CN1323460C - A novel composite electrolyte material - Google Patents
A novel composite electrolyte material Download PDFInfo
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- CN1323460C CN1323460C CNB2003101173508A CN200310117350A CN1323460C CN 1323460 C CN1323460 C CN 1323460C CN B2003101173508 A CNB2003101173508 A CN B2003101173508A CN 200310117350 A CN200310117350 A CN 200310117350A CN 1323460 C CN1323460 C CN 1323460C
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Abstract
The present invention relates to a novel composite electrolyte material. On the basis of a novel room-temperature molten salt or a low-temperature molten salt (also called weighing ionic liquid) material, a composite electrolyte formed by carrying out an addition reaction with an organic solvent, a polymeric material, etc. has the advantages of preferable heat stability, wide electrochemical window and superior ionic conductivity, and particularly in the aspect of safety, the present invention is superior to a liquid electrolyte used by the lithium ion batteries of commercialization at present. Various composite electrolytes of a room-temperature (or low-temperature) molten salt electrolyte, a gel polymer electrolyte, a solid polymer electrolyte, etc., which have good performance, are obtained by regulating the component and the proportioning of negative ions and positive ions in the molten salt and carrying out an addition reaction with the organic solvent, the polymer, etc. The present invention has the wide application prospect on the aspects of the lithium ion batteries, electrochemical super capacitors, etc.
Description
Technical field
The invention belongs to the electrolyte technical field, mainly towards the application of high energy battery such as lithium ion battery, electric chemical super capacitor, fuel cell and photovoltaic cell and electronic equipment technical field.
Technical background
Room temperature fused salt is the liquid of being made up of ion fully, is the salt that is in a liquid state under the low temperature (＜100 ℃), also claims ionic liquid (IonicLiquids), and it generally is made up of organic cation and inorganic anion.Ionic liquid is being subjected to extensive attention as green solvent aspect organic and the Polymer Synthesizing in recent years, and has carried out deep research aspect electrochemistry.Compare with electrolyte with traditional organic solvent, ionic liquid has a series of outstanding advantages: (1) does not almost have vapour pressure, and is non-volatile; Colourless, nothing is smelt; (2) has bigger stable temperature scope, the electrochemical stability potential window of better chemical stability and broad; (3) its dissolubility of design scalable by zwitterion to inorganic matter, water, organic substance and polymer, and its acidity can transfer to super acid or the like.At present ion liquid research is mainly concentrated on the sign of synthetic, its physics of novel ion liquid and chemical characteristic and as aspects such as solvent and electrolytical application studies.
The advantage of present widely used liquid electrolyte is the conductivity height, but owing to contain inflammable, volatile organic solvent, it discharges fuel gas in charge and discharge process, particularly under some unconventional condition of work (as high-powerly discharge and recharge, super-charge super-discharge etc.) generation that produces big calorimetric meeting accelerating gas, cause inner pressure of battery to increase, gas-liquid is leaked, even blast on fire, thereby has serious potential safety hazard.Liquid electrolytic plastidome also exists poor heat stability, the high deficiency of solidifying point simultaneously, and conductivity sharply descends at low temperatures, and electrolyte easily decomposes rotten under the high temperature.These problems have all seriously restricted the particularly development of high-power performance of novel battery and capacitor.
The objective of the invention is provides a kind of safe, compound electrolyte material that chemical property is good for the deficiency that solves prior art.The main constituent of this compound electrolyte material, both low temperature or room temperature fused salt by under the room temperature for solid, dystectic organic compound and lithium salts make after mixing, the material of formation down for liquid, has good thermal stability in room temperature (or low temperature).According to the ionic liquid action principle, in ionic compound, active force between the yin, yang ion is the Coulomb force, its size is relevant with the amount of charge and the radius of yin, yang ion, by composition and the proportioning of selecting to be fit to, mixes back yin, yang interionic and forms interactions such as coordinate bond, cause its intermolecular force to weaken, destroy original molecular grating energy, thereby the fusing point reduction, keep liquid in room temperature.Compare with liquid electrolyte, this molten salt system thermal stability height, conductivity is big, electrochemical window is wide, as is applied to lithium rechargeable battery, under the improper user mode such as can effectively avoid overcharging, the generation of lithium ion battery dendrite, the danger of avoiding short circuit to cause catching fire or explode.
