CN1242877A - Highly conductive ion exchange polymer and process - Google Patents
Highly conductive ion exchange polymer and process Download PDFInfo
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Abstract
Disclosed is a highly conductive polymer electrolyte membrane and a process for producing it. This invention also describes batteries which employ the polymer electrolyte membrane of this invention.
Description
Invention field
The present invention relates to high conductivity polymer dielectric film and production technology thereof.More particularly, the present invention relates in non-water environment, demonstrate greater than 10
-4The lithium ion exchange polymer dielectric film of the conductance of S/cm.The present invention also relates to adopt the battery of polymer dielectric film of the present invention.
The invention technical background
Guglielmi etc. [J.Appl.Electrochem., 19,167 (1989)] disclose perfluorinate lithium ion exchange polymer electrolyte gel.Disclosed gel is by making Nafion
1100 perfluorinate ionomer resins are dissolved in the middle formation of N-methylformamide (NMF), propylene carbonate (PC) and triethyl phosphate (TEP).Obtained surpassing 10
-4The conductance of S/cm.Also disclose when solution is heated to 80 ℃, had the ratio electricity of the property followed to lead increase, measured value reaches about 7.5 * 10 under this high temperature
-3S/cm.Solvent surpasses 3: 1 (weight) with the ratio of polymer in this gel.Disclosed gel can not form the self-supporting film in this article.
Aldbert etc. [Polymer Journal, 23,399 (1991)] disclose the perfluorinated sulfonic acid ionomer, and wherein cation is hydrogen, lithium, sodium and rubidium, and wherein ionomer is the form of a kind of solution or a kind of solvent swell film.50/50 mixture of PC and dimethoxy-ethane demonstrates and can increase they and lithium ionomer type Nafion especially effectively
The conductivity of 1100 gel solutions that form.Lithium ionomer type Nafion
1100 films that form are with PC, NMF and ethanol swelling.According to open, after about 10 minutes, the ratio electricity of this film is led and is not demonstrated further increase at the room temperature soaked in solvent.For the film that soaks in NMF less than 10 minutes, actual measurement is led up to 1.8 * 10 than electricity
-3S/cm.Film with the PC swelling provides 6 * 10
-5The ratio electricity of S/cm is led.Preceding a kind of solvent can not be used for lithium battery because of its proton transfer character.Propylene carbonate is known technically to be a kind of good lithium battery solvent, but Aldbert etc. are disclosed at Nafion
Conductivity in 1100 films is lower than 10
-4S/cm is too poor and do not have actual utility.Solvent and the ratio of polymer were less than 1: 1 in this solvent swell film.
At the J.Electrochem.Soc. of Zawodzinski etc., in 140,1041 (1993), a kind of Nafion
1100 films are heated to 105 ℃, are exposed to water in room temperature then.The effect of this heating is will prevent to reach the absorption maximum effect, thereby reduces the conductance of water-soluble bloated film.
" the ionic conducting polymer " of M.B.Armand [Solid State Batteries, Sequeira and Hopper compiles (1985)] discloses the lithium ionomer type Nafion that soaked 48 hours in PC
1100 show 2.1 * 10
-5The ratio conductivity of S/cm.The conductivity that Armand also discloses the solvent soaking film increases with temperature according to a kind of free volume pattern.The same with people such as Aldbert, conductivity disclosed herein is too poor, does not have actual utility in commercial lithium battery.
The metastable state that Miura etc. [Memoirs of Faculty of Tech.Tokyo MetropolitanUniv., No.40, pp 4349ff, 1990] have described its ion cluster form when perfluorinated ionomers is used ethanol swelling subsequent drying changes.
Gebel etc. [Polymer, v.34, pp 333ff, 1993] disclose the perfluor lithium ionomeric membrane of swelling in comprising numerous solvents of propylene carbonate and phosphate.According to open, phosphate can provide king-sized swelling amount.Disclose and in some solvents such as propylene carbonate, soaked the necessity that schedules to last several weeks.Ionic conductivity is not done any discussion.
[the ratio conductivity of two (fluoroform sulphonyl) imidization lithiums (LiTFSI) in non-proton transitivity solvent mixture such as Perron, Abstract 64 of Battery/EnergyTechnology Joint General Session of Meeting Abstracts, Electrochemical Society May 4-9,1997 meeting, Montreal, Quebec, Canada] dimethoxy-ethane (DME) that discloses as the lithium salts good solvent can provide the height ratio conductivity for its solution.According to open, the solution of non-polymer lithium salts in some non-proton transitivity solvent combination under the solubility condition of limited, can provide the extra high conductivity that compares at dielectric film in the solvent that can give high conductance.The mixture of DME and propylene carbonate is disclosed.A small amount of PC does not have significantly to change the conductivity of electrolyte solution among the DME.
The lithium battery non-aqueous electrolyte is disclosed in the U.S. Patent No. 5,525,443 of Okuno etc.Disclosed is the lithium salt solution that the solvent with linear ester and cyclic ester is combined to form, cyclic ester is selected from a group that ethylene carbonate, propylene carbonate, butylene carbonate and gamma-butyrolacton are formed, and linear ester is selected from a group that diethyl carbonate, dimethyl carbonate, Ethyl formate, methyl formate, ethyl acetate, methyl acetate and dimethyl sulfoxide (DMSO) are formed.
Brief summary of the invention
The invention provides and a kind ofly in non-aqueous media, demonstrate at least 10
-4The ionic conductivity of S/cm, highly fluorinated lithium ion exchange polymer dielectric film (FLIEPEM).FLIEPEM of the present invention is a kind of so-called single ion conductor, thereby, concentration polarization does not take place in electrochemical applications such as battery.The invention provides to demonstrate and surpass 10
-4The ionic conductivity of S/cm, the first kind of single ion conductor that is a kind of ion conductive polymer electrolyte membrane form and the disposable lithium-battery made from it.
The invention provides a kind of highly fluorinated lithium ion exchange polymer dielectric film (FLIEPEM) of the conductivity of 0.1mS/cm at least that demonstrates, wherein comprise a kind of highly fluorinated lithium ion exchange polymer membrane (FLIEPM), this polymer has side chain Fluoroalkyloxy sulfonic acid lithium group, and wherein this polymer is a cation exchange fully or partly; At least a non-proton transitivity solvent that is absorbed in the described film, this FLIEPEM are characterised in that as following defined conductivity parameter value (CPV) be 0.3mS/cm or bigger.
Further provide the technology of a kind of FLIEPEM of formation, this technology comprises allows a kind of FLIEPM contact in-40~200 ℃ temperature range in a kind of dry environment with at least a non-proton transitivity solvent, this solvent and combination of polymers have the CPV of 0.3mS/cm at least, form a kind of conductance and are the FLIEPEM of 0.1mS/cm at least.
The invention further provides a highly fluorinated lithium ion exchange polymer electrolyte membrane
(FLIEPEM), comprising a highly fluorinated lithium ion exchange polymer membrane , the polymer
Side chain fluoroalkoxy lithium sulfonate groups , wherein the polymer is completely or partially cation
Exchange ; and at least one absorbent polymer in the film in said aprotic solvent , the
FLIEPEM characterized in that the conductivity of at least 0.1mS/cm, one or more aprotic
Solvent is selected from the group : dimethylformamide (DMF), dimethoxyethane (DME),
Ethylene carbonate (EC), propylene carbonate (PC), dimethyl sulfoxide (DMSO),
γ- butyrolactone (GBL), N, N'- dimethyl propylene urea (DMPU), 1 - methyl-
-2 - Pyrrolidone (NMP), dimethylacetamide (DMA), N, N'- dimethyl-
Butyramide (DMB), triethyl phosphate (TEP), N, N'- di-n -butyl -acetamide
(DBA), and mixtures thereof ; or a PC from DME, EC, GBL, dimethyl carbonate
Ester (DMC) , and acrylonitrile (ACN) selected from the group consisting of a mixture of a solvent
Thereof; or EC from DME, GBL, DMSO, diethoxyethane (DEE)
And DMC selected from the group consisting of a mixture of solvents ; or NMP and from
DME, DMSO, GBL, DMF and DMA selected from the group consisting of a solvent
Mixture ; or GBL with DEE or DME mixture ; or EC and DME
From diethyl carbonate (DEC), DMC , and PC selected from the group consisting of a solvent
Mixture ; or DMF from the DMA, DMSO, NMP, methyl glycolate
(MG), GBL, TEP, EC, DME, PC, methyl formate (MF), four
Tetrahydrofuran (THF), sulfolane (SULF), DMC, ACN, methyl acetate (MA),
DEC, 1,3 - dioxolane (DIOX), DEE, ethyl acrylate (EA) and thionyl
Dimethyl ester (DMSU) selected from the group consisting of a mixture of a solvent ; or
DMA from DMSO, NMP, MG, GBL, TEP, EC, DME, PC,
MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE,
EA and DMSU selected from the group consisting of a mixture of solvents ; or DMSO
From NMP, MG, GBL, TEP, EC, DME, PC, MF, THF,
SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU
Selected from the group consisting of a mixture of a solvent ; or NMP from the MG,
GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC,
ACN, MA, DEC, DIOX, DEE, EA, and DMSU the group consisting of
A mixture of a solvent selected ; or MG from GBL, TEP, EC, DME,
PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX,
DEE, EA, and DMSU selected from the group consisting of a mixture of solvents ; or
GBL from the TEP, EC, DME, PC, MF, THF, ACN, MA,
DEC, DIOX, and EA selected from the group consisting of a mixture of solvents ; or
TEP from EC, PC, SULF, ACN , and DMSU selected from the group consisting of a
A mixture of solvents ; or a mixture of EC and DME ; or DME and ACN
Or mixtures DMSU ; or EC, DMF from the DMA, DMSO, NMP,
MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC,
ACN, MA, DEC, DIOX, DEE, EA, and DMSU group consisting of solvent
Agent in a solvent mixture selected ; or EC, DMA from the DMSO,
NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF,
DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU composition
A group selected from a solvent mixture ; or EC, DMSO and from NMP,
MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC,
ACN, MA, DEC, DIOX, DEE, EA, DMSU selected the group consisting of
A mixture of a solvent selected ; or EC, NMP from the MG, GBL, TEP,
DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC,
DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent mixture of
Thereof; or EC, MG from GBL, TEP, DME, PC, MF, THF,
SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU
Selected from the group consisting of a mixture of a solvent ; or EC, GBL from the TEP,
DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC,
DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent mixture of
Thereof; or EC, TEP from DME, PC, MF, THF, SULF, DMC,
ACN, MA, DEC, DIOX, DEE, EA, and DMSU the group consisting of
A mixture of a solvent selected ; or EC, DME from the MF, THF,
SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU
Selected from the group consisting of a mixture of a solvent ; or EC, MF and DEC or
DIOX mixture ; or EC, THF and mixtures of DEC or DIOX ; or
Yes EC, DMC and DIOX mixture ; or EC, DEC mixed with DIOX
Thereof; or a PC, DMF and from the DMA, DMSO, NMP, MG, GBL,
TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA,
DEC, DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent
Mixture ; or a PC, DMA from the DMSO, NMP, MG, GBL,
TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA,
DEC, DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent
Mixture ; or a PC, DMSO from NMP, MG, GBL, TEP, EC,
DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX,
DEE, EA, and DMSU selected from the group consisting of a mixture of solvents ; or
A PC, NMP and from the MG, GBL, TEP, EC, DME, MF, THF,
SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU
Selected from the group consisting of a mixture of a solvent ; or a PC, MG and from GBL,
TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA,
DEC, DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent
Mixture ; or a PC, GBL from the TEP, EC, DME, MF, THF,
DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU composition
A group selected from a solvent mixture thereof; or a PC, TEP from EC, DME,
MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE,
EA, and DMSU selected from the group consisting of a mixture of solvents ; or a PC,
DME from THF, DEC, and DIOX selected from the group consisting of a solvent mixture of
Thereof; or DMC, DMA from the DMSO, NMP, MG, GBL, TEP,
EC, DME, PC, MF, THF, SULF, ACN, MA, DEC,
DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent mixture of
Thereof; or DMC, DMSO from NMP, MG, GBL, TEP, EC,
DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX,
DEE, EA, and DMSU selected from the group consisting of a mixture of solvents ; or
The DMC, NMP and from the MG, GBL, TEP, EC, DME, PC, MF,
THF, SULF, ACN, MA, DEC, DIOX, DEE, EA, and DMSU
Selected from the group consisting of a mixture of a solvent ; or DMC, MG and from
GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA,
DEC, DIOX, DEE, EA, and DMSU selected from the group consisting of a solvent
Mixture ; or DMC, GBL from the TEP, EC, DME, PC, MF,
THF, ACN, MA, DEC, DIOX, and EA selected from the group consisting of a
Mixtures of solvents ; or DMC, TEP from EC, PC, SULF , and ACN group
Selected from the group into a mixture of a solvent ; or DMC, EC and DME or
DIOX mixture ; or DMC, DME and ACN mixture ; or DME,
DMF from the DMA, DMSO, NMP, MG, GBL, TEP, EC, PC,
MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE,
EA, and DMSU selected from the group consisting of a mixture of solvents ; or DME,
DMA from DMSO, NMP, MG, GBL, TEP, EC, PC, MF,
THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA,
And DMSU selected from the group consisting of a mixture of solvents ; or DME,
DMSO from NMP, MG, GBL, TEP, EC, PC, MF, THF,
SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, and DMSU
Selected from the group consisting of a mixture of a solvent ; or DME, NMP and from
MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN,
MA, DEC, DIOX, DEE, EA, and DMSU selected from the group consisting of a
A mixture of solvents ; or DME, MG from GBL, TEP, EC, PC,
MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE,
EA, and DMSU selected from the group consisting of a mixture of solvents ; or DME,
GBL from the TEP, EC, PC, MF, THF, SULF, DMC, ACN,
MA, DEC, DIOX, DEE, EA, and DMSU selected from the group consisting of a
A mixture of solvents ; or DME, TEP from EC, PC, SULF, ACN,
And DMSU selected from the group consisting of a mixture of solvents ; or DME, EC
From MF, THF, SULF, DMC, ACN, MA, DEC, DIOX,
DEE, EA, and DMSU selected from the group consisting of a mixture of solvents ; or
The DME, PC from THF, DEC, and DIOX selected from the group consisting of a solution
Mixtures ; or DME, MF and mixtures SULF or ACN ; or
DME, THF and the mixture of SULF or ACN ; or DME, SULF and DEC
Mixtures or DIOX ; or DME, DMC and ACN mixture ; or
DME, ACN and from MA, DEC, DIOX, DEE, EA and DMSU composition
A group selected from a solvent mixture thereof.
