Preparation method of ionic liquids and secondary batteries

Patent metadata

Field	Value
Publication number	US-10312551-B2
Application number	US-201615261942-A
Country	US
Kind code	B2
Filing date	Sep 10, 2016
Priority date	Sep 11, 2015
Publication date	Jun 4, 2019
Grant date	Jun 4, 2019

Abstract

The present invention relates to a preparation method of ionic liquids, particularly to a one-step reaction method used for synthesizing quaternary ammonium compounds or quaternary phosphonium compounds. In the method, a nitrogenous or phosphorous compound, a proton compound, and a carbonate ester are added into a reactor simultaneously to synthesize corresponding the quaternary ammonium ionic liquid or the quaternary phosphonium ionic liquid through said one-step reaction, i.e., ‘one-pot method’ reaction, during which three reactants are involved. The present invention also provides a lithium ion secondary battery comprising the ionic liquid prepared by above-mentioned preparation method. The ionic liquid preparation method of the present invention can widen the choice range of raw materials needed when preparing ionic liquids, and further widen the synthesized ionic liquid species.

First claim

What is claimed is:

1. A preparation method of an ionic liquid, wherein the ionic liquid is synthesized by a one-step reaction wherein a nitrogenous compound or a phosphorous compound, and a proton compound react with a carbonate ester in one step; wherein a temperature of said one-step reaction is controlled in 120˜180° C.; the nitrogenous compound is at least one selected from a group consisting of ammonia (NH 3 ), a primary amine(R 1 NH 2 ), a secondary amine(R 1 R 2 NH) and a tertiary amine(R 1 R 2 R 3 N); the phosphorous compound is at least one selected from a group consisting of phosphine(PH 3 ), a primary phosphine(R 1 PH 2 ), a secondary phosphine(R 1 R 2 PH) and a tertiary phosphine(R 1 R 2 R 3 P); wherein each of the R 1 , R 2 and R 3 is selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or each of the R 1 , R 2 and R 3 is an organic group comprising at least one element of the following: boron, silicon, oxygen, nitrogen, phosphorus, sulfur, fluorine, chlorine, bromine and iodine; each of the R 1 , R 2 and R 3 is a substituent group; or at least two of the R 1 , R 2 and R 3 adjacent to each other joined into a ring.

2. The preparation method of the ionic liquid of claim 1 , wherein said nitrogenous compound is at least one selected from a group consisting of

wherein each of said R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or each of said R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is an organic group comprising at least one element selected from the following: boron, silicon, oxygen, nitrogen, phosphorus, sulfur, fluorine, chlorine, bromine and iodine; each of said R 1 , R 2 , R 3 , R 4 , R 5 and R 6 is a substituent group; or at least two of said R 1 , R 2 , R 3 , R 4 , R 5 and R 6 adjacent to each other joined into a ring.

3. The preparation method of the ionic liquid of claim 1 , wherein said phosphorous compound is at least one selected from a group consisting of methylphosphine, dimethylphosphine, trimethylphosphine, ethylphosphine, diethylphosphine, triethylphosphine, tripropylphosphine, di-tert-butylphosphine, tri-tert-butylphosphine, tri-butylphosphine, tri-n-pentylphosphine, cyclohexylphosphine, dicyclohexylphosphine, tricyclohexylphosphine, trihexylphosphine, trioctylphosphine, phenyl phosphine, diphenylphosphine, triphenylphosphine, dimethylphenylphosphine, diethylphenylphosphine, diphenyl-butylphosphine, tribenzylphosphine, tris(hydroxymethyl)phosphine, 2-chloroethyl-diethylphosphine and tri(pentafluoroethyl) phosphine.

4. The preparation method of the ionic liquid of claim 1 , wherein said proton compound is at least one selected from a group consisting of an inorganic oxyacid, an inorganic oxygen-free acid, an organic acid and a non-acid proton compound.

5. The preparation method of the ionic liquid of claim 4 , wherein said inorganic oxyacid is at least one selected from a group consisting of HAlO 2 , HAl(OH) 4 , H 3 AsO 4 , HAsO 2 , H 3 AsO 3 , H 4 As 2 O 7 , H 3 BO 3 , (HBO 2 )n, H 2 B 4 O 7 ,HBO 3 , H 5 BW 12 O 40 , HBrO 3 , HBrO 2 , HBrO, HBrO 4 , H 4 CO 4 , H 2 C 2 O 6 , H 2 CO 4 or H 2 CO 3 , H 2 O 2 , HCIO 3 , HCIO 4 , HCIO 2 , HCIO, HONC, HOCN, HNCO, HIO 3 , HIO or IOH, HIO 4 , H 5 IO 6 , H 4 I 2 O 9 , HNO 3 , HNO 2 , H 3 PO 4 , H 5 PO 5 , (HPO 3 ) n , H 3 PO 3 , H 4 P 2 O 5 , HPO 2 , H 3 PO 2 , H 4 P 2 O 6 , H 4 P 2 O 7 , H 2 SO 4 , H 2 SO 3 , H 2 S 2 O 3 , H 2 S 2 O 7 , H 2 SO 2 , H 2 S x O 6 (x=2˜6), H 6 SO 6 , H 2 S 2 O 4 , H 2 SO 5 , H 2 S 2 O 8 , HSO 3 CI , HSO 3 F, H 2 SiO 3 or SiO 2 .H 2 O, H 4 SiO 4 , H 2 Si 2 O 5 or 2SiO 2 ,H 2 O, H 4 Si 3 O 8 , and H 6 Si 2 O 7 or 2SiO 2 .3H 2 O.

