5 is only the preferred embodiments of the present invention, and in the present invention, general structure is the grafting polysilane-series compounds of formula I structure, and polymerization degree n is 18 ~ 23 ,-CH
2-chain link number m is 0 ~ 6, and grafting Replacement rate x 0 ~ 0.8 all can implement, and all can be used as stablizer and be applied in battery electrolyte, reaches same or analogous technique effect.
Embodiment 6, the PMSVC application in battery electrolyte:
After NSC 11801 (EC), Methyl ethyl carbonate (EMC) by volume 1: 4 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane compound PMSVC light yellow viscous liquid embodiment 1 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
Embodiment 7, the PMSVC application in battery electrolyte:
After EC, methylcarbonate (DMC) by volume 1: 1 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVC light yellow viscous liquid embodiment 1 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
Embodiment 8, the PMSVC application in battery electrolyte:
After EC, EMC and DMC by volume 1: 1: 1 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVC light yellow viscous liquid embodiment 1 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification
Embodiment 9, the PMSVC10 application in battery electrolyte:
After EC, EMC by volume 1: 4 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVEC10 light yellow viscous liquid embodiment 2 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
Embodiment 10, the PMSVC10 application in battery electrolyte:
After EC, DMC by volume 1: 1 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVEC10 light yellow viscous liquid embodiment 2 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
Embodiment 11, the PMSVC40 application in battery electrolyte:
After EC, DMC by volume 1: 4 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVEC40 light yellow viscous liquid embodiment 3 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
Embodiment 12, the PMSVC70 application in battery electrolyte:
After EC, DMC by volume 1: 1 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVEC70 light yellow viscous liquid embodiment 4 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
Embodiment 13, the PMSVC100 application in battery electrolyte:
After EC, DMC by volume 1: 1 mixing, add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, control moisture content and make it lower than 10ppm, obtain basic lithium-ion battery electrolytes.Grafting polysilane additive PMSVEC100 light yellow viscous liquid embodiment 5 prepared is added in basic electrolyte by massfraction 0.5% and fully stirs, and standing 24h obtains the lithium-ion battery electrolytes of modification.
In embodiment 6 to 13, the addition of grafting polysilane-series compounds is that 0.1 ~ 2wt% all can implement, and reaches same or analogous technique effect.
Comparative example 1
By EC, EMC 1: 4 mixing by volume, then add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, obtain lithium-ion battery electrolytes.
Comparative example 2
By EC, DMC 1: 1 mixing by volume, then add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, obtain lithium-ion battery electrolytes.
Comparative example 3
By EC, EMC, DMC 1: 1: 1 mixing by volume, then add lithium hexafluoro phosphate, make it concentration and reach 1mol/L, obtain lithium-ion battery electrolytes.
Carry out high-temperature lithium ion battery cyclical stability mensuration to the battery electrolyte of embodiment 6 to 13 and comparative example 1 to 3, measuring method is as follows:
Adopt small-sized laminated batteries system (lamination size, positive plate: 3.0 × 4.0cm, negative plate size: 3.2 × 4.2cm, diaphragm size: 3.5 × 4.5).Layered cathode material selects the LiCoO of Jiangsu Cobalt Nickel Metal Co., Ltd.
2, negative pole graphite material selects the AGP-8 of Bei Terui company.
The preparation of Graphite Electrodes is by 90wt.% synthetic graphite powder, and the acetylene black of 5wt% and the PVDF of 5wt% are evenly coated on the thick Copper Foil of 0.1mm also fully dry after N-Methyl pyrrolidone ball milling mixing 1h.
LiCoO
2the preparation of electrode is by the LiCoO of 80%
2, the acetylene black of 10wt% and the PVDF of 10wt% be dissolved in after in METHYLPYRROLIDONE, ball milling 1h mixes, and is spread evenly across on high-purity aluminum foil, the pole piece made in vacuum drying oven in 110 DEG C of dry 12h.
Charge-discharge magnification 0.2C, charge and discharge process all carries out at same temperature, tests its cyclical stability at normal temperature and 60 DEG C.The programmable constant temperature and humid test machine that the temperature of battery in charge and discharge process controls to be provided by Dongguan City Gao Xin test set company limited completes.
Table 1 is after the battery electrolyte adopting the embodiment of the present invention 6 to 13 and comparative example 1 to 3 to prepare, LiCoO
2the cyclical stability test result of-graphite cell under normal temperature and 60 DEG C of high temperature.
Table 1: the ionic conductivity of electrolytic solution
As can be known from the results of Table 1: use grafting polysilane provided by the invention to significantly improve the high-temperature behavior of carbonic ester electrolyte, improving LiCoO
2successful in the high temperature circulation stability of-graphite cell.
Figure 11 is LiCoO
2high temperature cyclic performance in the electrolytic solution of-graphite cell in the embodiment of the present invention 6 and comparative example 1; Adopt the battery of the comparative example 1 electrolytic solution coulombic efficiency that circulates at 60 DEG C lower as can be known from Fig. 11, the decay of its specific discharge capacity obviously.Adopt after with the addition of the electrolytic solution of embodiment 6 of PMSVC, coulombic efficiency and specific discharge capacity are all significantly improved.Illustrate that the PMSVC that embodiment 1 is neutralized into can improve LiCoO effectively
2the high temperature cyclic performance of-graphite cell.
