CN103178297B - Lithium secondary battery and electrolyte thereof - Google Patents

Lithium secondary battery and electrolyte thereof Download PDF

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Publication number
CN103178297B
CN103178297B CN201310066997.6A CN201310066997A CN103178297B CN 103178297 B CN103178297 B CN 103178297B CN 201310066997 A CN201310066997 A CN 201310066997A CN 103178297 B CN103178297 B CN 103178297B
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lithium
electrolyte
ionic liquid
proton type
type ionic
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CN103178297A (en
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魏增福
刘世念
钟国彬
苏伟
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Electric Power Research Institute of Guangdong Power Grid Co Ltd
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Electric Power Research Institute of Guangdong Power Grid Co Ltd
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    • 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

Abstract

The invention discloses a kind of lithium secondary battery and electrolyte thereof, described electrolyte contains lithium salts and proton type ionic liquid or lithium salts, proton type ionic liquid and organic solvent, and described lithium salts addition is: add 0.1-2mol in every kilogram of proton type ionic liquid; The mass ratio of described proton type ionic liquid and organic solvent is 1:0-1; The structure of described proton type ionic liquid is as follows: r 1, R 2, R 3be selected from C separately nh 2n+1, C mh 2m+1oH or C ph 2p+1cN, 1≤n≤16,1≤m≤16,1≤p≤16; R 4for C qh 2q+1, q is 2 or 3; Described lithium secondary battery is containing housing, positive electrode, negative electrode, electrolyte and barrier film.Electrolyte of the present invention, viscosity is low, improves containing the high shortcoming of the electrolyte viscosity of ionic liquid, also can significantly improve the conductivity of electrolyte; Proton type ionic liquid also can promote the matching between electrolyte and electrode, barrier film.

