CN103896876A - Double-center piperazine ionic liquid, preparation method thereof, electrolyte and lithium-ion battery - Google Patents
Double-center piperazine ionic liquid, preparation method thereof, electrolyte and lithium-ion battery Download PDFInfo
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- CN103896876A CN103896876A CN201210584225.7A CN201210584225A CN103896876A CN 103896876 A CN103896876 A CN 103896876A CN 201210584225 A CN201210584225 A CN 201210584225A CN 103896876 A CN103896876 A CN 103896876A
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- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
- C07D295/084—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/088—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
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Abstract
The invention relates to a double-center piperazine ionic liquid, and the general formula is as shown in (I), wherein Y is a tetrafluoroborate anion, hexafluorophosphate anion, trifluoromethyl sulfonyl imide anion or trifluoromethylsulfonate anion; R is methoxy alkyl with the following general formula (II), wherein n is 2, 3 or 4. The invention further relates to a preparation method of the double-center piperazine ionic liquid, as well as an ionic liquid electrolyte and a lithium ion battery which are prepared by the double-center piperazine ionic liquid. The double-center piperazine ionic liquid prepared by the method provided by the invention adopts a framework configuration of double-center quaternary ammonium salt, so that the ionic liquid has structure designability and can enrich the types of the ionic liquid. In addition, the ionic liquid electrolyte and the lithium ion battery which are prepared by the double-center piperazine ionic liquid have excellent electrochemical performances.
Description
Technical field
The present invention relates to electrochemical field, relate in particular to Yi Leishuan center piperazines ionic liquid and preparation method thereof.The invention still further relates to and adopt on Gai Shuan center piperazines ionic liquid prepared electrolytic solution and lithium ion battery.
Background technology
Ionic liquid refers in room temperature range and (is generally below 100 ℃) and is in a liquid state, and is made up of organic cation and inorganic anion or organic anion.Ionic liquid has adjustability, need to change its zwitterion structure and can reach planner's object, thereby ionic liquid is called as planner's solvent according to difference.Just found first ionic liquid-nitro ethamine as far back as 1914, but the progress in this field is slow thereafter.Until 1992, Wikes leader's research group has synthesized low melting point, resistant to hydrolysis, 1-ethyl-3-methylimidazole tetrafluoroborate ion liquid ([EMIM] BF that stability is strong
4) after, the research of ionic liquid is just developed rapidly, has developed subsequently a series of ion liquid system.Initial ionic liquid is mainly used in electrochemical research, and ionic liquid comes into one's own for organic and Polymer Synthesizing as green solvent in recent years.Compare with ionogen with traditional organic solvent, ionic liquid has advantages of a series of outstanding: (1) fusing point lower than or approach room temperature, the temperature range being in a liquid state is wide; (2) steam force down, hardly volatilization, colourless, odorless; (3) there is larger equilibrium temperature scope, preferably chemical stability and wider electrochemical stability potential window; (4) good dissolution characteristics, all shows good dissolving power to a lot of inorganicss and organism; (5) without point of ignition and nonflammable; (6) can be recycled, free from environmental pollution etc.At present to the research of ionic liquid mainly concentrate on novel ion liquid synthetic, ionic liquid physics and chemistry characteristic sign and as the aspect such as solvent and electrolytical applied research.Ionic liquid, as the novel solvent of a class, medium, catalyzer, has been obtained many gratifying results in the research in the fields such as organic synthesis, catalyzed reaction, extracting and separating, material preparation, natural polymer, electrochemistry, has been subject to paying close attention to widely.
Summary of the invention
The first object of the present invention be to provide a kind of novel, security good, eco-friendly pair of center piperazines ionic liquid.
The second object of the present invention is to provide a kind of preparation method method of described pair of center piperazines ionic liquid.
The 3rd object of the present invention is to provide a kind of il electrolyte of being prepared by described pair of center piperazines ionic liquid.
The 4th object of the present invention is to provide a kind of lithium ion battery of being prepared by described il electrolyte.