Further provide the forming technology of FLIEPEM, this technology comprises makes a kind of FLIEPM contact in-40~200 ℃ temperature range in dry environment with at least a non-proton transitivity solvent, forms a kind of FLIEPEM of the conductivity of 0.1mS/cm at least that has; Described solvent is selected from the solvent in the preceding paragraph.
The present invention further provides a kind of lithium ion battery group, comprise one or more electrochemical cells, comprise wherein that a positive pole, negative pole, one are disposed between positive pole and the negative pole and with its be in that ionic conduction contacts, the FLIEPEM of 0.1mS/cm conductivity at least arranged, with a kind of means that these electrodes are connected with external electrical load or power supply of being used to.
The present invention also further provides a kind of porous electrode, wherein comprises a kind of electrode active material particles, a kind of highly fluorinated lithium ion exchange polymer and at least a being applicable to and implements non-proton transitivity solvent of the present invention.
The present invention further provides a kind of electrode forming again, and this technology comprises: form a kind of solution or dispersion liquid that the highly fluorinated polymers of side chain Fluoroalkyloxy sulfonic acid lithium or sulfuryl fluoride group is arranged; In this solution or dispersion liquid, sneak into a kind of electrode active material of a granular form, form a kind of coating paste; Form a kind of film from this coating paste; By heating, make the polymer in this film coalescent; With, if this side-chain radical is a sulfuryl fluoride, then make this polymer hydrolysis become a kind of lithium ionomer.
Brief Description Of Drawings
Fig. 1 shows Nafion
The correlation of (1100 EW) conductivity and solvent parameter.
Fig. 2 shows the lithiumation Nafion with the binary solvent mixture swelling
Correlation between the calculating conductivity of film and the actual measurement conductivity.
Detailed description of the invention
Ion-exchange polymer is known technically is single ion conductor, thereby concentration polarization can not occur in the electrochemistry application. Yet, until before the present invention's proposition, never incumbent what a kind of ion-exchange polymer electrolysis plasma membrane of human hair is suitable in the lithium battery group. The lithium battery group provides and has reached simultaneously high power and high-octane possibility, but to the electrolysis plasma membrane, especially the application of solid polymerization thing electrolysis plasma membrane has proposed strict demand. These requirements comprise the voltage stability to the distinctive height oxidation-reducing condition of lithium battery group, and when proton transitivity chemical seed does not exist at least 10-4The room-temperature conductivity of S/cm. In the past, both not known had such combination in ion-exchange polymer electrolysis plasma membrane, and also nobody proposed any method and can produce lithium ion exchange polymer dielectric film with it. Due to the astonishing discovery of high conductivity FLIEPEM of the present invention, the actual obstacle of lithium and the exploitation of lithium ion battery group has been overcome.
For the present invention, " highly fluoridize " in the hydro carbons hydrogen that this term means similar nonfluorinated polymer at least 90% (mole) by fluorine, replaced. The invention provides that a kind of height is fluoridized, better be fluoridized lithium ion exchange polymer dielectric film (FLIEPEM), comprise that a kind of height that has absorbed at least a non-proton transitivity solvent is fluoridized, better be fluoridized lithium ion exchange polymer membrane (FLIEPEM), this solvent, as following defined electrical conductivity parameter value (CPV) be 0.3 or more than.
For the present invention, " electrical conductivity " used herein this term specially refers to the ionic conductivity of measuring with so-called four-point probe technology, this technology sees the people such as Y.Sone for details at J. Electrochem.Soc., that delivers on 143,1254 (1996) is entitled as " with the Nafion of four electrode AC suspension methods mensuration117 proton conductivity " article. Described method is applicable to water base electrolysis plasma membrane. For the purpose of the measured value that obtains to report here, described device is put in a seal box that has purged with drying nitrogen, to making, any exposure of water is minimized, thereby the method is improved. Also by using parallel linear probe across the sample full duration to replace point probe in institute's presentation method, the method is improved.
Polymer of the present invention is a kind of fluoroolefins homopolymers or copolymer that pendant sulfonic acid lithium group is arranged preferably, and this polymer is completely or partially ion-exchange. Side-chain radical is the lithium salts of fluorine alkoxyl sulfonic acid preferably. Terpolymer contained in " copolymer " used herein this term.
Better polymer of the present invention be a kind of nonionic fluoroolefins monomer with can reach 50% (mole), better can reach 30% (mole), preferably can reach 20% (mole) a kind of copolymer that hand hay cutter chain group is arranged, comprise the ionic fluoroolefins of fluorine alkoxyl sulfonic acid lithium salts. Applicable nonionic fluoroolefins comprise tetrafluoroethene (TFE), hexafluoropropene, PVF, vinylidene fluoride, three PVFs, chlorotrifluoroethylene, perfluor (alkyl vinethene), and composition thereof. Applicable ionic fluoroolefins includes various fluorinated vinyl ether of desirable side chain can be provided in polymer functional group. Being preferably, is the copolymer of tetrafluoroethene and a kind of perfluoroethylene ether sulfonic acid lithium according to polymer of the present invention.
The better polymer that uses in the present invention be TFE with can reach 50% (mole) a kind of copolymer that the perfluoroethylene base monomer of side-chain radical shown in following formula is arranged:
-(O-CF
2CFR)
aO-CF
2CFR′SO
3Li, in formula, R and R ' are independently selected from F, Cl or the perfluorinated alkyl group that 1~10 carbon atom is arranged, a=0,1 or 2. Best is that R is CF3, R ' is F, and a=0 or 1. Polymer comprises preferably, for example, United States Patent (USP) 3,282, disclosed polymer in 875 and in United States Patent (USP) 4,358,545 and 4,940,525, these patents are classified this paper list of references as.
As disclosed in document cited above, better polymer of the present invention is by perfluorinate vinethene shown in tetrafluoroethene (TFE) and following formula.
CF
2=CF (O-CF
2CF (CF
3))
a-O-CF
2CF
2SO
2" a " difference=0 or 1 in the F formula, be perfluor (3-oxa--4-amylene sulfuryl fluoride) or perfluor (3,6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) copolymerization, make the hydrolysis of sulfuryl fluoride group subsequently and change into sulfonate groups, desirable form prepares to change into to carry out lithium ion exchange in case of necessity again.
In the ion-exchange polymer technical field, the concentration of ionic conduction unit is represented with so-called equivalent weight.Be expressed as the equivalent weight of gram/equivalent (g/eq.), mean the gram number of supplying with the needed polymer of monovalent ionic functional degree, can be with titration or spectrographic determination.Can consult, for example, people such as Gary E.Wnek, " based on the novel hydro carbons proton exchange membrane of sulfonated phenylethylene-ethylene/butylene-styrene triblock copolymer ", ElectrochemicalSociety Proceedings Volume 95-23, the 247-250 page or leaf.
The better perfluorinated ion exchange polymer that uses among the present invention, to it is characterized in that scope is arranged be 600~1500g/eq., be preferably the equivalent weight of 900~1200g/eq..
Other thing too, lower equivalent weight is corresponding to higher conductivity.This effect has two reasons.One only is that the per unit weight polymer has higher ion position concentration.Another is, in practice of the present invention, have been found that degree of crystallinity lower, than the film of low equivalent weight, compare with the film of higher equivalent weight, the representation of per unit film illustrates higher solvent absorbability.
In the better perfluorinated ion exchange polymer of Shi Yonging, the lithium group accounts for 1~100%, better 100% of side chain metal cation cation exchange groups sum in the present invention.Conversion deficiency to lithium cation will cause the higher effective equivalent weight.The sour exchanging form of complete hydrolysis can stay many acid groups (H to the conversion deficiency of lithium exchanging form
+), this will make other battery component degenerate, and active hydrogen also will be reduced into hydrogen on anode, thereby deprive in this battery active lithium ion on the electrochemistry.
Technical known any method for hydrolysis in practice of the present invention, all can be used for making perfluorinated ion-exchange polymer to change into perfluorinate lithium ion exchange polymer.Found to make satisfactorily a kind of unhydrolysed sulfuryl fluoride (SO
2F) precursor film changes into the ionomeric a kind of method of lithium and comprises:
1. hydrolysis film is not placed a beaker on the electric hot plate;
2. make this film be immersed in excessive 1.0M LiOH (1: 4 DMSO: water) in the solution, and be heated to T=60~80 ℃ about 2 hours fully;
3. from this beaker, take out the lithium ionomer that produces like this, and rinsing in distilled water, to remove excessive alkali;
4. in T=60~80 ℃, make film heating in the beaker that contains deionized water more than 2 or 2 hour;
5. at~100 ℃ and use N
2This film of heating in the vacuum drying oven that purges, dried overnight.
DMSO is the better solvent of hydrolysis and lithiumation step, but the methyl alcohol equal solvent also can use.
Hydrolysis degree can be in perfluorinated ion-exchange polymer in 1~100% scope of side-chain radical, is preferably 100% hydrolysis.
Then, allow this Li ionomer contact, better absorb until reaching the balance solvent with a kind of non-proton transitivity solvent of the present invention.The practitioner of this gate technique will be appreciated that and as shown below be, after the contact in this polymer contained amount of solvents will depend on exposure condition and the interactional specific nature of solvent/polymer.As what will see in the particular of the following stated, different films/solvent combination needs different exposure conditions just can reach purpose of the present invention.
The boiling point of solvent is not conclusive, but this solvent must be still a kind of liquid under the service condition of being expected.The solidifying point of expecting solvent can reduce because of FLIEPM, and therefore, the Li ionic mobility is expected below the solidifying point of this solvent in these systems.Therefore, boiling point is preferably at least 30 ℃, and best is at least 50 ℃.If this battery pressurizes, then can adopt the above temperature of atmospheric boil.
Have now found that the conductivity of better FLIEPEM of the present invention can be from being appointed as the numerical value of " conductivity parameter value " herein, the calculating of promptly relevant with a solvent parameter and a function of polymer parameter is predicted in high sensitivity.Combination that be suitable for using in the practice of the present invention, polymer and solvent (comprising solvent mixture) is feature with conductivity parameter value (CPV) for 0.3mS/cm at least.Have been found that in practice of the present invention that for the FLIEPEM that has absorbed single solvent the value of CPV can be determined from following equation.CPV (mS/cm)=4.902 * 10
-5((W
3D)/(
η iMW))
0.965In [2.0092-(0.0012EW)] formula
W=100[(W
w-W
d)/W
d] W wherein
wBe the weight that this film adds the solvent that this film absorbs, W
dBe the weight before this film lyosoption." D " is the density of this solvent, represents with g/cc; " η " is the viscosity at ambient temperature of this solvent, represents with centipoise; " MW " is the molecular weight of this solvent, represents with the g/ mole." EW " is the equivalent weight of this hydrolysis film, represents with gram/equivalent.D, η and MW all can obtain from disclosed source.W is to be that related film is measured with experimental technique.
