CN110165298B - Electrolyte solution - Google Patents
Electrolyte solution Download PDFInfo
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- CN110165298B CN110165298B CN201810281970.1A CN201810281970A CN110165298B CN 110165298 B CN110165298 B CN 110165298B CN 201810281970 A CN201810281970 A CN 201810281970A CN 110165298 B CN110165298 B CN 110165298B
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- electrolyte
- lithium
- carbonate
- ionic liquid
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- 239000008151 electrolyte solution Substances 0.000 title description 2
- 239000003792 electrolyte Substances 0.000 claims abstract description 80
- 239000002608 ionic liquid Substances 0.000 claims abstract description 43
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 17
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 17
- 239000011356 non-aqueous organic solvent Substances 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 3
- 230000000996 additive effect Effects 0.000 claims abstract description 3
- 239000011259 mixed solution Substances 0.000 claims description 67
- -1 ethoxy, phenyl Chemical group 0.000 claims description 65
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 51
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 51
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 14
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 6
- OZJPLYNZGCXSJM-UHFFFAOYSA-N 5-valerolactone Chemical compound O=C1CCCCO1 OZJPLYNZGCXSJM-UHFFFAOYSA-N 0.000 claims description 6
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- NMJJFJNHVMGPGM-UHFFFAOYSA-N butyl formate Chemical compound CCCCOC=O NMJJFJNHVMGPGM-UHFFFAOYSA-N 0.000 claims description 6
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 claims description 6
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 claims description 6
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 5
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 4
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 claims description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 3
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 3
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 claims description 3
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 claims description 3
- HTWIZMNMTWYQRN-UHFFFAOYSA-N 2-methyl-1,3-dioxolane Chemical compound CC1OCCO1 HTWIZMNMTWYQRN-UHFFFAOYSA-N 0.000 claims description 3
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical compound CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 3
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 3
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical compound CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 claims description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 3
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 claims description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 3
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 claims description 3
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 3
- NKDDWNXOKDWJAK-UHFFFAOYSA-N dimethoxymethane Chemical compound COCOC NKDDWNXOKDWJAK-UHFFFAOYSA-N 0.000 claims description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 3
- WBJINCZRORDGAQ-UHFFFAOYSA-N formic acid ethyl ester Natural products CCOC=O WBJINCZRORDGAQ-UHFFFAOYSA-N 0.000 claims description 3
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 claims description 3
- 150000003949 imides Chemical class 0.000 claims description 3
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 3
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 3
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 3
- 229940090181 propyl acetate Drugs 0.000 claims description 3
- HUAZGNHGCJGYNP-UHFFFAOYSA-N propyl butyrate Chemical compound CCCOC(=O)CCC HUAZGNHGCJGYNP-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 2
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 claims description 2
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 42
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 42
- 239000010405 anode material Substances 0.000 abstract description 5
- 239000003125 aqueous solvent Substances 0.000 abstract description 3
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 3
- 238000007614 solvation Methods 0.000 abstract description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 44
- 229910052786 argon Inorganic materials 0.000 description 22
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 22
- 239000001301 oxygen Substances 0.000 description 22
- 229910052760 oxygen Inorganic materials 0.000 description 22
- 238000003756 stirring Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 4
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 239000004743 Polypropylene Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002000 Electrolyte additive Substances 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- UZZWBUYVTBPQIV-UHFFFAOYSA-N dme dimethoxyethane Chemical compound COCCOC.COCCOC UZZWBUYVTBPQIV-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
Abstract
An electrolyte, comprising: the functional imidazole type ionic liquid comprises a functional imidazole type ionic liquid additive, a non-aqueous organic solvent and lithium salt. Compared with the prior art, the invention provides an electrolyte, which comprises a non-aqueous solvent, lithium salt and a functionalized imidazole type ionic liquid. Due to the coordination capacity of the phosphine functional group and the lithium ions, the solvation capacity of the lithium ions in the electrolyte is weakened, the movement of the lithium ions on the interface of the anode material and the electrolyte is greatly enhanced, and the cycle performance of the battery is improved. And secondly, the self property of the functionalized ionic liquid can play a role in flame retardance, so that the safety performance of the battery is improved.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to an electrolyte. .
