[summary of the invention]
Based on this, be necessary to provide the good azoles alkanes of a kind of stability ionic liquid.
In addition, be also necessary to provide the preparation method of the good azoles alkanes of a kind of stability ionic liquid.
In addition, be also necessary to provide a kind of electrolytic solution of this azoles alkanes ionic liquid and compound method of this electrolytic solution of using.
A kind of azoles alkanes ionic liquid, has following structural formula:
Wherein, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -.
A preparation method for azoles alkanes ionic liquid, comprises the steps:
Step 1, azoles alkanes and haloalkane are mixed to post-heating to 60 DEG C~80 DEG C for 1: 1 in molar ratio~1: 1.2, stirring reaction obtains alkyl azoles alkane halogenide, and wherein, described haloalkane is methoxy ethoxy methyl chloride or methoxy ethoxy monobromethane;
Step 2, be M by the alkyl azoles alkane halogenide of preparing in step 1 and general formula
+y
-salt add in deionized water after mixing with mol ratio 1: 1, stir ion exchange reaction occur, after separation and purification, obtain having the azoles alkanes ionic liquid of following structural formula:
Wherein, M
+for Na
+, K
+or NH
4 +, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -.
In a preferred embodiment, in step 1, the time of described azoles alkanes and described haloalkane stirring reaction is 48~72 hours, and reaction solution is cooling rear with ethyl acetate washing, and the product vacuum-drying that washing is obtained obtains the alkyl azoles alkane halogenide of purifying.
In a preferred embodiment, in step 1, described azoles alkanes carries out with reacting under the protective atmosphere of nitrogen or argon gas formation of described haloalkane.
In a preferred embodiment, in step 2, the temperature of described ion exchange reaction is room temperature, and the time is 8~24 hours.
In a preferred embodiment, described in step 2, purification procedures is as follows: by alkyl azoles alkane halogenide with there is formula M
+y
-salt stirring reaction after the mixed solution dichloromethane extraction that obtains, until saturated AgNO for the water obtaining
3aqueous solution titration produces without precipitation, by the dry dichloromethane extract evaporation concentration final vacuum azoles alkanes ionic liquid that obtains.
A kind of electrolytic solution, comprises azoles alkanes ionic liquid, organic solvent and lithium salts, and described azoles alkanes ionic liquid has following structural formula:
Wherein, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -, the mass ratio of described organic solvent and described azoles alkanes ionic liquid is 0~100, the concentration of described lithium salts is 0.3mol/L~1.2mol/L.
In a preferred embodiment, described lithium salts is selected from least one in LiBF4, lithium hexafluoro phosphate, two (fluoroform sulphonyl) imine lithium and two (fluorine sulphonyl) imine lithium.
In a preferred embodiment, described organic solvent is selected from least one in NSC 11801, Methyl ethyl carbonate, methylcarbonate and ethyl propionate.
A compound method for electrolytic solution, comprises the following steps:
Step 1, provide organic solvent, in described organic solvent, add azoles alkanes ionic liquid and stir, the mass ratio of described organic solvent and described azoles alkanes ionic liquid is 0~100, and described azoles alkanes ionic liquid has following structural formula:
Wherein, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -;
In step 2, the mixed solution that forms to described organic solvent and described azoles alkanes ionic liquid, add lithium salts stirring and dissolving, the concentration of described lithium salts is 0.3mol/L~1.2mol/L, is preferably 1mol/L.
The decomposition voltage of this azoles alkanes ionic liquid is high, stability is better, the solvent toxicity using in its preparation process is less, preparation technology is comparatively simple, be easy to extensive preparation thereby cost is lower, the electrolytic solution of applying this azoles alkanes ionic liquid has good stability in higher charge voltage range.
[embodiment]
Below in conjunction with the drawings and specific embodiments, azoles alkanes ionic liquid and its preparation method and application is further illustrated.
The azoles alkanes ionic liquid of one embodiment, structural formula is:
Wherein, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Above-mentioned azoles alkanes ionic liquid stability is higher.At the temperature up to 400 DEG C, this azoles alkanes ionic liquid can not decompose, and has the advantages that not fire, thereby can improve its security in electrolytic solution application.In addition, the electrochemical window of this ionic liquid exceedes 4V, has good electrochemical stability, can be applicable to the electrolytic solution of ultracapacitor and lithium cell.