6. The preparation method of the ionic liquid of claim 4 , wherein said inorganic oxygen-free acid is at least one selected from a group consisting of H[CHB 11 Cl 11 ], H 2 S, H 2 CS 4 , H 2 CS 3 , HCN, HSeCN, HSCN, HBF 4 , H 2 SiF 6 , HPF 6 , HF, HCl, HBr and HI.

7. The preparation method of the ionic liquid of claim 4 , wherein said organic acid is at least one selected from a group consisting of oxalic acid, methanoic acid, acetic acid, propionic acid, succinic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, methanesulfonic acid, mandelic acid, methylsulfate, ethylsulfate, oleic acid, stearic acid, acrylic acid, maleic acid, citric acid, bis(catecholato)boronic acid, bis(oxalate)boronic acid, bis(malonate)boronic acid, tri(pentafluoroethyl)trifluorophosphate, triethyltrifluorophosphate, tetracyanoboronic acid, tartaric acid, malic acid, citric acid, ascorbic acid, benzoic acid, benzenesulfonic acid, p-toluene sulfonic acid, salicylic acid, and caffeic acid.

8. The preparation method of the ionic liquid of claim 4 , wherein said non-acid proton compound is an imine compound; said imine compound has a structure as described by formula 1, formula 2 or formula 3:
HN(C m F 2m+1 SO 2 )(C n F 2n+1 SO 2 );  Formula 1:

HN(C n F 2n+1 SO 2 ) 2 ;  Formula 2:

HN(C x F 2x SO 2 ) 2 ;  Formula 3:

wherein m is an integer of 0 to 5, n is an integer of to 5, x is an integer of 1 to 10.

9. The preparation method of the ionic liquid of claim 8 , wherein said imine compound is at least one selected from a group consisting of

10. The preparation method of the ionic liquid of claim 4 , wherein said non-acid proton compound is at least one selected from a group consisting of tri(trifluoromethylsulfonyl)methane, phenol, p-methylphenol, β-naphthol, 2,4-dichlorophenol and p-aminophenol.

11. The preparation method of the ionic liquid of claim 1 , wherein said carbonate ester is at least one selected from a group consisting of dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, phenyl methyl carbonate, diphenyl carbonate and dibenzyl carbonate.

12. The preparation method of the ionic liquid of claim 11 , wherein said carbonate ester is at least one selected from a group consisting of dimethyl carbonate, ethyl methyl carbonate and diethyl carbonate.

13. The preparation method of the ionic liquid of claim 1 , wherein the temperature of said one-step reaction is controlled in 140˜160° C.

14. The preparation method of the ionic liquid of claim 1 , wherein the absolute pressure of said one-step reaction is controlled in 0.1˜3.0 Mpa.

15. The preparation method of the ionic liquid of claim 14 , wherein the absolute pressure of said one-step reaction is controlled in 0.8˜2.0 Mpa.

16. The preparation method of the ionic liquid of claim 15 , wherein the absolute pressure of said one-step reaction is controlled in 1.0˜1.5 Mpa.

17. The preparation method of the ionic liquid of claim 1 , wherein the reaction time of said one-step reaction is controlled in 0.1˜20 hours.

18. The preparation method of the ionic liquid of claim 17 , wherein the reaction time of said one-step reaction is controlled in 4˜15 hours.

19. The preparation method of the ionic liquid of claim 18 , wherein the reaction time of said one-step reaction is controlled in 9˜12 hours.

20. An electrolyte used in a secondary battery, comprising the ionic liquid prepared by the preparation method as described in claim 1 .

Assignees

• Microvast Power Systems Co Ltd

Inventors

• Zheng Zhuoqun
• Shen Dawei
• Qiu Jian
• Nie Yunhua
• Zhao Xiaozhen
• Li Danyi

Classifications

• H01M10/0568

  characterised by the solutes · CPC title

• H01M10/4235 Primary

  Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence) · CPC title

• H01M10/0525

  Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries · CPC title

• H01M2300/0028

  characterised by the solvent · CPC title

• H01M10/0569

  characterised by the solvents · CPC title