Ionic liquids and preparation method thereof

Patent metadata

Field	Value
Publication number	US-10411301-B2
Application number	US-201715413396-A
Country	US
Kind code	B2
Filing date	Jan 23, 2017
Priority date	Feb 2, 2016
Publication date	Sep 10, 2019
Grant date	Sep 10, 2019

Abstract

The present disclosure provides an ionic liquid and a preparation method thereof, in particular, the present disclosure provides an ionic liquid whose halogen anions content and moisture content are low, and a method for preparing the same. The total content of halogen anions in the ionic liquid is less than 10 ppm, and moisture content in the ionic liquid is less than 50 ppm. The ionic liquid prepared by the method of the present disclosure is suitable for electrochemical systems which have high requirements for moisture content, such as lithium ion secondary batteries and electrochemical supercapacitors.

First claim

What is claimed is:

1. A preparation method of an ionic liquid, wherein a total content of halogen anions in the ionic liquid is less than 10 ppm, and moisture content in the ionic liquid is less than 50 ppm; the halogen anions are Cl − , Br − and I − , comprising the following steps:
Step 1: preparing an ammonium salt or a phosphonium salt, reaction equations as below:
Q 4 Q 5 Q 6 N+[Q 1 Q 2 Q 3 NH] + A − →[Q 4 Q 5 Q 6 NH] + A − +Q 1 Q 2 Q 3 N  (a); or

Q 4 Q 5 Q 6 P+[Q 1 Q 2 Q 3 PH] + A − →[Q 4 Q 5 Q 6 PH] + A − +Q 1 Q 2 Q 3 P  (b); or

Q 4 Q 5 Q 6 N+[Q 1 Q 2 Q 3 PH] + A − →[Q 4 Q 5 Q 6 NH] + A − +Q 1 Q 2 Q 3 P  (c); or

Q 4 Q 5 Q 6 P+[Q 1 Q 2 Q 3 NH] + A − →[Q 4 Q 5 Q 6 PH] + A − +Q 1 Q 2 Q 3 N  (d);

Step 2: the ammonium salt or the phosphonium salt prepared in step 1 reacts with a carbonate ester to produce a quaternary ammonium salt or a quaternary phosphonium salt, reaction equations as below:
[Q 4 Q 5 Q 6 NH] + A − →+RCO 3 R′→[Q 4 Q 5 Q 6 NR] + A − +R′OH+CO 2 ; or

[Q 4 Q 5 Q 6 PH] + A − +RCO 3 R′→[Q 4 Q 5 Q 6 PR] + A − +R′OH+CO 2 ;

wherein each of Q 4 , Q 5 , Q 6 , Q 1 , Q 2 and Q 3 is selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or each of Q 4 , Q 5 , Q 6 , Q 1 , Q 2 and Q 3 is an organic group comprising at least one element selected from boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine and iodine; said organic group is alkyl, alkenyl, alkynyl, phenyl or aryl; wherein each of said Q 4 , Q 5 , Q 6 , Q 1 , Q 2 and Q 3 is an independent substituent group; or at least two of said Q 4 , Q 5 , Q 6 , Q 1 , Q 2 and Q 3 adjacent to each other joint into a ring;
wherein each of said R and R′ is selected from alkyl, alkenyl, alkynyl, phenyl or aryl; or each of said R and R′ is a group comprising at least one element selected from boron, silicon, nitrogen, phosphorus, oxygen, sulfur, fluorine, chlorine, bromine and iodine; wherein each of said R and R′ is an independent substituent group or R and R′ adjacent to each other joint into a ring;
in reaction equation (a) of step 1, alkalinity of the Q 4 Q 5 Q 6 N is stronger than that of Q 1 Q 2 Q 3 N; or Q 1 Q 2 Q 3 N is a volatile gas and Q 4 Q 5 Q 6 N is a liquid or a solid whose boiling point is higher than that of Q 1 Q 2 Q 3 N;
in reaction equation (b) of step 1, alkalinity of the Q 4 Q 5 Q 6 P is stronger than that of Q 1 Q 2 Q 3 P; or Q 1 Q 2 Q 3 P is a volatile gas and Q 4 Q 5 Q 6 P is a liquid or a solid whose boiling point is higher than that of Q 1 Q 2 Q 3 P;
in reaction equation (c) of step 1, alkalinity of the Q 4 Q 5 Q 6 N is stronger than that of Q 1 Q 2 Q 3 P; or Q 1 Q 2 Q 3 P is a volatile gas and Q 4 Q 5 Q 6 N is a liquid or a solid whose boiling point is higher than that of Q 1 Q 2 Q 3 P;
in reaction equation (d) of step 1, alkalinity of the Q 4 Q 5 Q 6 P is stronger than that of Q 1 Q 2 Q 3 N; or Q 1 Q 2 Q 3 N is a volatile gas and Q 4 Q 5 Q 6 P is a liquid or a solid whose boiling point is higher than that of Q 1 Q 2 Q 3 N.

2. The preparation method of the ionic liquid of claim 1 , wherein said Q 4 Q 5 Q 6 N is at least one selected from the group consisting of N-propylpyrrolidine, N-butylpyrrolidine, N-ethylpiperidine, N-propylpiperidine, N-butylpiperidine, triethylamine and dimethyloctylamine.

3. The preparation method of the ionic liquid of claim 1 , wherein said Q 4 Q 5 Q 6 N is at least one selected from dipropylamine, dioctyl amine, didecylamine and didodecylamine.