Description

Lithium secondary battery and electrolyte thereof
Technical field
The present invention relates to a kind of lithium secondary battery and electrolyte thereof, particularly relate to a kind of lithium secondary battery and the electrolyte thereof that contain proton type ionic liquid electrolyte.
Background technology
In today that energy and environment receive much concern, energy-storage battery has great advantages for development.Lithium battery is a kind of desirable selection in energy-storage battery, and it is born in the nineties in 20th century, is a kind of high energy green battery, has a lot of advantage, and as high voltage, high-energy-density, working temperature is wide, the life-span is long, self-discharge rate is low, memory-less effect etc.Lithium battery is used widely in military affairs and civil small-scale electrical equipment, as mobile phone, camera, notebook computer etc., and is progressively applied to the fields such as submarine, space flight and electric motor car.But still have many key issues need solve, could apply widely, as to ensure its high fail safe, environment friendly, need to improve its performance, reduce costs simultaneously.
Electrolyte improper use in lithium battery, may bring environmental problem, thus seeks a kind of environmentally friendly electrolyte newly imperative.And the novel liquid ionic compound-ionic liquid of a class occurred in recent years, substantially meet the principle of " Green Chemistry " that American scientist Ah that Stas once proposed.Ionic liquid (Ionicliquids is called for short ILs), therefore namedly thinks justice and refers to it is also at room temperature the fuse salt of liquid condition, also claims organic salt liquid, nonaqueous ionic liquid etc.General ionic compound is all at room temperature solid-state, and ionic liquid due to the volume of its anions and canons large, and it is asymmetric, so sterically hindered larger, therefore anions and canons can not rely on electrostatic force to make their internal microstructure tightly packed, reduces interionic active force, reduces lattice energy, molten boiling point is declined, so ionic liquid physical efficiency is at room temperature in liquid condition.Ionic liquid possesses some advantages that other chemical substances can not be compared, and it has wider electrochemical window, does not almost have vapour pressure, and wider thermal stable temperature scope, chemical stability is high.Owing to having above advantage, ionic liquid progressively becomes study hotspot as the research of electrolyte.
Ionic liquid is by the moon, a kind of ionic compound that cation is formed, not containing neutral molecule.By the cation classification forming ionic liquid, mainly contain following: quaternary ammonium salt, quaternary phosphonium salt, imidazole salt, pyrrolidines, piperidines, anion mainly contains AlCl4-, BF4-, PF6-, CF3SO3-, (CF3SO3) 2N-five kinds of ions, but the viscosity of these ionic liquids is all very large, its application in lithium ion battery is restricted.In the recent period, proton type ionic liquid due to its in room temperature close to water, there is comparatively low viscosity and receiving much concern.
Summary of the invention
Based on this, be necessary for the large problem of il electrolyte viscosity, provide in a kind of electrolyte containing the lithium secondary battery of proton type ionic liquid and electrolyte thereof.
The concrete technical scheme solved the problems of the technologies described above is as follows:
An electrolyte for lithium secondary battery, described electrolyte contains lithium salts and proton type ionic liquid or lithium salts, proton type ionic liquid and organic solvent; The addition of described lithium salts is: add 0.1-2mol in every kilogram of proton type ionic liquid; The mass ratio of described proton type ionic liquid and organic solvent is 1:0-1;
Described proton type ionic liquid is made up of cationic structural and anion structure, specific as follows:
Wherein:
R 1, R 2, R 3be selected from C separately nh 2n+1, C mh 2m+1oH or C ph 2p+1cN, wherein, 1≤n≤16,1≤m≤16,1≤p≤16;
R 4for C qh 2q+1, wherein, q is 2 or 3.
Wherein in some embodiments, R in described proton type ionic liquid 1, R 2, R 3be selected from C separately nh 2n+1, C mh 2m+1oH or C ph 2p+1cN, wherein, 1≤n≤3,1≤m≤3,1≤p≤3; R 4for ethyl.
Wherein in some embodiments, R in described proton type ionic liquid 1, R 2, R 3be selected from C separately nh 2n+1, C mh 2m+1oH or C ph 2p+1cN, wherein, 1≤n≤2,1≤m≤2,1≤p≤2; R 4for ethyl.
Wherein in some embodiments, the mass ratio of described proton type ionic liquid and organic solvent is 1:0-0.7.
Wherein in some embodiments, the addition of described lithium salts is: add 0.6-1mol in every kilogram of proton type ionic liquid.
Wherein in some embodiments, the addition of described lithium salts is: add 0.7-0.8mol in every kilogram of proton type ionic liquid.
Wherein in some embodiments, described lithium salts is one or more the mixture in tetrafluoro boric acid lithium salts, hexafluorophosphoric acid lithium salts, two (trimethyl fluoride sulfonyl) imines lithium salts, two (perfluoroethyl sulfonyl) imines lithium salts, two (perfluoro propyl sulphonyl) imines lithium salts, two (fluorine sulphonyl) imines lithium salts, lithium perchlorate salt, trifluoromethyl sulfonic acid lithium salt, biethyl diacid lithium borate salt, difluorine oxalic acid boracic acid lithium.
Wherein in some embodiments, described organic solvent is propene carbonate.
A kind of lithium secondary battery, comprise housing, positive electrode, negative electrode, electrolyte and barrier film, described electrolyte is the electrolyte described in above-mentioned any one.
Wherein in some embodiments, the material of described positive electrode is cobalt acid lithium, LiFePO 4, lithium nickelate, nickel cobalt lithium aluminate, lithium manganese phosphate, phosphoric acid vanadium lithium or lithium titanate;