The CPV equation that does not have bracketed equivalent weight correction factor, be to determine by the experimental data that the copolymer that fits within the following particular to the TFE of the about 1100g/eq. of equivalent weight and perfluor (3,6-diaza-4-methyl-7-octene sulfuryl fluoride) provides.As for the personnel that this gate technique technical ability is arranged with conspicuous, all experiments are proofreaied and correct all some intrinsic uncertainties.But, in practice of the present invention, have been found that with CPV be 0.3 or bigger value be that the film of feature has 90% probability to show that conductance is>10
-4S/cm, target promptly of the present invention.Have the personnel of this gate technique technical ability further to recognize, demonstrating conductance, will to be lower than 0.3mS/cm with CPV greater than some films of 0.1mS/cm be feature.
" CPV " used herein this term is contained the FLIEPEMs that has only absorbed a kind of single non-proton transitivity solvent and has been absorbed the FLIEPEMs of non-proton transitivity solvent mixture.Disclosed herein is the different CPV assay methods of single solvent film and solvent mixture film.Yet in both cases, CPV is the conductivity predicted value based on film parameter and solvent parameter, and with regard to purpose of the present invention, CPV is identical for the meaning of single solvent film and solvent mixture film.
Fig. 1 does not carry out bracketed equivalent weight correction with the relation of diagrammatic representation explanation disclosed experimental data and the defined line of CPV equation in following particular of the present invention.
The different sulfonic acid Li ionomer of equivalent weight and/or perfluoroolefine Fluoroalkyloxy sulfonate comonomer demonstrates in the CPV equation conductivity to the different functional dependences of solvent parameter, and is pointed as the factor in the CPV equation bracket.Equivalent weight correction factor determination of experimental method.
The weight intake of solvent can easily be determined with the minimum time cost with laboratory equipment in a kind of film of selecting.The sample of this film only needs weigh before solvent exposes, and is exposed to the alternative solvent under the anhydrous condition then, open-assembly time scope be 10 minutes~1000 hours, the Exposure Temperature scope is room temperature~230 ℃, be preferably room temperature~90 ℃, last, after from solvent is bathed, taking out, weighing again.
For the personnel that this gate technique technical ability is arranged, it is evident that, the conductivity of FLIEPEM partly depends on the weight % intake of solvent, and for any given solvent and FLIEPEM, weight % intake can accomplish one depend on the solvent contact conditions quite on a large scale in change, therefore, also can accomplish to change in quite on a large scale with the conductivity that a kind of specific FLIEPEM reached at one.Be suitable for the solvent of the present invention practice and film conductivity more than the 0.1mS/cm can be provided under at least some soaking conditionses.Under the situation of some solvents, a kind of specific FLIEPM has only the solvent condition of a certain narrow range can cause providing the film of target of the present invention.In other cases, target of the present invention is to provide in the solvent contact conditions scope of broadness.
Find on the battery pack designing technique that the combination of multiple solvent is favourable often.Although use above equation to determine that it is time-consuming but reasonably that necessity of the needed solvent parameter of conductivity of the alternative solvent that uses in the lithium battery group is measured, but, it is heavy especially carrying out all necessary mensuration that the solvent combined sorting uses.Yet,, just can avoid this point according to following conductivity of mixture method of estimation.Some solvents combinations have been listed in a kind of 1100g/eq. Li ionomer of making from the copolymer of TFE and perfluor (3,6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) greater than 0.3 CPV calculated value in table 1~5.The parameter of mixture equation makes up resulting actual experiment data by illustrational some solvent below the match and obtains.
Find in the embodiment of this invention, with the ionomeric CPV of a kind of lithium that a kind of group of solvents splice grafting touches can be from following Equation for Calculating
This equation is the binary solvent mixture that utilizes 1: 1 solvent volume ratio, determines with experimental technique.CPV
MixBe the conductivity who is used for making every kind of solvent in the mixture of this Nafion swelling
iThe summation of contribution, σ
iDetermine from following formula
σ in the formula
i MeasBe conductance measurement value with the film of the independent swelling of i kind solvent in the mixture, the mS/cm of unit; W%
MixThe weight percent of solvent intake in the film when being usefulness solvent mixture swelling is in order to following Equation for Calculating
X in the formula
iDetermine by following formula
In the formula to " j " and be to all solvent compositions in the mixture and, ε
iAnd DN
iBe respectively dielectric constant and coenosarc number; η
iBe the viscosity of i kind composition in the solvent mixture, represent with centipoise; ε
i MaxBe used to refer to the maximum in all dielectric constants; Promptly to every kind of solvent in the mixture do dielectric constant relatively and select maximum.The donor number is defined as a kind of basicity of solvent by Gutmann (V.Gutmann and E.Wychera, Inorg.Nucl.Chem.Letters, 2,257 (1966)).It is the negative enthalpy of this lewis acid reaction of this solvent and Antimony pentachloride.W%
i MeasIt is film measured value of weight intake in this film during with the independent swelling of i kind solvent; η
MixIt is the viscosity number of representing with centipoise with the solvent mixture that following approximate formula is calculated
" exp " is act function or antilogarithm in the formula, ∑ represent to all solvents in this mixture and, and ln is the natural logrithm function.
Table 1
The Conductivity Calculation value of binary solvent mixture
Solvent #2 | ?DMF | ??DMA | ?DMSO | ??NMP | ?MG | ??GBL | ?TEP | ??EC | ??DME | ?PC | ??MF | ?THF | ??SULF | ??DMC | ??ACN | ??MA | ??DEC | ??DIOX | ??DEE | ??EA | ???DMSU |
Solvent #1 | |||||||||||||||||||||
?DMF | ?1.67 | ??2.00 | ?2.18 | ??1.55 | ?1.82 | ??1.23 | ?1.40 | ??3.70 | ??1.65 | ?2.31 | ??1.59 | ?1.55 | ??1.61 | ??1.53 | ??1.54 | ??1.55 | ??1.57 | ??1.56 | ??1.62 | ??1.51 | ???1.55 |
?DMA | ?2.00 | ??2.43 | ?2.57 | ??1.87 | ?2.27 | ??1.36 | ?1.70 | ??4.07 | ??2.31 | ?2.55 | ??2.25 | ?2.16 | ??1.94 | ??2.11 | ??2.04 | ??2.18 | ??2.20 | ??2.18 | ??2.31 | ??2.09 | ???2.16 |
?DMSO | ?2.18 | ??2.57 | ?1.85 | ??1.87 | ?2.33 | ??1.16 | ?1.55 | ??2.37 | ??1.90 | ?1.44 | ??1.76 | ?1.69 | ??1.21 | ??1.65 | ??1.61 | ??1.70 | ??1.70 | ??1.69 | ??1.77 | ??1.63 | ???1.66 |
?NMP | ?1.55 | ??1.87 | ?1.87 | ??1.01 | ?1.18 | ??0.80 | ?0.83 | ??2.23 | ??1.07 | ?1.34 | ??1.01 | ?0.98 | ??0.96 | ??0.92 | ??1.19 | ??0.98 | ??0.97 | ??0.99 | ??0.98 | ??0.94 | ???0.92 |
?MG | ?1.82 | ??2.27 | ?2.33 | ??1.18 | ?0.53 | ??0.87 | ?0.39 | ??2.56 | ??0.56 | ?1.51 | ??0.54 | ?0.52 | ??1.10 | ??0.47 | ??1.57 | ??0.52 | ??0.52 | ??0.55 | ??0.51 | ??0.50 | ???0.72 |
?GBL | ?1.23 | ??1.36 | ?1.16 | ??0.80 | ?0.87 | ?0.51 | ??0.59 | ??0.42 | ?0.31 | ??0.34 | ?0.35 | ??0.31 | ??0.32 | ??0.35 | ??0.39 | ??0.32 | |||||
?TEP | ?1.40 | ??1.70 | ?1.55 | ??0.83 | ?0.39 | ??0.51 | ??1.17 | ?0.66 | ??0.48 | ??0.72 | ????0.32 | ||||||||||
?EC | ?3.70 | ??4.07 | ?2.37 | ??2.23 | ?2.56 | ??0.59 | ?1.17 | ??0.56 | |||||||||||||
?DME | ?1.65 | ??2.31 | ?1.90 | ??1.07 | ?0.56 | ??0.42 | ??0.56 | ??0.47 | ????0.31 | ||||||||||||
?PC | ?2.31 | ??2.55 | ?1.44 | ??1.34 | ?1.51 | ??0.31 | ?0.66 | ||||||||||||||
?MF | ?1.59 | ??2.25 | ?1.76 | ??1.01 | ?0.54 | ??0.34 | |||||||||||||||
?THF | ?1.55 | ??2.16 | ?1.69 | ??0.98 | ?0.52 | ??0.35 | |||||||||||||||
?SULF | ?1.61 | ??1.94 | ?1.21 | ??0.96 | ?1.10 | ?0.48 | |||||||||||||||
?DMC | ?1.53 | ??2.11 | ?1.65 | ??0.92 | ?0.47 | ||||||||||||||||
?ACN | ?1.54 | ??2.04 | ?1.61 | ??1.19 | ?1.57 | ??0.31 | ?0.72 | ??0.47 | |||||||||||||
?MA | ?1.55 | ??2.18 | ?1.70 | ??0.98 | ?0.52 | ??0.32 | |||||||||||||||
?DEC | ?1.57 | ??2.20 | ?1.70 | ??0.97 | ?0.52 | ??0.35 | |||||||||||||||
?DIOX | ?1.56 | ??2.18 | ?1.69 | ??0.99 | ?0.55 | ??0.39 | |||||||||||||||
?DEE | ?1.62 | ??2.31 | ?1.77 | ??0.98 | ?0.51 | ||||||||||||||||
?EA | ?1.51 | ??2.09 | ?1.63 | ??0.94 | ?0.50 | ??0.32 | |||||||||||||||
?DMSU | ?1.55 | ??2.16 | ?1.66 | ??0.92 | ?0.72 | ?0.32 | ??0.31 |
Table 2
The Conductivity Calculation value that contains the ternary solvent mixture of EC
Solvent #2 | ?DMF | ??DMA | ??DMSO | ??NMP | ??MG | ??GBL | ??TEP | ??DME | ??PC | ??MF | ??THF | ??SULF | ??DMC | ??ACN | ??MA | ??DEC | ??DIOX | ??DEE | ??EA | ????DMSU |
Solvent #1 | ||||||||||||||||||||
?DMF | ?4.63 | ??5.03 | ??4.05 | ??4.04 | ??4.59 | ??2.91 | ??3.52 | ??3.78 | ??2.57 | ??3.62 | ??3.57 | ??3.02 | ??3.50 | ??3.46 | ??3.56 | ??3.59 | ??3.60 | ??3.63 | ??3.49 | ????3.51 |
?DMA | ?5.03 | ??5.60 | ??4.39 | ??4.28 | ??4.93 | ??2.90 | ??3.68 | ??4.16 | ??2.52 | ??3.97 | ??3.89 | ??3.08 | ??3.79 | ??3.76 | ??3.88 | ??3.92 | ??3.94 | ??3.97 | ??3.79 | ????3.80 |
?DMSO | ?4.05 | ??4.39 | ??3.20 | ??3.20 | ??3.78 | ??1.97 | ??2.53 | ??2.57 | ??1.48 | ??2.35 | ??2.31 | ??1.80 | ??2.25 | ??2.23 | ??2.29 | ??2.31 | ??2.32 | ??2.32 | ??2.24 | ????2.22 |
?NMP | ?4.04 | ??4.28 | ??3.20 | ??3.00 | ??3.36 | ??1.79 | ??2.35 | ??2.47 | ??1.41 | ??2.29 | ??2.27 | ??1.66 | ??2.16 | ??2.21 | ??2.24 | ??2.25 | ??2.32 | ??2.21 | ??2.20 | ????2.13 |
?MG | ?4.59 | ??4.93 | ??3.78 | ??3.36 | ??3.60 | ??1.90 | ??2.64 | ??2.87 | ??1.54 | ??2.68 | ??2.67 | ??1.81 | ??2.48 | ??2.59 | ??2.61 | ??2.65 | ??2.80 | ??2.54 | ??2.58 | ????2.44 |