By compound with membrane for polymer or raw material, organic solvent, can form gel polymer electrolyte, it not only has the characteristics that thermoplastic polymer easily shapes, realize that simultaneously barrier film contacts with the complete of electrode, improved the compactness of adhering at interface, thereby reduced the interface impedance and the internal resistance of cell of electrolyte and electrode, helped large current density.In conjunction with characteristics such as its Heat stability is good, ionic conductivity height, chemical property be good, therefore can produce, be easy to design continuously, technology is simple, safe, at aspects such as lithium ion battery, electric chemical super capacitors wide application prospect is arranged, also be applicable to the fields such as electric automobile of demand high security, high-energy-density and high-power battery, capacitor.
Summary of the invention
Main contents of the present invention are:
1. compound electrolyte material is the low temperature that formed by organic compound that contains amide groups functional group and lithium salts or room temperature fused salt and the gelatinous material that is composited with macromolecular material and organic solvent;
The described organic compound that contains amide groups functional group is a kind of in the following structural formula:
R wherein
1-R
5Identical or different, optionally by the direct keyed jointing mutually of singly-bound or two key, and have following implication :-H ,-halogen ,-phenyl ,-trifluoromethyl or-alkyl; Wherein the H in the alkyl can partially or completely be replaced by other groups;
Described lithium salts comprises lithium perchlorate, lithium hexafluoro phosphate, LiBF4, trifluoromethyl sulfonic acid lithium, two (trifluoromethyl sulphonyl) imines lithium, two (polyfluoro alkoxyl sulphonyl) imines lithium, two (sulphonyl) imines lithiums of ring-type perfluoroalkyl, three (trifluoromethyl sulphonyl) lithium methide; They can use separately, also can two or more mixing use;
Lithium salts is selected foundation: first-selected monovalent anion (degree of ionization height, the animal migration of lithium ion is good), (radius is big, and intermolecular force is little, and molten point is low for suitable ionic radius; Excessive, then require too high to the membrane for polymer aperture) with polymer is compound.For example in lithium salts, the conductivity height of (1) lithium perchlorate, but its oxidizability is strong, easily burns in the time of in joining organic solvent, therefore only limits to experimental study at present and uses; And low, the Heat stability is good of the molten point of the room temperature of its formation (or low temperature) fused salt, chemical property is good, can be applicable to the commodity battery.(2) the lithium hexafluoro phosphate conductivity is the highest, but its heat decomposition temperature low (30 ℃) is easy to be decomposed into PF
5And LiF, and cause the electrolyte polymerization; And the room temperature of its formation (or low temperature) fused salt can effectively strengthen its thermal stability, prevents that electrolyte decomposition is rotten.(3) two (trifluoromethane sulfonic acid acyl) imines lithium conductivity in polyfluoro imines lithium system is the highest, and its thermal stability is good, its high comprehensive performance of coupled ion radius factor.(4) three (trifluoromethyl sulphonyl) lithium methide stability in present lithium salts is best, and the result of thermogravimetric analysis shows in nitrogen atmosphere, and it does not decompose in the time of 400 ℃ yet; Conductivity height, these advantageous properties are mainly bigger owing to its ionic radius, and its anion radius (0.375nm) is maximum in the present lithium salts, and therefore than easily ionizable, electrochemical window is more than 4.0V.
Described macromolecular material comprises the polyethers based material based on polyethylene glycol oxide; With the polyacrylonitrile is the polymer of base; Polymethacrylates; The Kynoar based polymer; Polypropylene, polythene material and composite membrane thereof; Poly-phosphine piperazine; Above-mentioned polymer adds the composite polymeric materials that inorganic powder prepares;
Described organic solvent comprises: expression formula is straight chain or the cyclic organic carbonates of R`OCOOR``, and R` and R`` are alkyl independently, as vinyl carbonate, propylene carbonate, diethyl carbonate, dimethyl carbonate; Expression formula is chain or the ring-type ethers of R`OR``, as dimethoxy-ethane, diethoxyethane, oxolane; Expression formula is chain or the cyclic carboxylic esters class of R`COOR``, as gamma-butyrolacton, methyl formate; The ketal class.
In the research above organic solvent is suitably controlled, because the addition of above-mentioned organic solvent is when too much, its inflammability will have influence on the thermal stability of compound electrolyte material itself.Therefore, also can use as the nonflammable solvent that generally is added in the electrolyte for lithium secondary batteries: phosphoric acid ester, as trimethyl phosphate, triethyl phosphate, tricresyl phosphate (trifluoromethyl) ester, tricresyl phosphate (three perfluor ethyls) ester.