Wherein in some embodiments, the material of described negative electrode is Delanium, native graphite, carbonaceous mesophase spherules, mesophase carbon fiber, soft carbon, hard carbon, lithium titanate or lithium sheet.
A kind of lithium secondary battery and electrolyte thereof containing proton type ionic liquid provided by the invention, tool has the following advantages and beneficial effect:
(1) the electrolyte viscosity in lithium secondary battery of the present invention is low, conductivity is high.
(2) the proton type ionic liquid described in lithium secondary battery of the present invention is conducive to promoting the matching between electrolyte and electrode, barrier film.
Embodiment
Because proton type ionic liquid has lower viscosity (in room temperature close to water), based on this, this character is applied in lithium rechargeable battery by the present invention, thus improves ionic liquid has viscosity higher shortcoming as electrolyte, improves the conductivity of electrolyte.
Technical scheme of the present invention is further illustrated below with reference to embodiment.
Embodiment 1
(1) electrolyte for lithium secondary battery, containing lithium salts and proton type ionic liquid in described electrolyte;
Specific as follows:
Under room temperature, in proton type ionic liquid N-ethanol-N, two (trimethyl fluoride sulfonyl) imines lithium salts is added in N-Dimethyl Ammonium propionic acid, wherein, the addition of two (trimethyl fluoride sulfonyl) imines lithium salts is: every kilogram of proton type ionic liquid N-ethanol-N, add 0.75mol in N-Dimethyl Ammonium propionic acid, can electrolyte be obtained;
In described proton type ionic liquid anion and cationic structural as follows:
After testing: in 25 DEG C, the conductivity of this electrolyte is 1.2mS/cm, and viscosity is 15cP.
(2) lithium secondary battery, comprises housing, positive electrode, negative electrode, electrolyte and barrier film, and the electrolyte of described electrolyte obtained by the present embodiment (1), wherein, described positive electrode is lithium titanate, and negative material is lithium sheet.
Embodiment 2
(1) electrolyte for lithium secondary battery, described electrolyte contains lithium salts, proton type ionic liquid and organic solvent;
Specific as follows:
Under room temperature, in proton type ionic liquid N-ethanol-N, N-Dimethyl Ammonium propionic acid with add two (trimethyl fluoride sulfonyl) imines lithium salts in organic solvent propene carbonate mixed liquor (3:2 mixes in mass ratio), wherein, the addition of two (trimethyl fluoride sulfonyl) imines lithium salts is: every kilogram of proton type ionic liquid N-ethanol-N, add 0.75mol in N-Dimethyl Ammonium propionic acid, can electrolyte be obtained.
In described proton type ionic liquid anion and cationic structural as follows:
After testing: in 25 DEG C, the conductivity of this electrolyte is 5.0mS/cm, and viscosity is 15cP.
(2) lithium secondary battery, comprises housing, positive electrode, negative electrode, electrolyte and barrier film, and the electrolyte of described electrolyte obtained by the present embodiment (1), described positive electrode is lithium titanate, and negative material is lithium sheet.
Embodiment 3
(1) electrolyte for lithium secondary battery, described electrolyte contains lithium salts and proton type ionic liquid;
Specific as follows:
At room temperature, in proton type ionic liquid N-propionitrile-N, two (trimethyl fluoride sulfonyl) imines lithium salts is added in N-Dimethyl Ammonium propionic acid, wherein, the addition of two (trimethyl fluoride sulfonyl) imines lithium salts is: every kilogram of proton type ionic liquid N-propionitrile-N, N-Dimethyl Ammonium propionic acid kind adds 0.75mol, can obtain electrolyte;
The structure of described proton type ionic liquid cationic and anion is as follows:
After testing: in 25 DEG C, the conductivity of this electrolyte is 1.0mS/cm, and viscosity is 10cP.
(2) lithium secondary battery, comprises housing, positive electrode, negative electrode, electrolyte and barrier film, and the electrolyte of described electrolyte obtained by the present embodiment (1), described positive electrode is lithium titanate, and negative material is lithium sheet.
Embodiment 4
(1) electrolyte for lithium secondary battery, described electrolyte contains lithium salts, proton type ionic liquid and organic solvent;
Specific as follows:
At room temperature, in proton type ionic liquid N-propionitrile-N, N-Dimethyl Ammonium propionic acid with add two (trimethyl fluoride sulfonyl) imines lithium salts in propene carbonate mixed liquor (3:2 mixes in mass ratio), wherein, the addition of two (trimethyl fluoride sulfonyl) imines lithium salts is: every kilogram of proton type ionic liquid N-propionitrile-N, add 0.75mol in N-Dimethyl Ammonium propionic acid, can electrolyte be obtained;
In described proton type ionic liquid anion and cationic structure as follows:
After testing: in 25 DEG C, the conductivity of this electrolyte is 4.0mS/cm, and viscosity is 10cP.
(2) lithium secondary battery, comprises housing, positive electrode, negative electrode, electrolyte and barrier film, and the electrolyte of described electrolyte obtained by the present embodiment (1), described positive electrode is LiFePO 4, and negative material is lithium sheet.
In above-described embodiment 1-4, the carboxyl of proton type solion anion, cationic itrile group, alcohol radical all can promote the matching between electrolyte and electrode, barrier film.
The above embodiment only have expressed several execution mode of the present invention, and it describes comparatively concrete and detailed, but therefore can not 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 range of patent of the present invention should be as the criterion with claims.