4. The preparation method of the ionic liquid of claim 1 , wherein said Q 4 Q 5 Q 6 N is at least one selected from n-hexylamine, ethanolamine, tetradecylamine and hexadecylamine.

5. The preparation method of the ionic liquid of claim 1 , wherein said Q 4 Q 5 Q 6 N is at least one selected from ethylimidazole, butylimidazole, pyridine and quinoline.

6. The preparation method of the ionic liquid of claim 1 , wherein said Q 4 Q 5 Q 6 P is at least one selected from methylphosphine, dimethylphosphine, trimethylphosphine, ethylphosphine, diethylphosphine, triethylphosphine, tripropylphosphine, di-butylphosphine, tri-tert-butylphosphine, tributylphosphine, tri-n-amyl phosphine, cyclohexyl phosphine, dicyclohexyl phosphine, tricyclohexyl phosphine, trihexylphosphine, trioctylphosphine, phenylphosphine, diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, diphenylbutylphosphine, tribenzylphosphine, trihydroxymethylphosphine, 2-chloroethanediethylphosphine and tris(pentafluoroethyl)phosphine.

7. The preparation method of the ionic liquid of claim 1 , wherein in reaction equation (a) of step 1, Q 1 Q 2 Q 3 N is selected from one of the following: an amine whose alkalinity is lower than that of Q 4 Q 5 Q 6 N, a volatile amine, an ammonia whose alkalinity is lower than that of Q 4 Q 5 Q 6 N, and a volatile ammonia; the anion A − is selected from at least one of the following: PF 6 − , BF 4 − , SO 4 2− , NO 3 − , F − , PO 4 3− , ClO 4 − , SiF 6 2− , (C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 )N − , (C x F 2x+1 SO 2 ) 2 N − , CF 3 SO 3 − , CH 3 CO 2 − , CF 3 CO 2 − , C 3 F 7 CO 2 − and (CN) 2 N − , wherein m is an integer from 0 to 5, n is an integer from 0 to 5, x is an integer from 1 to 10.

8. The preparation method of the ionic liquid of claim 1 , wherein in reaction equation (b) of step 1, Q 1 Q 2 Q 3 P is selected from one of the following: a phosphine whose alkalinity is lower than that of Q 4 Q 5 Q 6 P, a volatile phosphine or hydrogen phosphide; the anion A− is selected from at least one of the following: PF 6 − , BF 4 − , SO 4 2− , NO 3 − , F − , PO 4 3− , ClO 4 − , SiF 6 2− , (C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 )N − , (C x F 2x+1 SO 2 ) 2 N − , CF 3 SO 3 , CH 3 CO 2 − , CF 3 CO 2 − , C 3 F 7 CO 2 − and (CN) 2 N − ; wherein m is an integer from 0 to 5, n is an integer from 0 to 5, x is an integer from 1 to 10.

9. The preparation method of the ionic liquid of claim 1 , wherein in reaction equation (c) of step 1, Q 1 Q 2 Q 3 P is selected from one of the following: a phosphine whose alkalinity is lower than that of Q 4 Q 5 Q 6 N, a volatile phosphine or hydrogen phosphide, the anion A − is selected from at least one of the following: PF 6 − , BF 4 − , SO 4 2− , NO 3 − , F − , PO 4 3− , ClO 4 − , SiF 6 2− , (C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 )N − , (C x F 2x+1 SO 2 ) 2 N − , CF 3 SO 3 − , CH 3 CO 2 − , CF 3 CO 2 − , C 3 F 7 CO 2 − and (CN) 2 N − , wherein m is an integer from 0 to 5, n is an integer from 0 to 5, x is an integer from 1 to 10.

10. The preparation method of the ionic liquid of claim 1 , wherein in reaction equation (d) of step 1, Q 1 Q 2 Q 3 N is selected from one of the following: an amine whose alkalinity is lower than that of Q 4 Q 5 Q 6 P, a volatile amine, an ammonia whose alkalinity is lower than that of Q 4 Q 5 Q 6 P and a volatile ammonia; the anion A − is selected from at least one of the following: PF 6 − , BF 4 − , SO 4 2− , NO 3 − , F − , PO 4 3− , ClO 4 − , SiF 6 2− , (C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 )N − , (C x F 2x+1 SO 2 ) 2 N − , CF 3 SO 3 − , CH 3 CO 2 − , CF 3 CO 2 − , C 3 F 7 CO 2 − and (CN) 2 N − , wherein m is an integer from 0 to 5, n is an integer from 0 to 5, x is an integer from 1 to 10.

11. The preparation method of the ionic liquid of claim 7 , wherein said Q 1 Q 2 Q 3 N is selected from methylamine, dimethylamine, trimethylamine or ammonia.

12. The preparation method of the ionic liquid of claim 10 , wherein said Q 1 Q 2 Q 3 N is selected from methylamine, dimethylamine, trimethylamine or ammonia.

13. The preparation method of the ionic liquid of claim 1 , wherein a solvent is added into the reacti

Assignees

• Microvast Power Systems Co Ltd

Inventors

• Zheng Zhuoqun
• Shen Dawei
• Fei Zhenyu

Classifications

• C07C311/09

  the carbon skeleton being further substituted by at least two halogen atoms · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M10/0569

  characterised by the solvents · CPC title

• C07D295/037

  with quaternary ring nitrogen atoms · CPC title

• C07F9/5407

  Acyclic saturated phosphonium compounds · CPC title