The preparation method of the azoles alkanes ionic liquid of one embodiment, comprises the following steps:
Under step S11, the protective atmosphere that forms at nitrogen or argon gas, methyl azoles alkane and haloalkane are mixed to post-heating to 60 DEG C~80 DEG C, stirring reaction 48~72 hours for 1: 1 in molar ratio~1: 1.2.Reaction solution leaves standstill cooling rear with ethyl acetate washing three times, the product vacuum-drying after washing is obtained to the alkyl azoles alkane halogenide of purifying.
Reaction equation is as follows:
Wherein, wherein RX is the representative of methoxy ethoxy methyl chloride
or methoxy ethoxy monobromethane
x
-represent Cl
-, Br
-, R-representative
product after washing preferably at 80 DEG C vacuum-drying 48h obtain alkyl azoles alkane halogenide.
Be appreciated that the reaction times is not limited to 48~72 hours, as long as azoles alkanes and haloalkane are reacted completely; Azoles alkanes is not limited to carry out under the protective atmosphere of nitrogen or argon gas formation with reacting of haloalkane, as long as under protection of inert gas; After reaction solution is cooling, be not limited to, with three purification alkyl azoles alkane halogenide of ethyl acetate washing, also can use additive method purification alkyl azoles alkane halogenide in this area.
Step S12, by the alkyl azoles alkane halogenide of preparing in step S11 with there is formula M
+y
-salt add in deionized water after mixing with mol ratio 1: 1, alkyl azoles alkane halogenide with there is formula M
+y
-salt generation ion exchange reaction, temperature of reaction is room temperature, the reaction times is 8~24 hours, is M by alkyl azoles alkane halogenide and general formula
+y
-salt stirring reaction after the mixed solution dichloromethane extraction that obtains, until the saturated AgNO for deionization water obtaining
3aqueous solution titration without precipitation produce, by after methylene dichloride phase evaporation concentration at 80 DEG C vacuum-drying 48h obtain foregoing azoles alkanes ionic liquid.Reaction equation is as follows:
Wherein, M
+for Na
+, K
+or NH
4 +, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -.
The time that is appreciated that described ion exchange reaction is not limited to 8~24 hours, as long as make alkyl azoles alkane halogenide and have formula M
+y
-salt generation ion exchange reaction completely; Separating-purifying azoles alkanes ionic liquid also can adopt the common additive method in this area and other solvents.
Above-mentioned azoles alkanes ionic liquid preparation method, the solvent toxicity of use is less, and preparation technology is comparatively simple, is easy to extensive preparation thereby cost is lower.
The electrolytic solution of one embodiment, comprises azoles alkanes ionic liquid, organic solvent and lithium salts.
Azoles alkanes ionic liquid has following structural formula:
Wherein, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -.
The mass ratio of organic solvent and azoles alkanes ionic liquid is more than or equal to 0 and be less than or equal to 100.Organic solvent is selected from least one in NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), ethyl propionate (EP).
The concentration of lithium salts in electrolytic solution is 0.3mol/L~1.2mol/L.Lithium salts is selected from LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6), at least one in two (fluoroform sulphonyl) imine lithiums (LiTFSI) and two (fluorine sulphonyl) imine lithium (LiFSI).
The compound method of the electrolytic solution of one embodiment, comprises the following steps:
Step S21, provide organic solvent, in organic solvent, add azoles alkanes ionic liquid and stir, the mass ratio of organic solvent and azoles alkanes ionic liquid is more than or equal to 0 and be less than or equal to 100, and azoles alkanes ionic liquid has following structural formula:
Wherein, Y
-for BF
4 -, PF
6 -, (FSO
2)
2n
-, (CF
3sO
2)
2n
-or CF
3sO
3 -.
Organic solvent is selected from least one in NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), ethyl propionate (EP).
Preferably, step S21 carries out under the protection of rare gas element, and rare gas element can be nitrogen or argon gas.
In step S22, the mixed solution that forms to organic solvent and azoles alkanes ionic liquid, add lithium salts stirring and dissolving, form described electrolytic solution, wherein, the concentration of lithium salts is 0.3mol/L~1.2mol/L.Lithium salts is selected from LiBF4 (LiBF
4), lithium hexafluoro phosphate (LiPF
6), at least one in two (fluoroform sulphonyl) imine lithiums (LiTFSI) and two (fluorine sulphonyl) imine lithium (LiFSI).