Figure 12 is LiCoO
2specific storage-the voltage curve of the 2nd circulation in the electrolytic solution of-graphite cell in the embodiment of the present invention 6 and comparative example 1; Both charging and discharging curves are similar as can be known from Fig. 12, do not occur new voltage platform.Show that PMSVC additive substantially exhausts in circulation first, passivation layer may be formed on electrode, thus improve follow-up cycle efficiency, stable discharging specific storage, LiCoO
2the original charge-discharge mechanism of-graphite cell does not change.
Figure 13 is LiCoO
2high temperature cyclic performance in the electrolytic solution of-graphite cell in the embodiment of the present invention 9 and comparative example 1; The battery of comparative example 1 electrolytic solution is adopted to circulate at 60 DEG C as can be known from Fig. 13,0.2C (1C=140mAg
-1) coulombic efficiency is lower under multiplying power, the decay of its specific discharge capacity is obviously.Adopt after with the addition of the electrolytic solution of embodiment 9 of PMSVEC10, under 0.2C multiplying power, coulombic efficiency is significantly improved, and in circulation, specific discharge capacity decay is obviously slowed down.Illustrate that PMSVEC10 additive that embodiment 2 is neutralized into is for 1molL
-1liPF
6effectively LiCoO can be improved in/EC+EMC (1: 4) electrolytic solution
2the high temperature cyclic performance of-graphite cell.
Figure 14 is LiCoO
2high temperature cyclic performance in the electrolytic solution of-graphite cell in the embodiment of the present invention 10 and comparative example 2; Adopt the battery of comparative example 2 electrolytic solution to circulate at 60 DEG C as can be known from Fig. 14, the special capacity fade that discharges under 0.2C charge-discharge magnification is obvious.Adopt with the addition of the electrolytic solution of the embodiment 10 of PMSVEC10 after battery in the circulating cycle specific discharge capacity decay obviously slow down.Illustrate that PMSVEC10 additive that embodiment 2 is neutralized into is for 1molL
-1liPF
6effectively LiCoO can be improved in/EC+DMC (1: 1) electrolytic solution
2the high temperature cyclic performance of-graphite cell.
1molL
-1liPF
6/ EC+EMC (1: 4) and 1molL
-1liPF
6/ EC+DMC (1: 1) is two kinds of common lithium-ion battery electrolytes formulas.Known by the comparative benefits of table 1, Figure 13 and Figure 14, the grafting polysilane additive that this patent of the present invention provides can be widely used in carbonate group electrolytic solution, successful in the high temperature circulation stability improving cobalt acid lithium-graphite cell, improves the integral high-temperature performance of battery.
The above is only preferred embodiment of the present invention, not does any pro forma restriction to the present invention.Although the present invention discloses as above with preferred embodiment, but and be not used to limit the present invention.Any those of ordinary skill in the art, when not departing from spirit of the present invention and technical scheme, the Method and Technology content of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent replacement, equivalence change and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (10)
1. grafting polysilane-series compounds, is characterized in that, the chemical structural formula of described grafting polysilane-series compounds represents with formula I:
Wherein, polymerization degree n is 18 ~ 23;
-CH
2-chain link number m is 0 ~ 6;
Grafting Replacement rate x is 0 ~ 0.8.
2. the preparation method of grafting polysilane-series compounds described in a claim 1, it is characterized in that, comprise the following steps: the side chain alkenyl substituted thing of vinylene carbonate or vinylene carbonate being grafted to poly-hydrogen methyl-monosilane by addition reaction of silicon with hydrogen obtains grafting polysilane.
3. preparation method according to claim 2, is characterized in that, also comprises post-processing step: described grafting polysilane is added normal hexane under an ar atmosphere successively, methyl alcohol carries out separating and extracting and obtain grafting polysilane sterling.
4. preparation method according to claim 2, it is characterized in that, the concrete steps of described addition reaction of silicon with hydrogen are: the alkenyl substituted thing of vinylene carbonate or vinylene carbonate and poly-hydrogen methyl-monosilane are dissolved in organic solvent and obtain mixing solutions, reflux described mixing solutions at 60 ~ 70 DEG C 12h.
5. preparation method according to claim 4, is characterized in that, adds initiator, and then reflux in described mixing solutions.
6. preparation method according to claim 5, is characterized in that, described organic solvent is tetrahydrofuran (THF); Described initiator is Diisopropyl azodicarboxylate.
7. preparation method according to claim 6, is characterized in that, the addition of described initiator is 0.1wt% ~ 5wt%.
8. the preparation method according to any one of claim 2 to 7, it is characterized in that, the alkenyl substituted thing of described vinylene carbonate or vinylene carbonate and the mass ratio of described poly-hydrogen methyl-monosilane are 1: 10 ~ 2.5: 1, and the alkenyl substituted thing of described vinylene carbonate is vinylethylene carbonate.
9. a grafting polysilane-series compounds according to claim 1 or the grafting polysilane-series compounds for preparing according to preparation method described in any one of claim 2 to 8 are as the application of stablizer in battery electrolyte.
10. application according to claim 9, is characterized in that, the addition of described stablizer is 0.1 ~ 2wt%.
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