In order to realize first object of the present invention, the technical solution adopted in the present invention is:
One has following general formula (I) Shuan center piperazines ionic liquid,
Wherein, Y is Tetrafluoroboric acid negatively charged ion (BF
4 -), phosphofluoric acid negatively charged ion (PF
6 -), trifluoromethanesulp-onyl-onyl imide negatively charged ion ((CF
3sO
2)
2n
-) or trifluoromethane sulfonic acid negatively charged ion (CF
3sO
3 -);
R is for having the methoxyl group alkyl of following general formula (II):
CH
3o (CH
2)
n(II), wherein, n is 2,3 or 4.
In order to realize the second object of the present invention, the technical solution adopted in the present invention is:
A method for pair center piperazines ionic liquid, roughly technical process is as follows for it: Isosorbide-5-Nitrae-lupetazin → alkylpiperazine halogenide → bis-centers piperazine cationic ionic liquid.Particularly, above-mentioned preparation method comprises the steps:
(a) the halid preparation of dialkyl group piperazine: Isosorbide-5-Nitrae-lupetazin and the haloalkane RX reaction with following general formula (III) are made to the dialkyl group piperazine halogenide with following general formula (IV).
Wherein, R is for having the methoxyl group alkyl of following general formula (II):
CH
3o (CH
2)
n(II), wherein, n is 2,3 or 4;
X is halogen, preferably chlorine, bromine or iodine atom;
(b) preparation of described pair of center piperazines ionic liquid: the dialkyl group piperazine halogenide that described step (a) is made and inorganic salt MY and deionized water carry out ion exchange reaction, obtains described pair of center piperazines ionic liquid.
Wherein, Y is Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion;
M is sodium ion, potassium ion or ammonium ion.
The reaction that above step (a) and step (b) occur can represent with following reaction formula,
Wherein, in RX, R is the methoxyl group alkyl with following general formula (II):
CH
3o (CH
2)
n(II), wherein, n is 2,3 or 4;
X is halogen, preferably chlorine, bromine or iodine atom;
Be that RX represents CH
3o (CH
2)
ncl, CH
3o (CH
2)
nbr, CH
3o (CH
2)
ni, n=2,3,4.
In above-mentioned reaction formula, the positively charged ion M of inorganic salt MY
+for sodium ion (Na
+), potassium ion (K
+) or ammonium ion (NH
4+); Y is Tetrafluoroboric acid negatively charged ion (BF
4 -), phosphofluoric acid negatively charged ion (PF
6 -), trifluoromethanesulp-onyl-onyl imide negatively charged ion ((CF
3sO
2)
2n
-) or trifluoromethane sulfonic acid negatively charged ion (CF
3sO
3 -).
In above-mentioned preparation method; described step (a) is specially: under protection of inert gas; described Isosorbide-5-Nitrae-lupetazin and 1: 2.1 in molar ratio～1: 2.3 (preferably 1: 2.2) stirring reaction 20～60h at 60 ℃～80 ℃ of described haloalkane RX are obtained to described dialkyl group piperazine halogenide.
In above-mentioned preparation method, described step (b) is specially: described dialkyl group piperazine halogenide and described inorganic salt MY and described deionized water are at room temperature reacted to 5～20h and obtain described pair of center piperazines ionic liquid; Wherein, the mol ratio of described dialkyl group piperazine halogenide and described inorganic salt MY is 1: 2～1: 2.2, and preferably 1: 2.1, described dialkyl group piperazine halogenide was 1mol: 300mL～1mol: 200mL with the molecular volume ratio of described deionized water.
In order to realize the 3rd object of the present invention, the technical solution adopted in the present invention is:
A kind of il electrolyte, includes ionic liquid, organic solvent and lithium salts, and described ionic liquid is of the present invention pair of center piperazines ionic liquid.
In described il electrolyte, the mass ratio of described pair of center piperazines ionic liquid and described organic solvent is 1: 10～1: 1; The mass ratio of described organic solvent and lithium salts is 10: 1～20: 1.