In above-mentioned electrolytic solution and compound method thereof, the good stability of azoles alkanes ionic liquid, thus the decomposition voltage of electrolytic solution is high; Lithium salts is mainly to provide lithium ion in the application of lithium ion battery or lithium-ion capacitor etc., and organic solvent can reduce the viscosity of electrolytic solution.
Be specific embodiment below.
Synthesizing of embodiment 1 ionic liquid 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane a tetrafluoro borate
In the flask of 250mL, add respectively (87g, 1mol) methyl azoles alkane and (136.4g, 1.1mol) methoxy ethoxy methyl chloride.At N
2(or Ar
2) under atmosphere protection, be warming up to 60 DEG C, stirring reaction 48h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying at 80 DEG C, obtains lurid solid intermediate product: chlorination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, yield is 82%.
In 500mL flask, add (105.5g, 0.5mol) chlorination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, (55g, 0.5mol) NaBF
4with 100mL deionized water, at room temperature stir 8h.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid.Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation.After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid.
The proton nmr spectra test result of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane a tetrafluoro borate prepared by the present embodiment is as follows:
1H?NMR(CDCl
3,400MHz,ppm):4.73(s,2H),4.68(s,2H),3.84(m,2H),3.38(m,2H),3.32(m,2H),3.24(s,3H),2.81(m,2H),2.53(s,3H).
Synthesizing of embodiment 2 ionic liquid 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane hexafluorophosphates
In the flask of 250mL, add respectively (87g, 1mol) methyl azoles alkane and (160g, 1mol) methoxy ethoxy monobromethane.At N
2(or Ar
2) under atmosphere protection, be warming up to 70 DEG C, stirring reaction 60h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying at 80 DEG C, obtains lurid solid intermediate product: bromination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, yield is 76%.
In 500mL flask, add 0.5mol bromination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, (92g, 0.5mol) KPF6 and 120mL deionized water, at room temperature stir 12h.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid.Then at every turn with 60mL deionized water back extraction until with saturated AgNO3 aqueous solution titration water without precipitation generation.After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid.
The proton nmr spectra test result of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane hexafluorophosphate prepared by the present embodiment is as follows:
1H?NMR(CDCl
3,400MHz,ppm):4.74(s,2H),4.69(s,2H),3.85(m,2H),3.39(m,2H),3.34(m,2H),3.25(s,3H),2.83(m,2H),2.54(s,3H).
Synthesizing of two (fluoroform sulphonyl) inferior amine salts of embodiment 3 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane
In the flask of 250mL, add respectively (87g, 1mol) methyl azoles alkane and (138.6g, 1.2mol) methoxy ethoxy methyl chloride.At N
2(or Ar
2) under atmosphere protection, be warming up to 80 DEG C, stirring reaction 60h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying at 80 DEG C, obtains lurid solid intermediate product: chlorination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, yield is 83%.
In 500mL flask, add (105.5g, 0.5mol) chlorination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, (159.5g, 0.5mol) two (fluoroform sulphonyl) imines potassium (CF
3sO
2)
2nK and 140mL deionized water, at room temperature stir 18h.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid.Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation.After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid.
The proton nmr spectra test result of two (fluoroform sulphonyl) inferior amine salts of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane prepared by the present embodiment is as follows:
1H?NMR(CDCl
3,400MHz,ppm):4.75(s,2H),4.70(s,2H),3.86(m,2H),3.39(m,2H),3.34(m,2H),3.26(s,3H),2.84(m,2H),2.55(s,3H).
Synthesizing of two (fluorine sulphonyl) inferior amine salts of embodiment 4 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane
In the flask of 250mL, add respectively (87g, 1mol) methyl azoles alkane and (192g, 1.2mol) methoxy ethoxy monobromethane.At N
2(or Ar
2) under atmosphere protection, be warming up to 80 DEG C, stirring reaction 72h.Standing cooling, with ethyl acetate washing three times.Vacuum-drying at 80 DEG C, obtains lurid solid intermediate product: bromination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, yield is 84%.