?GBL | ?2.91 | ??2.90 | ??1.97 | ??1.79 | ??1.90 | ??0.72 | ??1.12 | ??0.81 | ??0.40 | ??0.66 | ??0.68 | ??0.45 | ??0.61 | ??0.63 | ??0.64 | ??0.68 | ??0.73 | ??0.60 | ??0.64 | ????0.58 |
?TEP | ?3.52 | ??3.68 | ??2.53 | ??2.35 | ??2.64 | ??1.12 | ??1.62 | ??1.46 | ??0.71 | ??1.26 | ??1.26 | ??0.83 | ??1.17 | ??1.21 | ??1.21 | ??1.24 | ??1.30 | ??1.17 | ??1.20 | ????1.12 |
?DME | ?3.78 | ??4.16 | ??2.57 | ??2.47 | ??2.87 | ??0.81 | ??1.46 | ??0.95 | ??0.62 | ??0.63 | ??0.36 | ??0.57 | ??0.53 | ??0.57 | ??0.64 | ??0.67 | ??0.56 | ??0.55 | ????0.51 | |
?PC | ?2.57 | ??2.52 | ??1.48 | ??1.41 | ??1.54 | ??0.40 | ??0.71 | |||||||||||||
?MF | ?3.62 | ??3.97 | ??2.35 | ??2.29 | ??2.68 | ??0.66 | ??1.26 | ??0.62 | ??0.30 | ??0.30 | ||||||||||
?THF | ?3.57 | ??3.89 | ??2.31 | ??2.27 | ??2.67 | ??0.68 | ??1.26 | ??0.63 | ??0.31 | ??0.32 | ??0.31 | |||||||||
?SULF | ?3.02 | ??3.08 | ??1.80 | ??1.66 | ??1.81 | ??0.45 | ??0.83 | ??0.36 | ||||||||||||
?DMC | ?3.50 | ??3.79 | ??2.25 | ??2.16 | ??2.48 | ??0.61 | ??1.17 | ??0.57 | ??0.30 | |||||||||||
?ACN | ?3.46 | ??3.76 | ??2.23 | ??2.21 | ??2.59 | ??0.63 | ??1.21 | ??0.53 | ||||||||||||
?MA | ?3.56 | ??3.88 | ??2.29 | ??2.24 | ??2.61 | ??0.64 | ??1.21 | ??0.57 | ||||||||||||
?DEG | ?3.59 | ??3.92 | ??2.31 | ??2.25 | ??2.65 | ??0.68 | ??1.24 | ??0.64 | ??0.30 | ??0.32 | ??0.32 | ??0.32 | ||||||||
?DIOX | ?3.60 | ??3.94 | ??2.32 | ??2.32 | ??2.80 | ??0.73 | ??1.30 | ??0.67 | ??0.30 | ??0.31 | ??0.30 | ??0.32 | ??0.30 | |||||||
?DEE | ?3.63 | ??3.97 | ??2.32 | ??2.21 | ??2.54 | ??0.60 | ??1.17 | ??0.56 | ||||||||||||
?EA | ?3.49 | ??3.79 | ??2.24 | ??2.20 | ??2.58 | ??0.64 | ??1.20 | ??0.55 | ||||||||||||
?DMSU | ?3.51 | ??3.80 | ??2.22 | ??2.13 | ??2.44 | ??0.58 | ??1.12 | ??0.51 |
Table 3
The Conductivity Calculation value that contains the ternary solvent mixture of PC
Solvent #2 | ??DMF | ?DMA | ?DMSO | ??NMP | ??MG | ??GBL | ??TEP | ??EC | ??DME | ??MF | ??THF | ??SULF | ??DMC | ??ACN | ??MA | ??DEC | ??DIOX | ??DEE | ??EA | ???DMSU |
Solvent #1 | ||||||||||||||||||||
?DMF | ??2.90 | ?3.16 | ?2.53 | ??2.52 | ??2.87 | ??1.80 | ??2.19 | ??2.57 | ??2.36 | ??2.26 | ??2.23 | ??1.87 | ??2.19 | ??2.16 | ??2.22 | ??2.24 | ??2.25 | ??2.27 | ??2.18 | ????2.19 |
?DMA | ??3.16 | ?3.52 | ?2.74 | ??2.67 | ??3.08 | ??1.79 | ??2.29 | ??2.52 | ??2.61 | ??2.49 | ??2.44 | ??1.90 | ??2.37 | ??2.35 | ??2.43 | ??2.45 | ??2.47 | ??2.48 | ??2.37 | ????2.38 |
?DMSO | ??2.53 | ?2.74 | ?1.98 | ??1.98 | ??2.34 | ??1.20 | ??1.55 | ??1.48 | ??1.58 | ??1.44 | ??1.41 | ??1.08 | ??1.37 | ??1.37 | ??1.40 | ??1.41 | ??1.42 | ??1.41 | ??1.37 | ????1.35 |
?NMP | ??2.52 | ?2.67 | ?1.98 | ??1.84 | ??2.06 | ??1.08 | ??1.43 | ??1.41 | ??1.50 | ??1.39 | ??1.37 | ??0.98 | ??1.30 | ??1.34 | ??1.35 | ??1.36 | ??1.40 | ??1.33 | ??1.33 | ????1.28 |
?MG | ??2.87 | ?3.08 | ?2.34 | ??2.06 | ??2.19 | ??1.13 | ??1.59 | ??1.54 | ??1.73 | ??1.61 | ??1.61 | ??1.05 | ??1.48 | ??1.56 | ??1.57 | ??1.59 | ??1.69 | ??1.51 | ??1.55 | ????1.45 |
?GBL | ??1.80 | ?1.79 | ?1.20 | ??1.08 | ??1.13 | ??0.41 | ??0.65 | ??0.40 | ??0.45 | ??0.36 | ??0.37 | ??0.33 | ??0.35 | ??0.35 | ??0.37 | ??0.41 | ??0.32 | ??0.35 | ????0.31 | |
?TEP | ??2.19 | ?2.29 | ?1.55 | ??1.43 | ??1.59 | ??0.65 | ??0.96 | ??0.71 | ??0.85 | ??0.72 | ??0.72 | ??0.46 | ??0.67 | ??0.70 | ??0.70 | ??0.71 | ??0.75 | ??0.66 | ??0.69 | ????0.63 |
?EC | ??2.57 | ?2.52 | ?1.48 | ??1.41 | ??1.54 | ??0.40 | ??0.71 | |||||||||||||
?DME | ??2.36 | ?2.61 | ?1.58 | ??1.50 | ??1.73 | ??0.45 | ??0.85 | ??0.51 | ??0.31 | ??0.31 | ??0.33 | |||||||||
?MF | ??2.26 | ?2.49 | ?1.44 | ??1.39 | ??1.61 | ??0.36 | ??0.72 | |||||||||||||
?THF | ??2.23 | ?2.44 | ?1.41 | ??1.37 | ??1.61 | ??0.37 | ??0.72 | ??0.31 | ||||||||||||
?SULF | ??1.87 | ?1.90 | ?1.08 | ??0.98 | ??1.05 | ??0.46 | ||||||||||||||
?DMC | ??2.19 | ?2.37 | ?1.37 | ??1.30 | ??1.48 | ??0.33 | ??0.67 | |||||||||||||
?ACN | ??2.16 | ?2.35 | ?1.37 | ??1.34 | ??1.56 | ??0.35 | ??0.70 | |||||||||||||
?MA | ??2.22 | ?2.43 | ?1.40 | ??1.35 | ??1.57 | ??0.35 | ??0.70 | |||||||||||||
?DEC | ??2.24 | ?2.45 | ?1.41 | ??1.36 | ??1.59 | ??0.37 | ??0.71 | ??0.31 | ||||||||||||
?DIOX | ??2.25 | ?2.47 | ?1.42 | ??1.40 | ??1.69 | ??0.41 | ??0.75 | ??0.33 | ||||||||||||
?DEE | ??2.27 | ?2.48 | ?1.41 | ??1.33 | ??1.51 | ??0.32 | ??0.66 | |||||||||||||
?EA | ??2.18 | ?2.37 | ?1.37 | ??1.33 | ??1.55 | ??0.35 | ??0.69 | |||||||||||||
?DMSU | ??2.19 | ?2.38 | ?1.35 | ??1.28 | ??1.45 | ??0.31 | ??0.63 |
Table 4
The Conductivity Calculation value that contains the ternary solvent mixture of DMC
Solvent #2 | ??DMF | ?DMA | ??DMSO | ??NMP | ??MG | ??GBL | ??TEP | ??EC | ??DME | ??PC | ??MF | ??THF | ??SULF | ??ACN | ??MA | ??DEC | ??DIOX | ??DEE | ??EA | ???DMSU |
Solvent #1 | ||||||||||||||||||||
??DMF | ??1.59 | ?1.89 | ??2.07 | ??1.47 | ??1.71 | ??1.17 | ??1.32 | ??3.50 | ??1.51 | ??2.19 | ??1.46 | ??1.43 | ??1.51 | ??1.42 | ??1.43 | ??1.45 | ??1.44 | ??1.48 | ??1.40 | ???1.42 |
??DMA | ??1.89 | ?2.26 | ??2.40 | ??1.75 | ??2.10 | ??1.27 | ??1.58 | ??3.79 | ??2.03 | ??2.37 | ??1.97 | ??1.90 | ??1.76 | ??1.80 | ??1.91 | ??1.93 | ??1.92 | ??2.02 | ??1.84 | ???1.90 |
??DMSO | ??2.07 | ?2.40 | ??1.74 | ??1.77 | ??2.18 | ??1.10 | ??1.46 | ??2.25 | ??1.70 | ??1.37 | ??1.57 | ??1.52 | ??1.13 | ??1.45 | ??1.52 | ??1.54 | ??1.52 | ??1.59 | ??1.47 | ???1.49 |
??NMP | ??1.47 | ?1.75 | ??1.77 | ??0.97 | ??1.13 | ??0.78 | ??0.79 | ??2.16 | ??0.97 | ??1.30 | ??0.91 | ??0.89 | ??0.93 | ??1.07 | ??0.88 | ??0.89 | ??0.91 | ??0.90 | ??0.86 | ???0.85 |
??MG | ??1.71 | ?2.10 | ??2.18 | ??1.13 | ??0.50 | ??0.85 | ??0.37 | ??2.48 | ??0.49 | ??1.48 | ??0.47 | ??0.46 | ??1.08 | ??1.37 | ??0.45 | ??0.46 | ??0.48 | ??0.46 | ??0.44 | ???0.64 |
??GBL | ??1.17 | ?1.27 | ??1.10 | ??0.78 | ??0.85 | ??0.50 | ??0.61 | ??0.41 | ??0.33 | ??0.33 | ??0.34 | ??0.30 | ??0.31 | ??0.34 | ??0.37 | ??0.31 | ||||
??TEP | ??1.32 | ?1.58 | ??1.46 | ??0.79 | ??0.37 | ??0.50 | ??1.17 | ??0.67 | ??0.49 | ??0.65 | ||||||||||
??EC | ??3.50 | ?3.79 | ??2.25 | ??2.16 | ??2.48 | ??0.61 | ??1.17 | ??0.57 | ??0.30 | |||||||||||
??DME | ??1.51 | ?2.03 | ??1.70 | ??0.97 | ??0.49 | ??0.41 | ??0.57 | ??0.37 | ||||||||||||
??PC | ??2.19 | ?2.37 | ??1.37 | ??1.30 | ??1.48 | ??0.33 | ??0.67 | |||||||||||||
??MF | ??1.46 | ?1.97 | ??1.57 | ??0.91 | ??0.47 | ??0.33 | ||||||||||||||
??THF | ??1.43 | ?1.90 | ??1.52 | ??0.89 | ??0.46 | ??0.34 | ||||||||||||||
??SULF | ??1.51 | ?1.76 | ??1.13 | ??0.93 | ??1.08 | ??0.49 | ||||||||||||||
??ACN | ??1.42 | ?1.80 | ??1.45 | ??1.07 | ??1.37 | ??0.30 | ??0.65 | ??0.37 | ||||||||||||
??MA | ??1.43 | ?1.91 | ??1.52 | ??0.88 | ??0.45 | ??0.31 | ||||||||||||||
??DEC | ??1.45 | ?1.93 | ??1.54 | ??0.89 | ??0.46 | ??0.34 | ||||||||||||||
??DIOX | ??1.44 | ?1.92 | ??1.52 | ??0.91 | ??0.48 | ??0.37 | ??0.30 | |||||||||||||
??DEE | ??1.48 | ?2.02 | ??1.59 | ??0.90 | ??0.46 | |||||||||||||||
??EA | ??1.40 | ?1.84 | ??1.47 | ??0.86 | ??0.44 | ??0.31 | ||||||||||||||
??DMSU | ??1.42 | ?1.90 | ??1.49 | ??0.85 | ??0.64 |
Table 5
The Conductivity Calculation value that contains the ternary solvent mixture of DME
Solvent #2 | ??DMF | ?DMA | ?DMSO | ??NMP | ??MG | ??GBL | ??TEP | ??EC | ??PC | ??MF | ??THF | ??SULF | ??DMC | ??CAN | ??MA | ??DEC | ??DIOX | ??DEE | ??EA | ??DMSU |
Solvent #1 | ||||||||||||||||||||
?DMF | ??1.66 | ??1.97 | ?2.17 | ??1.54 | ??1.80 | ??1.25 | ??1.40 | ??3.78 | ??2.36 | ??1.57 | ??1.54 | ??1.63 | ??1.51 | ??1.53 | ??1.54 | ??1.56 | ??1.55 | ??1.60 | ??1.50 | ??1.53 |
?DMA | ??1.97 | ??2.37 | ?2.54 | ??1.86 | ??2.23 | ??1.38 | ??1.70 | ??4.16 | ??2.61 | ??2.15 | ??2.08 | ??1.94 | ??2.03 | ??1.97 | ??2.09 | ??2.12 | ??2.10 | ??2.21 | ??2.02 | ??2.08 |
?DMSO | ??2.17 | ??2.54 | ?1.88 | ??1.90 | ??2.34 | ??1.22 | ??1.61 | ??2.57 | ??1.58 | ??1.80 | ??1.74 | ??1.30 | ??1.70 | ??1.65 | ??1.74 | ??1.76 | ??1.74 | ??1.82 | ??1.68 | ??1.71 |
?NMP | ??1.54 | ??1.86 | ?1.90 | ??1.04 | ??1.22 | ??0.87 | ??0.88 | ??2.47 | ??1.50 | ??1.05 | ??1.02 | ??1.09 | ??0.97 | ??1.23 | ??1.01 | ??1.02 | ??1.03 | ??1.03 | ??0.98 | ??0.97 |
?MG | ??1.80 | ??2.23 | ?2.34 | ??1.22 | ??0.55 | ??0.96 | ??0.41 | ??2.87 | ??1.73 | ??0.55 | ??0.53 | ??1.28 | ??0.49 | ??1.58 | ??0.53 | ??0.54 | ??0.56 | ??0.54 | ??0.51 | ??0.76 |
?GBL | ??1.25 | ??1.38 | ?1.22 | ??0.87 | ??0.96 | ??0.36 | ??0.59 | ??0.81 | ??0.45 | ??0.45 | ??0.45 | ??0.32 | ??0.41 | ??0.41 | ??0.43 | ??0.46 | ??0.49 | ??0.42 | ??0.42 | ??0.39 |
?TEP | ??1.40 | ??1.70 | ?1.61 | ??0.88 | ??0.41 | ??0.59 | ??1.46 | ??0.85 | ??0.64 | ??0.81 | ??0.38 | |||||||||
?EC | ??3.78 | ??4.16 | ?2.57 | ??2.47 | ??2.87 | ??0.81 | ??1.46 | ??0.35 | ??0.62 | ??0.63 | ??0.36 | ??0.57 | ??0.53 | ??0.57 | ??0.64 | ??0.67 | ??0.56 | ??0.55 | ??0.51 | |
?PC | ??2.36 | ??2.61 | ?1.58 | ??1.50 | ??1.73 | ??0.45 | ??0.85 | ??0.31 | ??0.31 | ??0.33 | ||||||||||
?MF | ??1.57 | ??2.15 | ?1.80 | ??1.05 | ??0.55 | ??0.45 | ??0.62 | ??0.31 | ??0.40 | |||||||||||
?THF | ??1.54 | ??2.08 | ?1.74 | ??1.02 | ??0.53 | ??0.45 | ??0.63 | ??0.31 | ??0.32 | ??0.40 | ||||||||||
?SULF | ??1.63 | ??1.94 | ?1.30 | ??1.09 | ??1.28 | ??0.32 | ??0.64 | ??0.36 | ??0.31 | ??0.32 | ??0.33 | ??0.35 | ||||||||
?DMC | ??1.51 | ??2.03 | ?1.70 | ??0.97 | ??0.49 | ??0.41 | ??0.57 | ??0.37 | ||||||||||||
?ACN | ??1.53 | ??1.97 | ?1.65 | ??1.23 | ??1.58 | ??0.41 | ??0.81 | ??0.53 | ??0.40 | ??0.40 | ??0.37 | ??0.36 | ??0.45 | ??0.44 | ??0.43 | ??0.32 | ??0.34 | |||
?MA | ??1.54 | ??2.09 | ?1.74 | ??1.01 | ??0.53 | ??0.43 | ??0.57 | ??0.36 | ||||||||||||
?DEC | ??1.56 | ??2.12 | ?1.76 | ??1.02 | ??0.54 | ??0.46 | ??0.64 | ??0.31 | ??0.33 | ??0.45 | ||||||||||
?DIOX | ??1.55 | ??2.10 | ?1.74 | ??1.03 | ??0.56 | ??0.49 | ??0.67 | ??0.33 | ??0.35 | ??0.44 | ||||||||||
?DEE | ??1.60 | ??2.21 | ?1.82 | ??1.03 | ??0.54 | ??0.42 | ??0.56 | ??0.43 | ||||||||||||
?EA | ??1.50 | ??2.02 | ?1.68 | ??0.98 | ??0.51 | ??0.42 | ??0.55 | ??0?32 | ||||||||||||
?DMSU | ??1.53 | ??2.08 | ?1.71 | ??0.97 | ??0.76 | ??0.39 | ??0.38 | ??0.51 | ??0.34 |