In described il electrolyte, described organic solvent by NSC 11801 (EC), methylcarbonate (DMC), diethyl carbonate (DEC) with 1～3: the configuration of 3～7: 1 volume ratio forms; Described lithium salts is LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6), trifluoromethyl sulfonic acid lithium (LiSO
3cF
3) or two (trimethyl fluoride sulfonyl) imine lithium (LiTFSI).
In order to realize the 4th object of the present invention, the technical solution adopted in the present invention is:
A kind of lithium ion battery of being assembled by above-mentioned il electrolyte, this lithium ion battery comprises the electrolytic solution between positive electrode, negative potential and described positive and negative electrode, described positive electrode comprises collector and is coated in this collector spreading mass, described electrolytic solution is above-mentioned il electrolyte, and described slurry is by cobalt-lithium oxide (LiCoO
2), acetylene black, polyvinylidene difluoride (PVDF) (PVDF), N-Methyl pyrrolidone (NMP) 9: 0.5: 0.5 in mass ratio: 20 are uniformly mixed and form.
Prepared ionic liquid, il electrolyte and the lithium ion battery of the present invention has the following advantages:
1. the prepared Shuan of the present invention center piperazines ionic liquid adopts the framework type bone of two centers quaternary ammonium salt, makes this class ionic liquid have structure designability, has enriched the kind of ionic liquid.
The prepared il electrolyte of the present invention and lithium ion battery with current commercial lithium-ion battery electrolytes compared with lithium ion battery, owing to having added a large amount of Shuan center piperazines ionic liquid, can greatly improve the stability of electrolytic solution and the safety performance of battery, meanwhile, electrolytic solution and the lithium ion battery that prepared by the present invention also have good chemical property.
Embodiment
Below in conjunction with embodiment, the present invention is given to elaboration further.Following examples are for the present invention is described, to instruct those skilled in the art to realize the present invention, the present embodiment does not limit the present invention in any way.
Apply and be specifically described on electrolytic solution and lithium ion battery with 1～4 pair of the present invention pair center piperazines ionic liquid of embodiment and preparation method thereof and its below.
Embodiment 1:
(1) the present embodiment 1 Shuan center piperazines ionic liquid that provides is specially: Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine tetrafluoroborate ion liquid, and its structural formula is:
(2) preparation method of above-mentioned Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine tetrafluoroborate ion liquid, comprises the following steps:
(a) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine villaumite:
In the flask of 250mL, add respectively 1mol (being 114g) Isosorbide-5-Nitrae-lupetazin and 2.2mol (being 108g) methoxychlor ethane.At N
2or Ar
2under atmosphere protection, be warming up to 70 ℃, stirring reaction 40h, then leaves standstill cooling and with ethyl acetate washing three times.Vacuum-drying at 80 ℃, obtains lurid solid and is Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine villaumite.
(b) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine tetrafluoroborate ion liquid:
In 250mL flask, add the prepared Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine villaumite of 0.5mol (being 151.6g) step (a), 1.06mol (being 116.6g) NaBF
4with 130mL deionized water, under room temperature, stir after 8h with 250mL dichloromethane extraction 3 times, combined dichloromethane extraction liquid, then uses the back extraction of 60mL deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected dichloromethane extraction liquid till producing without precipitation, and this dichloromethane extraction liquid is concentrated with Rotary Evaporators, again in 80 ℃ of vacuum-dryings 48 hours, obtain colourless liquid Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy-ethyl piperazine tetrafluoroborate ion liquid.
(3) preparation of il electrolyte
Above-mentioned Isosorbide-5-Nitrae-dimethyl-the Isosorbide-5-Nitrae making-dimethoxy-ethyl piperazine tetrafluoroborate ion liquid is prepared to il electrolyte.Concrete steps are as follows: at N
2or Ar
2under atmosphere protection; take out 10g 1; 4-dimethyl-1; 4-dimethoxy-ethyl piperazine tetrafluoroborate ion liquid; then the organic solvent (EC: DMC: DEC volume ratio is 2: 5: 1) that adds wherein 50g to be obtained by mixing by NSC 11801 (EC), methylcarbonate (DMC) and diethyl carbonate (DEC); and be heated to 40 ℃, stir and obtain uniform organic phase.Finally add 3.5g LiBF
4, continue stirring and make described LiBF
4dissolve completely, thereby obtain described il electrolyte.