Background
With the increasing concern of human beings on the increasingly worsening environment, the electric driving or hybrid driving of automobiles has become a major direction of automobile development in the future. Various automobile manufacturers increasingly develop research and development investment on electric automobiles, and the vital battery technology becomes the maximum resistance of the development of the electric automobiles. The most market-share battery is lithium ion battery, so it is necessary to research it in order to improve its performance and safety.
Lithium iron phosphate and lithium cobaltate are excellent anode materials of lithium ion batteries. The proportion of lithium iron phosphate in the field of Chinese power lithium batteries is large and almost reaches 70%. The theoretical capacity of lithium cobaltate is 274mAh/g, but the actual capacity is generally 120-130 mAh/g. The main reason is that the lithium cobaltate crystal form is distorted after the charging voltage exceeds 4.2V, and the performance is rapidly reduced. The composition of the traditional electrolyte is changed, so that lithium cobaltate can be charged and discharged under higher voltage, which is the best way for solving the problem. An electrolyte system which can be better adapted to the anode material of the lithium ion battery is found, so that the electrolyte system not only has great economic value, but also has profound social influence.
Electrolytes are an important component of lithium ion batteries. The excellent electrolyte can greatly prolong the service life of the battery and eliminate potential safety hazards generated in the use process of the battery. The method for obtaining the lithium ion battery electrolyte suitable for various use occasions is convenient, quick and low in cost. Due to excellent physical and chemical properties of good electrochemical stability, chemical stability, wide liquid range, high conductivity and the like, the ionic liquid becomes a potential functional electrolyte additive with important application prospect.
Disclosure of Invention
The invention aims to provide an electrolyte with lower cost, and the electrolyte provided by the invention improves the cycle performance of a lithium ion battery.
In order to solve the above technical problems, the present invention is solved by the following technical solutions.
An electrolyte, comprising: the functional imidazole type ionic liquid comprises a functional imidazole type ionic liquid additive, a non-aqueous organic solvent and lithium salt.
Preferably, the structure of the functionalized imidazole type ionic liquid is shown as the following formula:
wherein,R1selected from methyl, ethyl, propyl, butyl, pentyl, hexyl; r2Selected from ethoxy, phenyl; n is 3,4,5, 6; x-Selected from hexafluorophosphate anions, bis (trifluoromethylsulfonyl) imide anions.
Preferably, wherein R is1Selected from propyl, butyl, pentyl, hexyl; r2Is an ethoxy group; n is 3,4,5, 6; x-Selected from hexafluorophosphate anions and bis (trifluoromethylsulfonyl) imide anions.
Preferably, the non-aqueous organic solvent is selected from the group consisting of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, dimethoxymethane, ethylene glycol dimethyl ether dimethoxyethane, diethylene glycol dimethyl ether, sulfolane and dimethyl sulfoxide.
Preferably, the nonaqueous organic solvent is a mixed solution of ethylene carbonate and dimethyl carbonate.
Preferably, the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide.
Preferably, the lithium salt is selected from lithium bis (trifluoromethylsulfonyl) imide and lithium hexafluorophosphate.
Preferably, the molar concentration of the lithium salt in the non-aqueous organic solvent is 0.5M to 1.5M; the content of the ionic liquid is 0.1-50% by mass of the electrolyte.
Compared with the prior art, the invention has the following beneficial effects: the application provides an electrolyte, which comprises a non-aqueous solvent, a lithium salt and a functionalized imidazole type ionic liquid. Due to the coordination capacity of the phosphine functional group and the lithium ions, the solvation capacity of the lithium ions in the electrolyte is weakened, the movement of the lithium ions on the interface of the anode material and the electrolyte is greatly enhanced, and the cycle performance of the battery is improved. And secondly, the self property of the functionalized ionic liquid can play a role in flame retardance, so that the safety performance of the battery is improved.
Detailed Description
For a further understanding of the invention, reference will now be made to the preferred embodiments of the present invention by way of example, and it is to be understood that the description is intended to further illustrate features and advantages of the present invention and is not intended to limit the scope of the claims which follow.
The embodiment of the invention discloses an electrolyte, which comprises: a non-aqueous organic solvent, a lithium salt and a functionalized ionic liquid.
