# US 10,312,551 B2 · Preparation method of ionic liquids and secondary batteries

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- Number: US 10,312,551 B2
- Document ID: US10312551B2
- Status: Granted
- Kind: B2
- Application number: 15/261,942
- Filed: 2016-09-10
- Published: 2017-03-16
- Granted: 2019-06-04
- Earliest claimed: 2015-09-11
- Assignees: Microvast Power Systems Co., Ltd.
- Applicants: Microvast Power Systems Co., Ltd.
- Inventors: Zhuoqun Zheng; Dawei Shen; Jian Qiu; Yunhua Nie; Xiaozhen Zhao; Danyi Li
- Web page: https://patentgrep.com/patent/US10312551B2

## CPC

- H01M 10/4235: {Safety or regulating additives or arrangements in electrodes, separators or electrolyte (H01M10/4242 takes precedence)}
- H01M 4/525: of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
- H01M 10/0525: Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
- H01M 10/0567: characterised by the additives
- H01M 10/0568: characterised by the solutes
- H01M 10/0569: characterised by the solvents
- H01M 2300/0028: characterised by the solvent
- Y02E 60/10: Energy storage using batteries
- H01M: PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- Y02E: REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION

## 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.

## Claims

### Claim 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 (NH3), a primary amine(R1NH2), a secondary amine(R1R2NH) and a tertiary amine(R1R2R3N); the phosphorous compound is at least one selected from a group consisting of phosphine(PH3), a primary phosphine(R1PH2), a secondary phosphine(R1R2PH) and a tertiary phosphine(R1R2R3P); wherein each of the R1, R2 and R3 is selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or each of the R1, R2 and R3 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 R1, R2 and R3 is a substituent group; or at least two of the R1, R2 and R3 adjacent to each other joined into a ring.

### Claim 2 (depends on 1)

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 R1, R2, R3, R4, R5 and R6 is selected from hydrogen, alkyl, alkenyl, alkynyl, phenyl or aryl; or each of said R1, R2, R3, R4, R5 and R6 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 R1, R2, R3, R4, R5 and R6 is a substituent group; or at least two of said R1, R2, R3, R4, R5 and R6 adjacent to each other joined into a ring.

### Claim 3 (depends on 1)

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.

### Claim 4 (depends on 1)

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.

### Claim 5 (depends on 4)

The preparation method of the ionic liquid of claim 4, wherein said inorganic oxyacid is at least one selected from a group consisting of HAlO2, HAl(OH)4, H3AsO4, HAsO2, H3AsO3, H4As2O7, H3BO3, (HBO2)n, H2B4O7,HBO3, H5BW12O40, HBrO3, HBrO2, HBrO, HBrO4, H4CO4, H2C2O6, H2CO4 or H2CO3, H2O2, HCIO3, HCIO4, HCIO2, HCIO, HONC, HOCN, HNCO, HIO3, HIO or IOH, HIO4, H5IO6, H4I2O9, HNO3, HNO2, H3PO4, H5PO5, (HPO3)n, H3PO3, H4P2O5, HPO2, H3PO 2, H4P2O6, H4P2O7, H2SO4, H2SO3, H2S2O3, H2S2O7, H2SO2, H2SxO6(x=2˜6), H6SO6, H2S2O4, H2SO5, H2S2O8, HSO3CI , HSO3F, H2SiO3 or SiO2.H2O, H4SiO4, H2 Si2O5 or 2SiO2,H2O, H4Si3O8, and H6Si2O7 or 2SiO2.3H2O.

### Claim 6 (depends on 4)

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[CHB11Cl11], H2S, H2CS4, H2CS3, HCN, HSeCN, HSCN, HBF4, H2SiF6, HPF6, HF, HCl, HBr and HI.

### Claim 7 (depends on 4)

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.

### Claim 8 (depends on 4)

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(CmF2m+1SO2)(CnF2n+1SO2); Formula 1:
HN(CnF2n+1SO2)2; Formula 2:
HN(CxF2xSO2)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.

### Claim 9 (depends on 8)

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

### Claim 10 (depends on 4)

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.

### Claim 11 (depends on 1)

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.

### Claim 12 (depends on 11)

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.

### Claim 13 (depends on 1)

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

### Claim 14 (depends on 1)

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.

### Claim 15 (depends on 14)

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.

### Claim 16 (depends on 15)

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.

### Claim 17 (depends on 1)

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.

### Claim 18 (depends on 17)

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.

### Claim 19 (depends on 18)

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.

### Claim 20 (depends on 1)

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