(4) preparation of lithium ion battery
The above-mentioned il electrolyte making is prepared to lithium ion battery.Concrete steps are as follows: take 9.0g LiCoO
2, 0.5g acetylene black and 0.5g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into LiCoO in 10MPa pressure lower roll
2electrode, and be cut into anodal disk, PP is as barrier film, and lithium sheet is as negative pole.The il electrolyte that embodiment 1 is made is placed between positive and negative electrode, and on stamping machine, the lithium ion battery of button is made in sealing.
Embodiment 2:
(1) the present embodiment 2 Shuan center piperazines ionic liquid that provides is specially Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine hexafluorophosphate ionic liquid, and its structural formula is:
(2) preparation method of above-mentioned Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine hexafluorophosphate ionic liquid, comprises the following steps:
(a) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine bromine salt:
In the flask of 250mL, add respectively 1mol (being 114g) Isosorbide-5-Nitrae-lupetazin and 2.1mol (321.4g) methoxyl group N-PROPYLE BROMIDE.At N
2or Ar
2under atmosphere protection, be warming up to 60 ℃, stirring reaction 60h, then leaves standstill cooling and with ethyl acetate washing three times.Vacuum-drying at 80 ℃, obtains lurid solid and is Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine bromine salt.
(b) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine hexafluorophosphate ionic liquid:
In 250mL flask, add 0.5mol (210.1g) step (a) prepared Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine bromine salt, 1.0mol (184g) KPF
6with 100mL deionized water, at room temperature stir after 20h with 250mL dichloromethane extraction 3 times, combined dichloromethane extraction liquid, then uses the back extraction of 60mL deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected dichloromethane extraction liquid till producing without precipitation, and this dichloromethane extraction liquid is concentrated with Rotary Evaporators, carry out again 80 ℃ of vacuum-dryings 48 hours, obtain colourless liquid Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine hexafluorophosphate ionic liquid.
(3) preparation of il electrolyte
Above-mentioned Isosorbide-5-Nitrae-dimethyl-the Isosorbide-5-Nitrae making-dimethoxy propyl group piperazine hexafluorophosphate ionic liquid is prepared to il electrolyte.Concrete steps are as follows: at N
2or Ar
2under atmosphere protection; take out 10g1; 4-dimethyl-1; 4-dimethoxy propyl group piperazine hexafluorophosphate ionic liquid; then the organic solvent (EC: DMC: DEC volume ratio is 1: 3: 1) that adds wherein 10g to be obtained by mixing by NSC 11801 (EC), methylcarbonate (DMC) and diethyl carbonate (DEC); and be heated to 40 ℃ of stirrings, obtain uniform organic phase.Finally add 1.0g LiPF
6, continue stirring and make LiPF
6dissolve completely, thereby obtain described il electrolyte.
(4) preparation of lithium ion battery
The above-mentioned il electrolyte making is prepared to lithium ion battery.Concrete steps are as follows: take 9.0gLiCoO
2, 0.5g acetylene black and 0.5g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into LiCoO in 10MPa pressure lower roll
2electrode, and be cut into anodal disk, PP is as barrier film, and lithium sheet is as negative pole.The il electrolyte that above-described embodiment 2 is made is placed between positive and negative electrode, and on stamping machine, the lithium ion battery of button is made in sealing.
Embodiment 3:
(1) the present embodiment 3 Shuan center piperazines ionic liquid that provides is specially: Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine fluoroform sulfimide salt ion liquid, and its structural formula is:
(2) preparation method of above-mentioned Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine fluoroform sulfimide salt ion liquid, comprises the following steps:
(a) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine salt compounded of iodine:
In the flask of 250mL, add respectively 1mol (being 114g) Isosorbide-5-Nitrae-lupetazin and 2.3mol (being 492.2g) methoxyl group butyl iodide.At N
2or Ar
2under atmosphere protection, be warming up to 80 ℃, stirring reaction 20h, then leaves standstill cooling and with ethyl acetate washing three times.Vacuum-drying at 80 ℃, obtains lurid solid and is Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine salt compounded of iodine.