With an organic solvent be not limited to these, they can use separately, also can two or more mixing use.Different composition, proportioning and applications selects appropriate organic solvent to carry out modification in the combined electrolysis plastidome based on room temperature (or low temperature) fused salt, reduces system viscosity, further improves conductivity.Directly add a little organic solvent in molten salt system (volume content 10%～30%), than the liquid electrolyte that commodity use, conductivity is suitable, and electrochemical stability and thermal stability height, high safety.
2. by regulating the composition and the proportioning of interior organic compound of low temperature or room temperature fused salt and lithium salts, carry out addition with macromolecular material, organic solvent, be compounded to form the gelatin polymer composite electrolyte and have low-corrosiveness, bigger liquid range, good thermal stability and chemical property, can effectively be used at aspects such as battery (as lithium ion battery, solar cell etc.), ultracapacitor and electro-deposition.
Embodiment
Embodiment 1:
With LiN (CF
3SO
2)
2With put into glove box (content of water is less than 1ppm), weighing 20gLiN (CF after the acetamide drying
3SO
2)
2And the 30g acetamide at room temperature becomes transparent liquid through stirring, the formation room temperature fused salt in measuring cup.Measure its thermal property with DSC2010 (TA company, the U.S.) differential scanning calorimeter, its fusing point is-60 ℃.
This sample is put in the bright conductance electrode of platinum (Russell, Shanghai), used CHI 660A (U.S.) type electrochemical workstation to adopt the AC impedance method to measure its conductivity in the 1Hz-100KHz scope, its room temperature (25 ℃) conductivity is 1.2mS/cm; With WD4005 (F) type high-low temperature chamber (milky way, Chongqing) coupling, the conductivity under the sample different temperatures to be measured, conductivity varies with temperature curved line relation and meets the VTF equation.This sample work electrode of packing into is platinized platinum, is in the glass three-electrode electro Chemical cell of metal lithium sheet to electrode and reference electrode, use CHI 660A (U.S.) type electrochemical workstation to adopt the cyclic voltammetric method to measure its electrochemical window, sweep speed is 0.1mV/s, measuring range is 1-4.5V, occurs oxidation peak near the 3.8V.
Based on above-mentioned preparation room temperature fused salt good electrochemistry, thermal property, itself and vinylidene fluoride-hexafluoropropylene copolymer and EC+PC organic solvent are compounded to form gel electrolyte.
This composite gel electrolyte is packed in the lithium ion Analog battery die, and pole piece is a stainless steel substrates, and take out from glove box the sealing back.Use CHI 660A type electrochemical workstation to adopt the AC impedance method to measure its conductivity in the 1Hz-100KHz scope, 25 ℃ of conductivity of room temperature can reach 1.1mS/cm.
The electrochemical window of composite polymer electrolyte adopts the cyclic voltammetric method to measure.Sample is sandwiched between the stainless steel blocking electrode (as work electrode) and metal lithium sheet electrode (as to electrode and reference electrode) of finishing polish, take out from glove box the sealing back, and the sweep speed with 0.2mV/s in 2.0～5.0V voltage range is carried out linear scan.Along with the increase of all numbers of scanning, the oxidation peak current potential is stabilized in about 4.0V.
Embodiment 2:
Good electric chemistry, thermal property based on preparation room temperature fused salt among the embodiment 1 combine the formation composite electrolyte with it with Kynoar or vinylidene fluoride-hexafluoropropylene copolymer.
The preparation method adds vinylidene fluoride-hexafluoropropylene copolymer particle wiring solution-forming in acetone, LiTFSI-acetamide electrolyte solution with configuration joins in the above-mentioned solution again, fully mix, make gel polymer electrolyte solution, gel polymer electrolyte solution is coated in the electrode surface of having made respectively, is assembled in then in the ultracapacitor simulated battery.
This ultra-capacitor Heat stability is good than electric capacity height, has good environmental stability and useful life, no leakage, and than the easier assembling of liquid electrolyte ultra-capacitor, environmentally safe.