Technology of the present invention comprises first solvent contact procedure at least, wherein comprises to allow dry FLIEPM be exposed to first kind of solvent or solvent mixture.If implementation of processes scheme of the present invention includes only first solvent contact procedure, then first kind of solvent or solvent mixture must be solvents of the present invention disclosed herein.If implementation of processes scheme of the present invention comprises second or solvent contact procedure subsequently, then first kind of solvent or solvent mixture can be also can not be solvent of the present invention or solvent mixture.
In a kind of embodiment of technology of the present invention, in first solvent contact procedure, adopt a kind of solvent of the present invention, and adopt a kind of in second solvent contact procedure itself can be also can not be non-proton transitivity solvent of the present invention, thereby forms a kind of solvent mixture in this film.
In a kind of better embodiment of technology of the present invention, in first solvent contact procedure, adopt a kind of solvent of the present invention, carry out second solvent contact procedure subsequently, what wherein adopt is second kind of solvent, and first kind of solvent more effectively makes this ionomer swelling than second kind of solvent.In practice of the present invention, have been found that and first kind of solvent and comparing that second kind of solvent can reach originally of simple combination in the single solvent contact procedure, reached the higher intake of second kind of solvent and higher conductivity.
In the another embodiment of technology of the present invention, prepared the mixture of non-proton transitivity solvent, wherein at least a solvent is of the present invention, and makes this film be exposed to this mixture in a single solvent contact procedure.
In yet another embodiment of the present invention, adopt for example methyl alcohol of a kind of proton transfer solvent in first solvent contact procedure of technology of the present invention, in the hope of causing this lithium ionomer swelling, methyl alcohol is the ionomeric a kind of especially effectively sweller of this lithium.When being exposed to second kind of non-proton transitivity solvent in second solvent contact procedure of ionomer in technology of the present invention of this methyl alcohol swelling, have been found that, with comparing of can reaching originally as if first solvent contact procedure of omission, the higher intake of second kind of solvent and higher conductivity have been reached.Why not so good this embodiment is, be because some that it is believed that first kind of solvent still exists after remaining in second or solvent contact procedure subsequently, may produce adverse effect life-span and performance from the film formed lithium battery group of such production.
Adopt solvent mixture desirable often, because each solvent all provides a kind of benefit.For example, a kind of solvent can provide higher stability under the condition that battery pack is used, and is another kind of then higher ionic conductivity can be provided.By the combination of these two kinds of solvents, higher stability that can provide than a kind of solvent and the higher conductance that can provide than another kind of solvent are provided resulting polymer dielectric film.Under the known technically certain situation, the performance that is reached is also better than the prediction of the simple rule of mixture.
Some non-proton transitivity solvents and non-proton transitivity solvent mixture are also arranged, having adopted in first swelling step when them a kind ofly not belong to the present invention but be used for second of technology of the present invention or subsequently during the solvent contact procedure after causing the solvent of the extensive swelling of this polymer, is to belong to of the present invention.Only comprised this first swelling step before second or subsequently swelling step, the conductivity of resulting polymer dielectric film just can be greater than 10
-4S/cm.
Have that many solvents and group of solvents are suitable to be share in practice of the present invention.As shown in above, aspect the conductivity of the film that determines explained hereafter of the present invention, the solvent intake is a key factor, although be not unique factor.For some solvents, this film can contact about 24 hours or the shorter time just reaches high balance solvent intake and produces FLIEPEM of the present invention simply in room temperature with solvent.For other solvents, may in excessive solvent, flood to reach for 2 weeks or just can reach balance for more time and absorb.In some cases, have been found that under about 60~90 ℃ high temperature, to be impregnated with to be beneficial to and reduce necessary dip time.
The concrete mode of solvent contact depends on specific solvent and the film that is adopted similarly.In some cases, purpose of the present invention has only when this film floods a period of time that reaches a couple of days or several weeks or at high temperature floods in excessive solvent and just can reach.Yet, in other cases, make this film be exposed to a certain quantity of solvent that this film can be fully and promptly absorbed, do not stay any excessive that this film must separate with it.
Be suitable for implementing solvent of the present invention and solvent mixture and comprise those that select from following composition one group: dimethyl formamide (DMF), dimethoxy-ethane (DME), ethylene carbonate (EC), propylene carbonate (PC), dimethyl sulfoxide (DMSO) (DMSO), gamma-butyrolacton (GBL), N, N '-dimethylpropylene urea (DMPU), 1-Methyl-2-Pyrrolidone (NMP), dimethylacetylamide (DMA), N, N '-amide dimethyl butyrate (DMB), triethyl phosphate (TEP), N, N '-di-n-butyl acetamide (DBA), and composition thereof; The perhaps mixture of PC and a kind of solvent of from DME, EC, GBL, dimethyl carbonate (DMC) and acrylonitrile (ACN) composition one group, selecting; Or the mixture of a kind of solvent of selecting EC and form from DME, GBL, DMSO, diethoxyethane (DEE) and DMC one group; Or the mixture of a kind of solvent of selecting NMP and form from DME, DMSO, GBL, DMF and DMA one group; Or the mixture of GBL and DEE or DME; Or the mixture of a kind of solvent of selecting EC and DME and form from diethyl carbonate (DEC), DMC and PC one group; Or DMF and from DMA, DMSO, NMP, methyl glycollate (MG), GBL, TEP, EC, DME, PC, methyl formate (MF), oxolane (THF), sulfolane (SULF), DMC, ACN, methyl acetate (MA), DEC, 1, the mixture of a kind of solvent of selecting in one group that 3-dioxolanes (DIOX), DEE, ethyl acrylate (EA) and dimethyl sulfite (DMSU) are formed; Or DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMSO and from NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or NMP and from MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or MG and from GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or GBL and from TEP, EC, DME, PC, MF, THF, ACN, MA, DEC, the mixture of a kind of solvent of selecting in one group that DIOX and EA form; Or the mixture of a kind of solvent of selecting TEP and form from EC, PC, SULF, ACN and DMSU one group; Or the mixture of EC and DME; Or the mixture of DME and ACN or DMSU; Or EC, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group of solvent that EA and DMSU form; Or EC, DMA and from DMSO, NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, DMSO and from NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, the mixture of a kind of solvent of selecting in one group that DMSU forms; Or EC, NMP and from MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, MG and from GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, GBL and from TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, TEP and from DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, DME and from MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of EC, MF and DEC or DIOX; Or the mixture of EC, THF and DEC or DIOX; Or the mixture of EC, DMC and DIOX; Or the mixture of EC, DEC and DIOX; Or PC, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, DMSO and from NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, NMP and from MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, MG and from GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, GBL and from TEP, EC, DME, MF, THF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, TEP and from EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of a kind of solvent of selecting PC, DME and form from THF, DEC and DIOX one group; Or DMC, DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, DMSO and from NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, NMP and from MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, MG and from GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, GBL and from TEP, EC, DME, PC, MF, THF, ACN, MA, DEC, the mixture of a kind of solvent of selecting in one group that DIOX and EA form; Or the mixture of a kind of solvent of selecting DMC, TEP and form from EC, PC, SULF and ACN one group; Or the mixture of DMC, EC and DME or DIOX; Or the mixture of DMC, DME and ACN; Or DME, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, DMA and from DMSO, NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, DMSO and from NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, NMP and from MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, MG and from GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, GBL and from TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, TEP and from EC, PC, SULF, the mixture of a kind of solvent of selecting in one group that ACN and DMSU form; Or DME, EC and from MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of a kind of solvent of selecting DME, PC and form from THF, DEC and DIOX one group; Or the mixture of DME, MF and SULF or ACN; Or the mixture of DME, THF and SULF or ACN; Or the mixture of DME, SULF and DEC or DIOX; Or the mixture of DME, DMC and ACN; Or the mixture of a kind of solvent of selecting DME, ACN and form from MA, DEC, DIOX, DEE, EA and DMSU one group.