(b) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine fluoroform sulfimide salt ion liquid:
In 250mL flask, add the prepared Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine salt compounded of iodine of 0.5mol (being 271.1g) step (a), 1.1mol (being 351g) (CF
3sO
2)
2nK and 150mL deionized water, at room temperature stir after 5h with 250mL dichloromethane extraction 3 times, and combined dichloromethane extraction liquid, then uses the back extraction of 60mL deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected dichloromethane extraction liquid till producing without precipitation, and this dichloromethane extraction liquid is concentrated with Rotary Evaporators, carry out again 80 ℃ of vacuum-dryings 48 hours, obtain colourless liquid Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy butyl piperazine fluoroform sulfimide salt ion liquid.
(3) preparation of il electrolyte
Above-mentioned Isosorbide-5-Nitrae-dimethyl-the Isosorbide-5-Nitrae making-dimethoxy butyl piperazine fluoroform sulfimide salt ion liquid is prepared to il electrolyte.Concrete steps are as follows: at N
2or Ar
2under atmosphere protection; take out 10g 1; 4-dimethyl-1; 4-dimethoxy butyl piperazine fluoroform sulfimide salt ion liquid; then the organic solvent (EC: DMC: DEC volume ratio is 3: 6: 1) that adds wherein 100g to be obtained by mixing by NSC 11801 (EC), methylcarbonate (DMC) and diethyl carbonate (DEC), and be heated to 40 ℃ of stirrings and obtain uniform organic phase.Finally add 5g (CF
3sO
2)
2nLi, continues stirring and makes (CF
3sO
2)
2nLi dissolves completely, thereby obtains described il electrolyte.
(4) preparation of lithium ion battery
The above-mentioned il electrolyte making is prepared to lithium ion battery.Concrete steps are as follows: take 9.0gLiCoO
2, 0.5g acetylene black and 0.5g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into LiCoO in 10MPa pressure lower roll
2electrode, and be cut into anodal disk, PP is as barrier film, and lithium sheet is as negative pole.The il electrolyte that embodiment 3 is made is placed between positive and negative electrode, and on stamping machine, the lithium ion battery of button is made in sealing.
Embodiment 4:
(1) the present embodiment 4 Shuan center piperazines ionic liquid that provides is specially: Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine fluoroform sulphonate ionic liquid, and its structural formula is:
(2) preparation method of above-mentioned Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine fluoroform sulphonate ionic liquid, comprises the following steps:
(a) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine villaumite:
In the flask of 250mL, add respectively 1mol (being 114g) Isosorbide-5-Nitrae-lupetazin and 2.2mol (being 238.8g) methoxychlor propane.At N
2or Ar
2under atmosphere protection, be warming up to 65 ℃, stirring reaction 45h, then leaves standstill cooling and with ethyl acetate washing three times.Vacuum-drying at 80 ℃, obtains lurid solid and is Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine villaumite.
(b) preparation of Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine fluoroform sulphonate ionic liquid:
In 250mL flask, add the prepared Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine villaumite of 0.5mol (being 165.7g) step (a), 1.05mol (being 175.3g) CF
3sO
3nH
4with 120mL deionized water, at room temperature stir after 15h with 250mL dichloromethane extraction 3 times, combined dichloromethane extraction liquid, then uses the back extraction of 60mL deionized water repeatedly, until with saturated AgNO
3aqueous solution titration water is collected dichloromethane extraction liquid till producing without precipitation, and this dichloromethane extraction liquid is concentrated with Rotary Evaporators, again in 80 ℃ of vacuum-dryings 48 hours, obtain colourless liquid Isosorbide-5-Nitrae-dimethyl-Isosorbide-5-Nitrae-dimethoxy propyl group piperazine fluoroform sulphonate ionic liquid.