The electrolyte is added with the functionalized ionic liquid, and the structure of the functionalized ionic liquid is preferably shown as formulas (I-1), (I-2) and (I-3).
The non-aqueous organic solvent herein is selected from two or more of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, ethyl methyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, dimethoxymethane, dimethoxyethane, diethyleneglycol dimethyl ether, sulfolane and dimethyl sulfoxide. When two or more of the non-aqueous organic solvents are mixed, the ratio of mixing thereof is not particularly limited in the present application. The non-aqueous organic solvent is preferably a mixture of ethylene carbonate and dimethyl carbonate, and the volume ratio of the ethylene carbonate to the dimethyl carbonate is preferably 1: 1.
the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide and lithium bis (fluorosulfonato) imide. More preferably, the lithium salt is lithium hexafluorophosphate. The concentration of the lithium salt in the nonaqueous organic solvent is preferably 0.3M to 2.5M, more preferably 0.8M to 1.5M.
The application provides an electrolyte, which comprises a non-aqueous solvent, a lithium salt and a functionalized imidazole type ionic liquid. The non-aqueous organic solvent and lithium salt used in the present application are all commercially available. The coordination capacity of the phosphine functional group and the lithium ions weakens the solvation capacity of the lithium ions in the electrolyte, greatly enhances the movement of the lithium ions at the interface of the anode material and the electrolyte, and improves the cycle performance and the rate capability of the battery. And secondly, the self property of the functionalized ionic liquid can play a role in flame retardance, so that the safety performance of the battery is improved.
For further understanding of the present invention, the electrolyte provided by the present invention is described in detail below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1: ionic liquids (I-1), (I-2) and (I-3) were prepared. The ionic liquids (I-1), (I-2) and (I-3) were placed in a vacuum oven and dried at 100 ℃ for 24 hours.
Example 2: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-1) prepared in the example 1, which is 0.1% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Example 3: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-1) prepared in the example 1, which is 1% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 4: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (3) adding lithium hexafluorophosphate into the organic mixed solution according to the volume ratio of 1:1 of dimethyl carbonate to ensure that the molar concentration of the lithium hexafluorophosphate is 1mol/L, finally slowly adding the functionalized ionic liquid prepared in the example 1, which accounts for 5% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 5: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-1) prepared in the example 1, which is 10% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example (b): in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-1) prepared in the example 1, which is 20% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 7: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-1) prepared in the example 1, which accounts for 30% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 8: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-1) prepared in the example 1, which accounts for 40% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 9: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which is 0.1% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Example 10: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which is 1% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 11: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which is 5% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 12: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which is 10% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 13: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which is 20% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 14: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which accounts for 30% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 15: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-2) prepared in the example 1, which accounts for 40% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 16: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which is 0.1% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the lithium ion battery electrolyte.
Example 17: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which is 1% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 18: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which is 5% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 19: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which is 10% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 20: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which is 20% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 21: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which accounts for 30% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Example 22: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (2) adding lithium hexafluorophosphate into the organic mixed solution to enable the molar concentration of the lithium hexafluorophosphate to be 1mol/L according to the volume ratio of 1:1 of dimethyl carbonate, finally slowly adding the functionalized ionic liquid (I-3) prepared in the example 1, which accounts for 40% of the total mass of the electrolyte, into the mixed solution, and uniformly stirring to obtain the electrolyte of the lithium ion battery.
Comparative example 1: in a glove box filled with argon (moisture <1ppm, oxygen <1ppm), 10mL of an organic mixed solution of ethylene carbonate and dimethyl carbonate, ethylene carbonate, was taken. And (3) adding lithium hexafluorophosphate into the organic mixed solution according to the volume ratio of 1:1 of dimethyl carbonate to ensure that the molar concentration of the lithium hexafluorophosphate is 1mol/L, and uniformly stirring to obtain the lithium ion battery electrolyte.