To implement the present invention preferably solvent and solvent mixture comprise DMF, DME, EC, PC, DMSO, GBL, DMPU, NMP, DMA, DMB, TEP, DBA, and composition thereof form one group; Or the mixture of a kind of solvent of selecting PC and form from DME, EC, GBL, DMC and ACN one group; Or the mixture of a kind of solvent of selecting EC and form from DME, GBL, DMSO, DEE and DMC one group; Or the mixture of a kind of solvent of selecting NMP and form from DME, DMSO, GBL, DMF and DMA one group; Or the mixture of GBL and DEE or DME; Or the mixture of a kind of solvent of selecting EC and DME and form from DEC, DMC and PC one group.
Better solvent comprise DMSO, DMF, PC, EC, NMP, GBL, and composition thereof and they and the mixture of at least a solvent of from DMC, DME and DEC composition one group, selecting.
For implementing the present invention, best is the mixture of EC and DMC, and the mixture of they and the another kind of at least solvent selected from GBL, PC, DEC, DMSO and DME composition one group.
Be not to be suitable for all solvents of the present invention all to be suitable for every lithium battery group configuration on an equal basis well.With regard to the actual utility in the lithium battery group, this electrolyte not only must conduct electricity, and must demonstrate the stability of the electrochemical environment that will work therein for it.Electrochemistry operational environment major part is decided by selection of electrode materials.As [people such as Tarascon, " and 0~5V voltage range stable and also can with Li 1+xMn
2O
4The new dielectric film composition of/carbon Li ion battery compatibility ", Solid St.Lonics, 69,293 (1994)] described in, a kind of specific solvent depends on the dynamics that can't use the solvolysis process of theoretical prediction to a kind of stability of special electrodes.Therefore, the applicability of using any specific solvent to select in a kind of specific lithium battery group configuration need determine by example by this electrolyte of test in the operational environment that is proposed.The solvent that adopts in the specific embodiments of the following stated, many is technical known solvents that show good stability in far-ranging lithium battery group operational environment.
FLIEPEM of the present invention need not any given shape, and can form desirable any geometry with any means known.Yet the form of flat membranous type film is preferably.Thicker film needs the long time just can reach desirable conductivity level.5~200 microns thickness is preferably, and best is that thickness is the film of micron below 50 or 50.
The form of flat sheet membranes can be easily by cast the not hydrolysed form of this film of melt extrusion, carry out the above such hydrolysis process subsequently and realize.
In addition, dull and stereotyped lithium ionomeric membrane can be produced by solution-cast.In a kind of embodiment of this method, make unhydrolysed polymer hydrolysis become the potassium ionomer earlier, ion-exchange to be to generate acid then, at high temperature is dissolved in alcohol such as methyl alcohol, ethanol, propyl alcohol or butanols then, better is in the mixture of propyl alcohol and water.This type of liquid dispersion of perfluorinate ion exchange resin is disclosed in United States Patent (USP) 4,453,991.The acid-based polymer of solution or dispersion carries out ion-exchange with LiOH subsequently, provides the lithium ionomer.In order to improve the film strength that will cast, the water of this solution and propyl alcohol can utilize the rotary evaporation method to replace to the higher liquid of boiling point such as 1-butanols.The solids content of this dispersion liquid is intended to improve the viscosity of this dispersion liquid or solution by driving some solvents out of or adding other material and improve.Resulting paste utilizes a medical scraper to deposit to a kind of matrix for example can be available from the Teflon of E.I.Du Pont Company
On the PFA.Then, make such deposition the film drying, take off.Technical other known solution and dispersion liquid coating technique also are effectively same.
In the another embodiment of solution technology of the present invention, FLIEPM is scattered in a kind of low-boiling point alcohol for example in the methyl alcohol.In this dispersion liquid, add the high boiling solvents such as mixture of EC and PC.Resulting dispersion liquid is cast on a kind of matrix.The methyl alcohol preferential evaporation stays the film that has absorbed desired solvent.Heating resulting film then condenses making it.Do not need impregnation steps in the extra solvent.
The present invention further provides a kind of porous electrode again, wherein comprises a kind of particle of electrode active material, a kind of highly fluorinated lithium ion exchange polymer of the present invention and at least a non-proton transitivity solvent of the present invention.The example of avaivable electrode active material includes but not limited to carbon (graphite or coke type), and metal lithium nitride is Li for example
2.6Co
0.4N, tin-oxide, transition metal oxide is LiMn for example
2O
4, LiCoO
2, LiNiO
2, and organosulfur compound.Be preferably, the ionomeric volume fraction of lithium is between 4~40% in the finished electrode.
In a kind of embodiment of electrode forming, the coating paste is at a kind of polar protic transitivity solvent water for example with highly fluorinated lithium ion exchange polymer of the present invention, alcohol, or the mixture of water and alcohol, be preferably a kind of non-proton transitivity solvent, best be that dispersion liquid or solution in the mixture of propylene carbonate and a kind of alcohol forms, in this dispersion liquid, add a kind of electrode active material that better is powder type, better also in this dispersion liquid, added optional plasticizer and optional electron conduction particle.Make thin film deposition that this coating paste forms on a kind of matrix, and make solvent evaporation.Then, utilize heating and/or pressurization, more fortunately in 180~200 ℃ the temperature range, this film condensed.Then, resulting electrode is the form that is suitable for being laminated on the FLIEPM.Then, allow the electrode film that condenses absorb at least a non-proton transitivity solvent of the present invention, form electrode of the present invention.Can adopt technical known any method to make the paste thin film deposition on a kind of matrix.Known method comprises knife coating, inverse roller coating, the coating of plane-of-weakness joint type mould and extrudes.
Form in the another embodiment of technology at electrode of the present invention, the coating paste is to have the highly fluorinated polymers of side chain sulfuryl fluoride group for example can to form available from dispersion liquid or the solution in FC40, optional plasticizer, optional electron conduction particle and the electrode active material of 3M company (Minn. Minneapolis) at a kind of perfluoroparaffin solvent with a kind of; Utilize above-described technical any means known to form a kind of film from this coating paste; Make solvent evaporation; Make the hydrolysis of sulfuryl fluoride type polymer become the lithium type with using such as LiOH.
In a kind of embodiment preferably, battery pack is to comprise that with a kind of each electrode layer can condense simultaneously and form this battery pack under this temperature by make the above electrode and a kind of FLIEPEM technology formation in being laminated in the pressurization of about 180 ℃ temperature.
Further specify the present invention in the following specific embodiments.
Example
In following specific embodiments and comparative example, conductivity is measured with above-described four-point probe technology.The % weight intake (W%) of solvent is that the 0.001 laboratory balance that restrains is measured as follows with PM400 type (Mettler instrument company, N.J. Hai Cidun) precision: measure film dry weight (W
d).Be exposed to film after the solvent weight (W that " wet "
w) be formerly film to be taken out from solvent, with paper handkerchief it blotted to remove after the excessive surface solvent then and measure.All wt all is to fill in the drying box of nitrogen to measure.The weight intake of solvent is defined as:
W%=100·(W
w-W
d)/(W
d)
Comparative example 1
The 980g/eq. copolymer of a kind of TFE and perfluor (3,6-two oxa-s-4-methyl-7-octene sulfuryl fluoride), the melt cast membrane of thickness 127 μ m are at 80 ℃, 16%KOH, 20%DMSO and 64%H
2Flooded 2~4 hours in a kind of bath that O forms, make it to be hydrolyzed into the potassium ionomer, use water rinse subsequently.Then, the potassium ionomer of Sheng Chaning makes it to change into acid type with 5% aqueous solution of nitric acid in room temperature treatment about 48 hours like this.This acid polymer subsequently at 85 ℃ with the H that contains 68% (volume) water
2Excessive 6.2M LiOH solution-treated is about 35 minutes among O and the MeOH, changes into the lithium ionomer, cool overnight subsequently, in 110 ℃ of vacuum drying ovens dry about 64 hours.
1.1cm * 2cm sample immerses and accounts for an about 10cm diameter * 1.25cm and accompany deeply in the propylene carbonate for about 1/3 volume of lining culture dish, builds.This sample flooded 48 hours in about 22 ℃ room temperature, took out from solvent then.Remove surface solvent with the tapping method, measure than conductivity with above-described four-point probe technology then, measured value is 3.4 * 10
-5S/cm.
Comparative example 2
Identical in material and program and the comparative example 1, different is that this solvent is a dimethoxy-ethane.This film immersion 3.7 hours.Conductivity is 1.7 * 10
-5S/cm.
Example 1
Identical in material and program and the comparative example 1, different is that this solvent is 50/50 (volume) mixture of propylene carbonate and dimethoxy-ethane.This film immersion 48 hours.Than conductivity is 3.5 * 10
-4S/cm.The weight percent of absorbent of solvent is 57%.
Comparative example 3
Repeat the program of comparative example 1, different is that this film is a kind of 1268g/eq., the thick film of 178 μ m.This film immersion 48 hours.Conductivity is 5.6 * 10
-6S/cm.
Comparative example 4
Repeat the material and the program of comparative example 3, different is that this solvent is a dimethoxy-ethane.This film immersion 3.8 hours.Than conductivity is 2.2 * 10
-5S/cm.
Comparative example 5
Repeat the material and the program of comparative example 3, different is that this solvent is 50/50 (volume) mixture of propylene carbonate and dimethoxy-ethane.This film immersion 48 hours.Than conductivity is 7.5 * 10
-5S/cm.
Example 2 and comparative example 6
Adopt the material and the program of comparative example 1, membrane sample flooded 45.3 hours in room temperature in propylene carbonate.Then, the sample in the dipping is heated to 60 ℃, and kept about 1.5 hours.It further is heated to 90 ℃ and keep more than 30 minutes, subsequently cool to room temperature gradually on experimental bench.
Second sample at room temperature flooded 44.8 hours in carbonic acid glyceride.Then the sample in the dipping is heated to 60 ℃ and kept about 1.5 hours.With its further 90 ℃ of row of heating and keeping more than 30 minutes, cool to room temperature gradually on experimental bench subsequently.The results are shown in following table 6 and the table 7:
Table 6
Propylene carbonate, example 2
Time-temperature compares conductivity
(hour) (℃) be % weight intake (S/cm)
45.3????????23????????7.3×10
-6???39
48.8????????60????????6.2×10
-5???73
69.7????????90????????3.0×10
-4???132
Table 7
Carbonic acid glyceride, comparative example 6
Time-temperature compares conductivity
(hour) (℃) (S/cm)
44.8????????23???????????3.6×10
-6
48.2????????60???????????3.4×10
-6
70.4 90 92 * 10
-6Example 3~35 and comparative example 7 and 8
In these examples, Nafion
3 " * 3 " sample of 117, be a kind of can be available from E.I.Du Pont Company, from TFE and perfluor (3,6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) melt casting copolymer about 1100g/eq. acid hydrolysis flat sheet membrane that form, the about 180 μ m of thickness, by at water and DMSO (HPLC level, Burdick ﹠amp; Jackson, Michigan State MAERSK root) in 1: 1 (volume) mixture at T=60 ℃ to excessive 1.0 moles of LiOH (98%, the EM scientific company, the New Jersey gibbs is paused) expose 2 hours and change into the lithium ionomer, then, this film washed 2 hours with distilled water at T=80 ℃, and in nitrogen reflux formula baking oven (633 types, Electric Hotpack company, philadelphia, pa) in 100 ℃ of dryings 96 hours.
Desciccator diaphragm transferred in the airtight container still keep warm simultaneously, and send in the glove box of normal pressure of the drying nitrogen that feeds to some extent, this film is taken out and make it to get back to room temperature here from airtight container.Then this film is cut into some that are of a size of 1.0cm * 1.5cm, for the usefulness of in following pointed solvent, flooding.
Comparative example 7
Membrane sample in room temperature, is solvent impregnated 2 hours of a kind of proton transfer with excessive N-methylformamide (99.8%, Alfa Aesar, Ward, Massachusetts Xi Er) in a tubular bottle of seal glass.This film is taken out from the N-methylformamide is bathed, blot to remove excessive solvent, with above-described four-point probe method test with paper handkerchief.The solvent intake is determined with the above method.The solvent intake is 137.5%, and conductivity is 4.60 * 10
-3S/cm.