(3) preparation of il electrolyte
Above-mentioned Isosorbide-5-Nitrae-dimethyl-the Isosorbide-5-Nitrae making-dimethoxy propyl group piperazine fluoroform sulphonate ionic liquid is prepared to il electrolyte.Concrete rapid as follows: at N
2or Ar
2under atmosphere protection; take out 10g1; 4-dimethyl-1; 4-dimethoxy propyl group piperazine fluoroform sulphonate ionic liquid; then add wherein the organic solvent (EC: DMC: DEC volume ratio is 2: 7: 1) being obtained by mixing by NSC 11801 (EC), methylcarbonate (DMC) and diethyl carbonate (DEC) by 60g, and be heated to 40 ℃ of stirrings and obtain uniform organic phase.Finally add 3.7g CF
3sO
3li, continues stirring and makes described CF
3sO
3li dissolves completely, thereby obtains described il electrolyte.
(4) preparation of lithium ion battery
The above-mentioned il electrolyte making is prepared to lithium ion battery.Concrete steps are as follows: take 9.0gLiCoO
2, 0.5g acetylene black and 0.5g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into LiCoO in 10MPa pressure lower roll
2electrode, and be cut into anodal disk, PP is as barrier film, and lithium sheet is as negative pole.The il electrolyte that embodiment 4 is made is placed between positive and negative electrode, and on stamping machine, the lithium ion battery of button is made in sealing.
Comparative example
Make the not electrolytic solution containing ionic liquid: at N
2or Ar
2under atmosphere protection, take out 3.5g LiBF
4then add wherein 50g is obtained by mixing by NSC 11801 (EC), methylcarbonate (DMC) and diethyl carbonate (DEC) and EC: DMC: the organic solvent that DEC volume ratio is 2: 5: 1, thus and be heated to 40 ℃ and be uniformly mixed and obtain described electrolytic solution.
The above-mentioned electrolytic solution making is prepared to lithium ion battery.The step of preparing lithium ion battery is as follows: take 9.0g LiCoO
2, 0.5g acetylene black and 0.5g PVDF, and add 20g NMP, fully stir and make it to become the slurry mixing.Then by its blade coating on the aluminium foil cleaning through ethanol, under the vacuum of 0.01MPa, 80 ℃ are dried to constant weight, and are pressed into LiCoO in 10MPa pressure lower roll
2electrode, and be cut into anodal disk, PP is as barrier film, and lithium sheet is as negative pole.The electrolytic solution that described comparative example is made is placed between positive and negative electrode, and on stamping machine, the lithium ion battery of button is made in sealing.
The specific conductivity that adopts DDS-11C conductivitimeter to test prepared electrolytic solution in embodiment 1～4 and comparative example, its conductivity data is listed in the table below 1.In addition, in the voltage range of 2.5～4.2V, utilize charge-discharge test instrument to carry out 0.2C charge-discharge test to the lithium ion battery preparing described in the present embodiment 1～4 and comparative example, its performance data is also listed in the table below 1.
Table one
| Embodiment | 1 | 2 | 3 | 4 | Comparative example |
| The specific conductivity ms/cm of prepared electrolytic solution | 12 | 13 | 11 | 12 | 7 |
| First discharge specific capacity mAh/g | 118 | 105 | 110 | 114 | 98 |
As can be seen from Table 1, the specific conductivity of the il electrolyte of preparing by embodiment 1～4 method be greater than comparative example prepared not containing the specific conductivity of the electrolytic solution of ionic liquid, and reach 13ms/cm in embodiment 2; All be greater than the specific storage in comparative example by the first discharge specific capacity of the lithium ion battery of embodiment 1～4 method assembling, and arrived 118mAh/g than electric capacity in embodiment 1.
Can draw such conclusion from above data, on il electrolyte provided by the present invention and lithium ion battery, there is good chemical property.
Foregoing; it is only preferred embodiment of the present invention; not for limiting embodiment of the present invention; those of ordinary skills are according to main design of the present invention and spirit; can carry out very easily corresponding flexible or modification, therefore protection scope of the present invention should be as the criterion with the desired protection domain of claims.