Claims (8)

1. an electrolyte for lithium secondary battery, is characterized in that, containing lithium salts and proton type ionic liquid or lithium salts, proton type ionic liquid and organic solvent in described electrolyte; The addition of described lithium salts is: add 0.1-2mol in every kilogram of proton type ionic liquid; The mass ratio of described proton type ionic liquid and organic solvent is 1:0-1;
Described proton type ionic liquid is made up of following cationic structural and anion structure, specific as follows:
Wherein:
R 1, R 2, R 3be selected from C separately nh 2n+1, C mh 2m+1oH or C ph 2p+1cN, wherein, 1≤n≤3,1≤m≤3,1≤p≤3;
R 4for C qh 2q+1, wherein, q is 2; Described organic solvent is propene carbonate.
2. the electrolyte of lithium secondary battery according to claim 1, is characterized in that, the addition of described lithium salts is: add 0.6-1mol in every kilogram of proton type ionic liquid.
3. the electrolyte of lithium secondary battery according to claim 2, is characterized in that, the addition of described lithium salts is: add 0.7-0.8mol in every kilogram of proton type ionic liquid.
4. the electrolyte of lithium secondary battery according to claim 1, is characterized in that, the mass ratio of described proton type ionic liquid and organic solvent is 1:0-0.7.
5. the electrolyte of lithium secondary battery according to claim 1, it is characterized in that, described lithium salts is one or more the mixture in tetrafluoro boric acid lithium salts, hexafluorophosphoric acid lithium salts, two (trimethyl fluoride sulfonyl) imines lithium salts, two (perfluoroethyl sulfonyl) imines lithium salts, two (perfluoro propyl sulphonyl) imines lithium salts, two (fluorine sulphonyl) imines lithium salts, lithium perchlorate salt, trifluoromethyl sulfonic acid lithium salt, biethyl diacid lithium borate salt, difluorine oxalic acid boracic acid lithium.
6. a lithium secondary battery, comprises housing, positive electrode, negative electrode, electrolyte and barrier film, it is characterized in that, described electrolyte is the electrolyte described in any one of the claims 1-5.
7. lithium secondary battery according to claim 6, is characterized in that, the material of described positive electrode is cobalt acid lithium, LiFePO 4, lithium nickelate, nickel cobalt lithium aluminate, lithium manganese phosphate, phosphoric acid vanadium lithium or lithium titanate.
8. lithium secondary battery according to claim 6, is characterized in that, the material of described negative electrode is Delanium, native graphite, carbonaceous mesophase spherules, mesophase carbon fiber, soft carbon, hard carbon, lithium titanate or lithium sheet.
CN201310066997.6A 2013-03-01 2013-03-01 Lithium secondary battery and electrolyte thereof Active CN103178297B (en)

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CN103972589B (en) * 2014-05-19 2016-07-13 陕西科技大学 A kind of preparation method of the electrolyte improving lithium ion battery security
CN107565165A (en) * 2017-09-29 2018-01-09 合肥工业大学 A kind of method that electrolyte improves lithium battery performance
CN113540563B (en) * 2020-04-17 2023-04-07 中国石油化工股份有限公司 Additive and modification method of lithium battery electrolyte

Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1997620A (en) * 2004-04-07 2007-07-11 约克大学 Ionic liquids comprising nitrogen containing cations
CN102124599A (en) * 2008-05-29 2011-07-13 莱登能源公司 Electrochemical cells with ionic liquid electrolyte

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KR100861916B1 (en) * 2001-03-26 2008-10-09 닛신보세키 가부시키 가이샤 Ionic liquid, electrolyte salt for storage device, electrolytic solution for storage device, electric double layer capacitor, and secondary battery

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1997620A (en) * 2004-04-07 2007-07-11 约克大学 Ionic liquids comprising nitrogen containing cations
CN102124599A (en) * 2008-05-29 2011-07-13 莱登能源公司 Electrochemical cells with ionic liquid electrolyte

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Address after: 510080 Dongfeng East Road, Dongfeng, Guangdong, Guangzhou, Zhejiang Province, No. 8

Patentee after: ELECTRIC POWER RESEARCH INSTITUTE, GUANGDONG POWER GRID CO., LTD.

Address before: 510080 Dongfeng East Road, Dongfeng, Guangdong, Guangzhou, Zhejiang Province, No. 8

Patentee before: Electrical Power Research Institute of Guangdong Power Grid Corporation