Comparative example 8
Still be in film in the solvent from comparative example 7, use a hot plate (PMC 730 series subsequently, Dataplate Digital Hot Plate) be heated to 60 ℃ and kept 120 minutes, bathe the solvent that contains this film and take off from hot plate this moment, made it to cool off about 2 hours.This film is taken out from the N-methylformamide is bathed, blot to remove excessive solvent, with above-described four-point probe method test with paper handkerchief.The solvent intake is determined with the above method.The solvent intake is 283.9%.Conductivity is 4.66 * 10
-3S/cm.
Example 3
This film is handled according to the method for comparative example 7, and different is that solvent is dimethyl formamide (ACS level, 99.8%, Alfa Aesar, Ward, Massachusetts Xi Er).The solvent intake is 125.5%, and conductivity is 3.47 * 10
-3S/cm.
Example 4
This film is handled according to the method for comparative example 7, and different is that solvent is dimethoxy-ethane (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin).The solvent intake is 25.9%, and conductivity is 2.24 * 10
-4S/cm.
Example 5
This film is handled according to the method for comparative example 7, and different is, solvent is a propylene carbonate (99) and 1: 1 (volume) mixture of dimethoxy-ethane, and this film at room temperature stopped in this solvent 5 hours.The solvent intake is 56.5%, and conductivity is 2.57 * 10
-4S/cm.
Example 6
This film is handled according to the method for comparative example 7, different is, solvent be propylene carbonate and ethylene carbonate (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin) 1: 1 (volume) mixture, membrane sample at room temperature stopped in these solvents 7 days.This time after date, heat-treat according to the method described in the comparative example 8.The solvent intake is 85.5%, and conductivity is 1.34 * 10
-4S/cm.
Example 7
This film is handled according to the method for comparative example 7, and different is, solvent is dimethyl sulfoxide (DMSO) (ACS level, 99.9+%, Alfa Aesar, Ward, Massachusetts Xi Er), and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 135.6%, and conductivity is 1.52 * 10
-3S/cm.
Example 8
This film is handled according to the method for comparative example 7, and different is, solvent is gamma-butyrolacton (99), and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 88.3%, and conductivity is 4.75 * 10
-4S/cm.
Example 9
This film is handled according to the method for comparative example 7, and different is, solvent is N, N '-dimethylpropylene urea (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin), and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 230.4%, and conductivity is 5.77 * 10
-4S/cm.
Example 10
This film is handled according to the method for comparative example 7, after this adds equivalent propylene carbonate (ACS level, 99.8+%, Alfa Aesar, Ward, Massachusetts Xi Er) in original N-methylformamide solvent.After at room temperature 24 hours, the solvent intake is 278.6%, and conductivity is 3.44 * 10
-3S/cm.
Example 11
This film is handled according to the method for comparative example 7, and different is that this solvent is 1: 1 (volume) mixture of propylene carbonate and diethyl carbonate (99%, Aldrich chemical company, Milwaukee, the state of Wisconsin).After 12 days by a definite date, add a certain amount of dimethoxy-ethane, make the solution of these three kinds of solvents always consist of 1: 1: 1 (volume).After at room temperature 24 hours by a definite date, the solvent intake is 39.0%, and conductivity is 1.39 * 10
-4S/cm.
Example 12
Handle according to wherein said method by 1.0cm * 1.5cm membrane sample that the mode of example 11 prepares, different is that initial solvent is 1: 1 (volume) mixture of ethylene carbonate and propylene carbonate.The solvent intake is 69.1%, and conductivity is 3.12 * 10
-4S/cm.
Example 13
This film is handled according to the method for example 11, different is, initial solvent is a dimethoxy-ethane, and after 32 days to wherein adding dimethyl carbonate (99%, Alfa Aesar, Ward, Massachusetts Xi Er) with 1: 1 mixture of propylene carbonate, finally consists of 1: 1: 1 (volume) in the hope of making.After 24 hours by a definite date, this film heats according to the program described in the comparative example 8.The solvent intake is 46.6%, and conductivity is 1.12 * 10
-4S/cm.
Example 14
This film is handled according to the method for comparative example 7, and different is, this solvent is 1-Methyl-2-Pyrrolidone (99.5%, Aldrich chemical company, Milwaukee, the state of Wisconsin), and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 134.3%, and conductivity is 1.25 * 10
-3S/cm.
Example 15
This film is handled by the mode of example 14, and different is that this solvent is 1: 1 (volume) mixture of 1-Methyl-2-Pyrrolidone and dimethyl sulfoxide (DMSO).The solvent intake is 132.2%, and conductance is 1.52 * 10
-3S/cm.
Example 16
This film is handled by the mode of example 14, and different is that this solvent is 1: 1 (volume) mixture of 1-Methyl-2-Pyrrolidone and dimethoxy-ethane.The solvent intake is 100.0%, and conductivity is 1.35 * 10
-3S/cm.
Example 17
This film is handled by the mode of example 14, and different is that this solvent is 1: 1 (volume) mixture of 1-Methyl-2-Pyrrolidone and gamma-butyrolacton.The solvent intake is 86.5%, and conductivity is 1.18 * 10
-3S/cm.
Example 18
This film is handled by the mode of example 14, and different is that this solvent is 1: 1 (volume) mixture of 1-Methyl-2-Pyrrolidone and dimethyl formamide.The solvent intake is 136.5%, and conductivity is 2.07 * 10
-3S/cm.
Example 19
This film is handled by the mode of example 14, and different is that this solvent is 1: 1 (volume) mixture of propylene carbonate and gamma-butyrolacton.The solvent intake is 86.5%, and conductivity is 3.39 * 10
-4S/cm.
Example 20
This film is handled by the mode of example 14, and different is that this solvent is 1: 1 (volume) mixture of propylene carbonate and dimethyl formamide.The solvent intake is 129.4%, and conductivity is 2.59 * 10
-3S/cm.
Example 21
This film is handled according to the method for comparative example 7, and different is, this solvent is 1: 1 (volume) mixture of dimethoxy-ethane and ethylene carbonate, and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 64.1%, and conductivity is 4.23 * 10
-4S/cm.
Example 22
This film is handled according to the method for comparative example 7, and different is that this solvent is 1: 1 (volume) mixture of gamma-butyrolacton and ethylene carbonate, and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 81.2%, and conductivity is 3.1I * 10
-4S/cm.
Example 23
This film is handled according to the method for comparative example 7, and different is that this solvent is 1: 1 (volume) mixture of dimethyl sulfoxide (DMSO) and ethylene carbonate, and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 122.0%, and conductivity is 1.53 * 10
-3S/cm.
Example 24
This film is handled according to the method for comparative example 7, and different is that this solvent is 1: 1: 1 (volume) mixture of ethylene carbonate, propylene carbonate and dimethoxy-ethane, and this film at room temperature stopped in this solvent 3 hours.The solvent intake is 40.1%, and conductivity is 1.57 * 10
-4S/cm.
Example 25
This film is handled according to the method for comparative example 7, different is, this solvent be gamma-butyrolacton and diethoxyethane (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin) 1: 1 (volume) mixture, and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 56.2%, and conductivity is 1.34 * 10
-4S/cm.
Example 26
This film is handled according to the method for comparative example 7, and different is that this solvent is 1: 1 (volume) mixture of ethylene carbonate and diethoxyethane, and this film at room temperature stopped in this solvent 24 hours.The solvent intake is 75.0%, and conductivity is 1.65 * 10
-4S/cm.
Example 27
This film is handled according to the method for comparative example 7, and different is that this solvent is dimethylacetylamide (99.5+%, Alfa Aesar, Ward, Massachusetts Xi Er).The solvent intake is 166.7%, and conductivity is 3.05 * 10
-3S/cm.
Example 28
The film of example 27 continues to flood 4 days in dimethylacetylamide, and add a certain amount of N-methyl pyrrolidone this moment, so that solvent is always formed up to 1: 1 (volume).After 24 hours by a definite date, the solvent intake is 89.4%, and conductivity is 1.16 * 10
-3S/cm.
Example 29
This film is handled according to the method for comparative example 7, and different is that this solvent is N, N '-amide dimethyl butyrate (98%, Lancaster Synesis Company, state of New Hampshire Wen Dehan nurse).The solvent intake is 123.8%, and conductivity is 5.48 * 10
-4S/cm.
Example 30
This film is handled according to the method for comparative example 7, and different is, this solvent is N, N '-di-n-butyl acetamide (98%, Lancaster Synesis Company, state of New Hampshire Wen Dehan nurse), and this film at room temperature stopped in this solvent 16 days.The solvent intake is 243.7%, and conductivity is 1.41 * 10
-4S/cm.
Example 31
This film is handled according to the method for comparative example 7, and different is that this solvent is triethyl phosphate (99+%, Alfa Aesar, Ward, Massachusetts Xi Er).The solvent intake is 154.4%, and conductivity is 3.45 * 10
-4S/cm.
Example 32
Handle according to wherein said method with 1.0cm * 1.5cm film that the mode of comparative example 7 prepares, different is, this solvent is 1: 1 (volume) mixture of ethylene carbonate and propylene carbonate, and solvent adds on the film surface in this film by with micropipette 40 microlitre solvents being dripped to.Ionic conductivity is to measure after 15 minutes, and measured value is 1.00 * 10
-4S/cm.
Example 33
This film is handled according to the method for comparative example 7, and different is that this solvent is 1: 1 (volume) mixture of propylene carbonate and dimethyl carbonate, and this film at room temperature stopped 9 days by a definite date in this solvent.The solvent intake is 28.8%, and conductivity is 1.32 * 10
-4S/cm.
Example 34
This film is handled by the mode of example 33, and different is that this solvent is 1: 1 (volume) mixture of propylene carbonate and acetonitrile (99.8%, Aldrich chemical company, Milwaukee, the state of Wisconsin).The solvent intake is 30.4%, and conductivity is 1.19 * 10
-4S/cm.
Example 35
1 " * 1 " sample of the 805g/eq. flat sheet membrane that the 92 μ m that form from the copolymer of TFE and perfluor (3-oxa--4-amylene sulfuryl fluoride) are thick, at T=85 ℃, in water and methyl alcohol (SILVER REAGENT, the EM scientific company, the New Jersey gibbs is paused) 1: 1 (volume) mixture in, to LiOH (EM scientific company, the New Jersey gibbs is paused) saturated solution expose 6 hours, after this this film was at 1: 1 water: spend the night at the room temperature dipping in the methanol solution, then at fresh 1: 1 water: be heated in the methanol solution T=60 ℃ 4 hours.After this, this film in nitrogen circulation formula baking oven (Electric Hotpack company, 633 types, philadelphia, pa) in 100 ℃ of dryings 96 hours.
This desciccator diaphragm is taken advantage of warm transferring in the airtight container, and is transported in the glove box that feeding drying nitrogen malleation wherein arranged, and at this this film is taken out and make it to get back to room temperature from airtight container.Then, this film is cut into some of 1.0cm * 1.5cm size.
Then 1.0cm * 1.5cm the membrane sample of cooling being put into a sealed glass phial at room temperature flooded 3 hours with excessive propylene carbonate.This film is taken out from propylene carbonate is bathed, blot to remove excessive solvent, with above-described four-point probe method of testing test with paper handkerchief.The solvent intake is measured with the above method.The solvent intake is 580.8%.Although the solvent intake is very high, do not form gel; This film still keeps its structural intergrity.Conductivity is 4.57 * 10
-4S/cm.
Example 36
Handle according to wherein said method with the membrane sample that the mode of example 35 prepares, different is that this solvent is a dimethoxy-ethane.The solvent intake is 63.6%, and conductivity is 1.71 * 10
-4S/cm.
Example 37
Handle according to wherein said method with the membrane sample that the mode of example 35 prepares, different is that this solvent is 1: 1: 1 (volume) mixture of ethylene carbonate, propylene carbonate and dimethoxy-ethane.The solvent intake is 553.8%.Although the solvent intake is very high, do not form gel; This film still keeps its structural intergrity.Conductivity is 6.81 * 10
-4S/cm.
Example 38
A kind of TFE and perfluor (3, thick 1 " * 1 " the flat sheet membrane sample of 112 μ m of 750g/eq. copolymer 6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) at T=85 ℃ to LiOH (EM scientific company, the New Jersey gibbs is paused) in water and methyl alcohol (SILVER REAGENT, the EM scientific company, the New Jersey gibbs is paused) 1: 1 (volume) mixture in saturated solution expose 6 hours, this film was at 1: 1 water then: in the methanol solution at room temperature dipping spend the night, then at fresh 1: 1 water: be heated in the methanol solution T=60 ℃ 4 hours.After this, this film in a nitrogen circulation formula baking oven (Electric Hotpack company, 633 types, philadelphia, pa) 100 ℃ of dryings 96 hours.