Claims (10)
1. there is following general formula (I) Shuan center piperazines ionic liquid,
Wherein, Y is Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion;
R is for having the methoxyl group alkyl of following general formula (II):
CH
3o (CH
2)
n(II), wherein, n is 2,3 or 4.
The preparation method of 2.Yi Zhongshuan center piperazines ionic liquid, is characterized in that, comprises the steps:
(a) the halid preparation of alkyl quaternary ammonium salts: Isosorbide-5-Nitrae-lupetazin and the haloalkane RX reaction with following general formula (III) are made to the dialkyl group piperazine halogenide with following general formula (IV),
Wherein, R is for having the methoxyl group alkyl of following general formula (II):
CH
3o (CH
2)
n(II), wherein, n is 2,3 or 4;
X is halogen;
(b) preparation of described pair of center piperazines ionic liquid: the dialkyl group piperazine halogenide that described step (a) is made and inorganic salt MY and deionized water carry out ion exchange reaction, obtains described pair of center piperazines ionic liquid;
Wherein, Y is Tetrafluoroboric acid negatively charged ion, phosphofluoric acid negatively charged ion, trifluoromethanesulp-onyl-onyl imide negatively charged ion or trifluoromethane sulfonic acid negatively charged ion; M is sodium ion, potassium ion or ammonium ion.
3. the preparation method of according to claim 2 pair of center piperazines ionic liquid; it is characterized in that; described step (a) is specially: under protection of inert gas; described Isosorbide-5-Nitrae-lupetazin and described haloalkane RX 1: 2.1 in molar ratio～1: 2.3 stirring reaction 20～60h at 60 ℃～80 ℃ is obtained to described dialkyl group piperazine halogenide.
4. according to the preparation method of Shuan center piperazines ionic liquid described in claim 2 or 3, it is characterized in that, described step (b) is specially: described dialkyl group piperazine halogenide and described inorganic salt MY and described deionized water are at room temperature reacted to 5～20h and obtain described pair of center piperazines ionic liquid; Wherein, the mol ratio of described dialkyl group piperazine halogenide and described inorganic salt MY is 1: 2～1: 2.2, and described dialkyl group piperazine halogenide is 1mol: 300mL～1mol: 200mL with the molecular volume ratio of described deionized water.
5. the preparation method of according to claim 4 pair of center piperazines ionic liquid, it is characterized in that: described 1, the mol ratio of 4-lupetazin and described haloalkane RX is preferably 1: 2.2, and the mol ratio of described dialkyl group piperazine halogenide and described inorganic salt MY is preferably 1: 2.1.
6. according to the preparation method of Shuan center piperazines ionic liquid described in claim 2 or 5, it is characterized in that, described halogen X is chlorine, bromine or iodine atom.
7. an il electrolyte, includes ionic liquid, organic solvent and lithium salts, it is characterized in that, described ionic liquid is claimed in claim 1 pair of center piperazines ionic liquid.
8. il electrolyte according to claim 7, is characterized in that, the mass ratio of described pair of center piperazines ionic liquid and described organic solvent is 1: 10～1: 1; The mass ratio of described organic solvent and lithium salts is 10: 1～20: 1.
9. il electrolyte according to claim 8, is characterized in that, described organic solvent by NSC 11801, methylcarbonate and diethyl carbonate with 1～3: the configuration of 3～7: 1 volume ratio forms; Described lithium salts is LiBF4, lithium hexafluoro phosphate, trifluoromethyl sulfonic acid lithium or two (trimethyl fluoride sulfonyl) imine lithium.
10. a lithium ion battery, comprise the electrolytic solution between positive electrode, negative potential and described positive and negative electrode, described positive electrode comprises collector and is coated in this collector spreading mass, described slurry was by cobalt-lithium oxide, acetylene black, polyvinylidene difluoride (PVDF), N-Methyl pyrrolidone 9: 0.5: 0.5 in mass ratio: 20 are uniformly mixed and form, it is characterized in that, described electrolytic solution is the il electrolyte described in claim 7 to 9 any one.
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