In 500mL flask, add 0.5mol bromination 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, (93.5g, 0.5mol) two (fluoroform sulphonyl) imines potassium (FSO
2)
2nK and 150mL deionized water, at room temperature stir 24h.After having reacted, mixed solution 250mL dichloromethane extraction 3 times, combining extraction liquid.Then at every turn with 60mL deionized water back extraction until with saturated AgNO
3till aqueous solution titration water produces without precipitation.After methylene dichloride is concentrated with Rotary Evaporators, 80 DEG C of vacuum-drying 48h obtain colourless liquid.
The proton nmr spectra test result of two (fluorine sulphonyl) inferior amine salts of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane prepared by the present embodiment is as follows:
1H?NMR(CDCl
3,400MHz,ppm):4.74(s,2H),4.70(s,2H),3.85(m,2H),3.38(m,2H),3.33(m,2H),3.24(s,3H),2.83(m,2H),2.54(s,3H).
The preparation of azoles alkane il electrolyte:
Embodiment 5
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 10: 1 adds 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane tetrafluoroborate ion liquid, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of LiBF
4, and to make the volumetric molar concentration of lithium salts be 1mol/L (the volume V based on organic phase
eC+ eMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
Refer to Fig. 1, taking Graphene as electrode materials, the target organic electrolyte being obtained taking embodiment 5 is as electrolytic solution, be assembled into button cell, utilize CHI660A electrochemical workstation to carry out constant current charge-discharge test to it, in the electrochemical window of 0~2.7V, record its charging and discharging curve with the electric current of 0.25A/g.
As we know from the figure, this electrolytic solution and electrode materials composition ultracapacitor is carried out to conventionally test and has obtained the charging and discharging curve of standard, prove that the electrolytic solution configuring is suitable for the electrolytic solution of ultracapacitor, and there is good stability at the charging voltage electrolyte inside up to 2.7V.
Embodiment 6
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 1: 100 adds two (fluoroform sulphonyl) the inferior amine salt ionic liquids of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of lithium salts (as LiTFSI), the volumetric molar concentration that makes lithium salts is 0.3mol/L (the volume V based on organic phase
eC+EMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
Embodiment 7
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 1: 10 adds two (fluorine sulphonyl) the inferior amine salt ionic liquids of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of lithium salts (as LiFSI), the volumetric molar concentration that makes lithium salts is 0.5mol/L (the volume V based on organic phase
eC+EMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
Embodiment 8
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 1: 1 adds 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane tetrafluoroborate ion liquid, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of LiBF
4, and to make the volumetric molar concentration of lithium salts be 0.7mol/L (the volume V based on organic phase
eC+EMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
Embodiment 9
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 40: 1 adds 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane hexafluorophosphate ionic liquid, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of LiPF
6, and to make the volumetric molar concentration of lithium salts be 0.9mol/L (the volume V based on organic phase
eC+EMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
Embodiment 10
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 70: 1 adds two (fluoroform sulphonyl) the inferior amine salt ionic liquids of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of lithium salts (as LiTFSI), the volumetric molar concentration that makes lithium salts is 1.1mol/L (the volume V based on organic phase
eC+EMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
Embodiment 11
At N
2(or Ar
2) under atmosphere protection, by NSC 11801 (EC), Methyl ethyl carbonate (EMC), methylcarbonate (DMC), diethyl carbonate (DEC), ethyl butyrate (EB) with 2: 2: 1: the volume ratio of 1: 2 is configured to organic solvent (referred to as mixed solvent
eC+EMC+DMC+DEC+EB).Then compare mixed solvent according to quality
eC+EMC+DMC+DEC+EB: the proportioning that azoles alkane ionic liquid is 100: 1 adds two (fluorine sulphonyl) the inferior amine salt ionic liquids of 1-methoxy ethoxy methyl isophthalic acid-methyl azoles alkane, and is heated to 40 DEG C of stirrings and obtains uniform organic phase.Finally add a certain amount of lithium salts (as LiFSI), the volumetric molar concentration that makes lithium salts is 1.2mol/L (the volume V based on organic phase
eC+EMC+DMC+DEC+EB+ azoles alkane ionic liquiddecide the consumption of lithium salts), continue stirring lithium salts is dissolved completely, thereby obtain target organic electrolyte.
The above embodiment has only expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but can not therefore be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.