The lithium ion battery electrolytes prepared in the embodiments 2 to 22 and the lithium ion battery electrolyte prepared in the comparative example 1 are respectively injected into a CR2032 button cell with a positive electrode made of lithium iron phosphate, a negative electrode made of lithium, and a diaphragm made of Celgard polypropylene, and the rated capacity of the cell is 170 mAh. Cycling at 1C rate for 100 weeks at 2.6-3.8V. The battery was subjected to charge and discharge tests, and the test results are shown in table 1.
The lithium ion battery electrolytes prepared in the embodiments 2 to 22 and the lithium ion battery electrolyte prepared in the comparative example 1 are respectively injected into a CR2032 button cell with a positive electrode of lithium cobaltate, a negative electrode of lithium and a diaphragm of Celgard polypropylene, and the rated capacity of the cell is 160 mAh. Cycling at 0.5C rate for 100 weeks at 3-4.3V. The battery was subjected to charge and discharge tests, and the test results are shown in table 2.
As can be seen from the cycling performance test data in table 1, the cycling performance of the cell with the addition of the functionalized ionic liquid electrolyte was superior to that of the comparative cell without the addition.
Table 1 example and comparative example cycle test results.
| Group of | Capacity retention rate at 100 cycles |
| Comparative example 1 | 70％ |
| Example 2 | 80％ |
| Example 3 | 82％ |
| Example 4 | 85％ |
| Example 5 | 85％ |
| Example 6 | 90％ |
| Example 7 | 88％ |
| Example 8 | 86％ |
| Example 9 | 77％ |
| Example 10 | 78％ |
| Example 11 | 84％ |
| Example 12 | 83％ |
| Example 13 | 91％ |
| Example 14 | 87％ |
| Example 15 | 76％ |
| Example 16 | 78％ |
| Example 17 | 81％ |
| Example 18 | 81％ |
| Example 19 | 84％ |
| Example 20 | 89％ |
| Example 21 | 85％ |
| Example 22 | 75％ |
TABLE 1
Table 2 examples and comparative examples cycle test results.
TABLE 2
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (7)
1. An electrolyte, comprising: a functionalized imidazole type ionic liquid additive, a non-aqueous organic solvent and a lithium salt;
the structure of the functionalized imidazole ionic liquid is shown in the following figure:
wherein R is1Selected from methyl, ethyl, propyl, butyl, pentyl, hexyl; r2Selected from ethoxy, phenyl; n is 3,4,5 or 6; x-Selected from hexafluorophosphate anions and bis (trifluoromethylsulfonyl) imide anions.
2. The electrolyte of claim 1, wherein R is1Selected from propyl, butyl, pentyl, hexyl; r2Is an ethoxy group; n is 3,4,5 or 6; x-Selected from hexafluorophosphate anions and bis (trifluoromethylsulfonyl) imide anions.
3. The electrolyte as claimed in claim 1, the non-aqueous organic solvent is selected from a mixed solution of two or more of ethylene carbonate, propylene carbonate, butylene carbonate, fluoroethylene carbonate, vinylene carbonate, dimethyl carbonate, methylethyl carbonate, diethyl carbonate, methyl formate, ethyl formate, propyl formate, butyl formate, methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, ethyl butyrate, propyl butyrate, gamma-butyrolactone, delta-valerolactone, tetrahydrofuran, 2-methyltetrahydrofuran, 1, 3-dioxolane, 4-methyl-1, 3-dioxolane, 2-methyl-1, 3-dioxolane, dimethoxymethane, dimethoxyethane, diethylene glycol dimethyl ether, sulfolane and dimethyl sulfoxide.
4. The electrolyte of claim 3, wherein the non-aqueous organic solvent is a mixture of ethylene carbonate and dimethyl carbonate.
5. The electrolyte of claim 1, wherein the lithium salt is selected from one or more of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bis (oxalato) borate, lithium difluoro (oxalato) borate, lithium bis (trifluoromethylsulfonyl) imide, and lithium bis (fluorosulfonato) imide.
6. The electrolyte of claim 4, wherein the lithium salt is selected from the group consisting of lithium bis (trifluoromethylsulfonyl) imide and lithium hexafluorophosphate.
7. The electrolyte of claim 1, wherein the molar concentration of the lithium salt in the non-aqueous organic solvent is from 0.5M to 1.5M; the content of the ionic liquid is 0.1-50% by mass of the electrolyte.
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