Claims (2)
1. compound electrolyte material is characterized in that: low temperature that this composite electrolyte is formed by organic compound that contains amide groups functional group and lithium salts or room temperature fused salt and the gelatinous material that is composited with macromolecular material and organic solvent;
The described organic compound that contains amide groups functional group is a kind of in the following structural formula:
R wherein
1-R
5Identical or different, optionally by the direct keyed jointing mutually of singly-bound or two key, and have following implication :-H ,-halogen ,-phenyl ,-trifluoromethyl or-alkyl; Wherein the H in the alkyl can partially or completely be replaced by other groups; Described lithium salts comprises lithium perchlorate, lithium hexafluoro phosphate, LiBF4, trifluoromethyl sulfonic acid lithium, two (trifluoromethyl sulphonyl) imines lithium, two (polyfluoro alkoxyl sulphonyl) imines lithium, two (sulphonyl) imines lithiums of ring-type perfluoroalkyl, three (trifluoromethyl sulphonyl) lithium methide;
Described macromolecular material comprises the polyethers based material based on polyethylene glycol oxide; With the polyacrylonitrile is the polymer of base; Polymethacrylates; The Kynoar based polymer; Polypropylene, polythene material and composite membrane thereof; Poly-phosphine piperazine; Above-mentioned polymer adds the composite polymeric materials that inorganic powder prepares;
Described organic solvent comprises that expression formula is chain or the cyclic organic carbonates of R`OCOOR``; Expression formula is chain or the ring-type ethers of R`OR``; Expression formula is chain or the cyclic carboxylic esters class of R`COOR``; The ketal class; Nonflammable solvent phosphoric acid ester.
2. by the described compound electrolyte material of claim 1, it is characterized in that: by the composition and the proportioning of organic compound and lithium salts in adjusting low temperature or the room temperature fused salt, carry out addition, form the gelatin polymer composite electrolyte with macromolecular material, organic solvent.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2003101173508A CN1323460C (en) | 2003-12-11 | 2003-12-11 | A novel composite electrolyte material |
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| CNB2003101173508A CN1323460C (en) | 2003-12-11 | 2003-12-11 | A novel composite electrolyte material |
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| CN1547216A CN1547216A (en) | 2004-11-17 |
| CN1323460C true CN1323460C (en) | 2007-06-27 |
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Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100526355C (en) * | 2006-12-22 | 2009-08-12 | 中国科学院兰州化学物理研究所 | Polymeric ionic liquid based gel polymer electrolyte and preparation thereof |
| CN101162650B (en) * | 2007-05-29 | 2010-06-30 | 中南大学 | Flexible thin film type solid-state super capacitor and its manufacture process |
| CN101386711B (en) * | 2008-10-24 | 2012-05-23 | 武汉大学 | Solid-liquid compound material and preparation method and application thereof |
| CN101768176B (en) * | 2010-01-25 | 2014-07-02 | 北京理工大学 | Ionic liquid |
| CN103387731A (en) * | 2012-05-08 | 2013-11-13 | 海洋王照明科技股份有限公司 | Gel polymer electrolyte membrane and preparation method thereof |
| CN103456506A (en) * | 2012-05-31 | 2013-12-18 | 海洋王照明科技股份有限公司 | Preparation method of polypropylene nitrile gel polymer electrolyte capacitor |
| KR20140045880A (en) | 2012-10-09 | 2014-04-17 | 가부시키가이샤 한도오따이 에네루기 켄큐쇼 | Power storage device |
| CN106654365A (en) * | 2013-01-23 | 2017-05-10 | 浙江地坤键新能源科技有限公司 | Solid polymer electrolyte-based composite gel polymer electrolyte and preparation method and application thereof |
| JP6613474B2 (en) * | 2016-01-14 | 2019-12-04 | 国立大学法人 東京大学 | Aqueous electrolyte for power storage device and power storage device including the aqueous electrolyte |
| CN106967998B (en) * | 2017-05-19 | 2018-10-02 | 东北大学 | The method for preparing Al-Li master alloys as the nearly room temperature electro-deposition of raw material using lithia |
| CN112701420A (en) * | 2021-01-23 | 2021-04-23 | 山东天瀚新能源科技有限公司 | Multifunctional diaphragm for lithium battery, preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1064584A (en) * | 1996-08-13 | 1998-03-06 | Fujitsu Ltd | Nonaqueous electrolyte for lithium secondary battery |
| JPH11273728A (en) * | 1998-01-22 | 1999-10-08 | Sony Corp | Nonaqueous electrolyte battery |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH1064584A (en) * | 1996-08-13 | 1998-03-06 | Fujitsu Ltd | Nonaqueous electrolyte for lithium secondary battery |
| JPH11273728A (en) * | 1998-01-22 | 1999-10-08 | Sony Corp | Nonaqueous electrolyte battery |
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Granted publication date: 20070627 Termination date: 20161211 |