Desciccator diaphragm is taken advantage of warm transferring in the airtight container, is transported in the glove box that feeding drying nitrogen malleation wherein arranged, and here film is taken out from airtight container, and makes it to get back to room temperature.Then this film is cut into some of size 1.0cm * 1.5cm.
Then, at room temperature soaked 3 hours in the excessive propylene carbonate of the 1.0cm of cooling * 1.5cm membrane sample in a tubular bottle of seal glass.This film takes out from the N-methylformamide is bathed, and blots to remove excessive solvent with paper handkerchief, utilizes above-described four-point probe method of testing test.Measure the solvent intake with the above method.The solvent intake is 175.8%, and conductivity is 2.70 * 10
-4S/cm.
Example 39
Handle according to wherein said method with the membrane sample that the mode of example 38 prepares, different is that this solvent is 1: 1 (volume) mixture of ethylene carbonate and propylene carbonate.The solvent intake is 176.5%, and conductivity is 3.40 * 10
-4S/cm.
Example 40
Handle according to wherein said method with the membrane sample that the mode of example 38 prepares, different is that this solvent is 1: 1: 1 (volume) mixture of ethylene carbonate, propylene carbonate and dimethoxy-ethane.The solvent intake is 145.5%, and conductivity is 7.47 * 10
-4S/cm.
Example 41
A kind of TFE and perfluor (3,125 μ m of 834g/eq. copolymer 6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) thick 1 " * 1 " flat sheet membrane sample is in 86% water and 14%DMSO (GR level, the EM scientific company, the New Jersey gibbs is paused) mixture at T=80 ℃ to 2.0 moles of excessive LiOH (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin) exposes 4.75 hours, after this, this film washed 3 times 30 minutes with distilled water at T=80 ℃, in a nitrogen circulation formula baking oven (Electric Hotpack company, 633 types, philadelphia, pa) 100 ℃ of drying 96 hours.
Desciccator diaphragm is taken advantage of warm transferring in the airtight container, is transported in the glove box that feeding drying nitrogen malleation wherein arranged, and here film is taken out from airtight container, and makes it to get back to room temperature.Then this film is cut into some of size 1.0cm * 1.5cm.
Then, at room temperature flooded 24 hours in the excessive propylene carbonate of the 1.0cm of cooling * 1.5cm membrane sample in the tubular bottle of seal glass.Film is taken out from propylene carbonate is bathed, blot to remove excessive solvent, with above-described four-point probe method of testing test with paper handkerchief.The solvent intake is measured with the above method.The solvent intake is 187.1%, and conductivity is 2.76 * 10
-4S/cm.
Example 42
Handle according to wherein said method with the membrane sample that the mode of example 41 prepares, different is that this solvent is a gamma-butyrolacton.The solvent intake is 184.4%, and conductivity is 7.30 * 10
-4S/cm.
Example 43
Handle according to wherein said method with the membrane sample that the mode of example 41 prepares, different is that this solvent is a dimethyl sulfoxide (DMSO).The solvent intake is 386.1%, and conductivity is 1.65 * 10
-3S/cm.
Example 44
According to people's United States Patent (USP)s 3 such as Connoly, 282, the TFE that method described in 875 is synthetic, 17.8% (mole) perfluor (3,6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) and 2 " * 2 " sample of the terpolymer of 9.6% (mole) perfluorinated methyl ethylene ether, at T=80 ℃ in 86% water and 14%DMSO (GR level, the EM scientific company, the New Jersey gibbs is paused) in the mixture to excessive 2.0 moles of LiOH (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin) exposes 4.75 hours, this film washed 3 times 30 minutes with distilled water at T=80 ℃ then, in a nitrogen circulation formula baking oven (Electric Hotpack company, 633 types, philadelphia, pa) in 100 ℃ of dryings 96 hours.
Desciccator diaphragm is taken advantage of warm transferring in the airtight container, is transported in the oriented glove box that wherein feeds the drying nitrogen malleation, here film is taken out from airtight container and allows it get back to room temperature.Then, this film is cut into some of 1.0cm * 1.5cm size.
1.0cm * 1.5cm the membrane sample (175 μ m are thick) of cooling flooded 24 hours in room temperature in the excessive propylene carbonate in the tubular bottle of seal glass subsequently.This film is taken out from propylene carbonate is bathed, blot to remove excessive solvent, with above-described four-point probe method of testing test with paper handkerchief.The solvent intake is measured with the above method.The solvent intake is 146.9%, and conductivity is 3.11 * 10
-4S/cm.
Example 45
Handle according to wherein said method with the membrane sample that the mode of example 44 prepares, different is that this solvent is a gamma-butyrolacton.The solvent intake is 173.2%, and conductivity is 6.70 * 10
-4S/cm.
Example 46
Handle according to wherein said method with the membrane sample that the mode of example 44 prepares, different is that this solvent is a dimethyl sulfoxide (DMSO).The solvent intake is 528.2%.Though the solvent intake is very high, do not form gel; This film still keeps its structural intergrity.Conductivity is 1.15 * 10
-3S/cm.
Example 47
Handle according to wherein said method with the membrane sample that the mode of example 41 prepares, different is that this solvent is 1: 1 (volume) mixture of ethylene carbonate and diethyl carbonate, and this sample stopped in this solvent 2 hours by a definite date.The solvent intake is 88.9%, and conductivity is 1.81 * 10
-4S/cm.
Example 48
Handle according to wherein said method with the membrane sample that the mode of example 44 prepares, different is, this solvent is 1: 1: 1 (volume) mixture of ethylene carbonate, dimethyl carbonate and dimethoxy-ethane, and this sample was at room temperature stayed in this solvent 48 hours.The solvent intake is 141.4%, and conductivity is 9.32 * 10
-4S/cm.
Example 49
TFE and perfluor (3,77 μ m of 890g/eq. copolymer 6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) thick 1 " * 1 " flat sheet membrane sample, at T=80 ℃ in 86% water and 14%DMSO (GR level, the EM scientific company, the New Jersey gibbs is paused) in the mixture to excessive 2.0 moles of LiOH (98%, Aldrich chemical company, Milwaukee, the state of Wisconsin) exposes 4.75 hours, this film washed 3 times 30 minutes with distilled water at T=80 ℃ then, in a nitrogen circulation formula baking oven (Electric Hotpack company, 633 types, philadelphia, pa) in 100 ℃ of dryings 96 hours.
Desciccator diaphragm is taken advantage of warm transferring in the airtight container, and is transported in the glove box that feeding drying nitrogen malleation wherein arranged, and film is taken out and make it to get back to room temperature here from airtight container.Then this film is cut into some of 1.0cm * 1.5cm size.
1.0cm * 1.5cm the membrane sample of cooling flooded 48 hours in room temperature in 1: 1 (volume) mixture of excessive ethylene carbonate and dimethyl carbonate in a tubular bottle of seal glass subsequently.This film is taken out from this solvent is bathed, blot to remove excessive solvent, with above-described four-point probe method of testing test with paper handkerchief.The solvent intake is measured with the above method.The solvent intake is 72.0%, and conductivity is 1.51 * 10
-4S/cm.
Example 50
Handle according to wherein said method with the membrane sample that the mode of example 49 prepares, different is that this solvent is 1: 1 (volume) mixture of ethylene carbonate and propylene carbonate.The solvent intake is 115.0%, and conductivity is 4.44 * 10
-4S/cm.
Example 51
Being hydrolyzed into the dispersion liquid of 1070g/eq. copolymer acid type, TFE and perfluor (3,6-two oxa-s-4-methyl-7-octene sulfuryl fluoride) with the method for comparative example 1, is according to United States Patent (USP) 4,453,991 usefulness methyl alcohol, the preparation of 1-third alcohol and water.Solvent removes with the rotary evaporation method, gets highly viscously until this solution becomes, adds ethanol then, provides a kind of solution that contains 5.2% (weight) acid-based polymer, 5% water and about 90% ethanol.In 400g acid-based polymer dispersion liquid, add 8.7ml 1.9M lithium hydroxide aqueous solution, make this acid neutralization and generation lithium ionomer.Hereinto and during, observe pH and rise to 7.2 from 1.7.(PC 5g) with 1-butanols (100g), and makes this mixture be rotated evaporation at 50 ℃ to add propylene carbonate.This dispersion liquid concentrates that to contain 18% ionomer, 3.5% propylene carbonate and all the other major parts until it be the 1-butanols.
Diffusion barrier be by with one the scraper of the high 0.75mm of the edge of a knife above-mentioned dispersion liquid be cast to a kind of can be available from the TEFLON of E.I.Du Pont Company
Prepare on the PFA basement membrane.Behind the air drying, obtain the thick film of 50-55 μ m around.
Cathodic coating is by the ionomeric PC/ butanols of 40g 18%Li-dispersion liquid, 6.9g spinelle LiMn
2O
4Combine with 0.69g SP carbon black and to prepare.This mixture stirs some hrs, adds 5ml 1-butanols in paste, with one the scraper of the high 1mm of the edge of a knife it be cast to can TEFLON fep film base available from E.I.Du Pont Company on.This negative electrode is air drying around, provides the heavy 21mg/cm of coating
2
Anode film be by the propylene carbonate of 40g 15.6%Li-Nafion/1-butanols dispersion liquid, with 6.93g mesophase-carbon micro-beads (MCMB 25-28 Osaka Gas, AluminaTrading Co, New Jersey Puckridge) and 0.69g SP carbon black combine and prepare.This mixture stirred 4 hours.With the scraper of a high 0.75mm of the edge of a knife anode casting to PFA film base, provide the heavy 16mg/cm of coating
2Film.
Current-collector is to make from hammering flat expanded metal net (Delker, the vigorous blue Ford in the Connecticut State) into shape, makes anode collector with copper, makes cathode collector with aluminum.The aluminum current collector precoating from ADCOTE 50C12 (Morton international corporation, Chicago, Illinois) and the SP carbon black is made, with the adhesion promotor of ethanol dilution.
25cm
2The battery of area is laminated on becomes S/Cu/A/S/S/C/Al/C together, and wherein S, A and C are above-described diffusion barrier, anode film and cathodic coating.Laminating machine (WesternMagnum XRL-14, California Ai Ersai rolls many) uses and is heated to 140 ℃, the wide 2.8 pounds of pressure of per inch roll gap, the roller that has rubber to cover.Laminate was heated to 120 ℃ of dryings 1 hour under vacuum.In filling the glove box of nitrogen, this laminate flooded 30 minutes in 1: 1 (weight) mixture of 2-dimethoxy-ethane at normal temperatures in ethylene carbonate and 1, and the weight of this laminate is increased to 3.25g from 2.76g during this period.This laminate allows copper and aluminium net lappet stretch out from this bag with aluminium/Polythene Bag sealing.
This battery arrives 4.2V with the constant current charge of 10mA, makes this moment voltage keep constant, drops to below the 1mA until electric current.The electric charge that charges into is 62mAh.Make this battery with the constant current discharge of 10mA to 2.8V, discharge capacity is 31mAh.Make it 26 circulations of voltage range charging-discharge subsequently at 2.8~4.2V.Charging and discharge are what the constant current with 5mA carried out, until reaching voltage limit, keep constant voltage then, drop to below the 0.5mA until electric current.The capacity of the 26th circulation is 26mAh.
Example 52~63
In these examples, demonstration be that the conductivity CPV that calculates from solvent parameter and actual % (weight) intake is very closely-related with the actual measurement conductivity.And then, find out that from these examples when calculating conductivity above 0.3mS/cm, the actual measurement conductivity surpasses 0.1mS/cm.
Nafion
117, promptly a kind of can be to change into the lithium ionomer and be exposed to solvent listed in the table 8 according to the above method available from the 1100g/eq. perfluorinated ion-exchange membrane of E.I.Du Pont Company (Wilmington, the Delaware State).The results are shown in Table 8 for result of calculation and measuring.
Table 8:Nafion
117 actual measurement conductivity and calculating in selected solvent
Conductivity (CPV) relatively
Conductivity
% weight, calculated value, measured value example number, solvent, MW, density, dielectric constant, viscosity y, intake, donicity, (mS/cm), (mS/cm), 52, DMF, 73, 1, 0.944, 36.71, 0.8, 225, 26.6, 5.90, 3.09, 53, DMA, 87.12, 0.937, 37.78, 0.84, 167, 27.8, 1.99, 3.05, 54, DMSO, 78.13, 1.101, 46.68, 1.1, 136, 29.8, 1.10, 1.52, 55, NMP, 99.15, 1.03, 32, 1.67, 134, 27.3, 0.52, 1.13, 56, GBL, 86.09, 1.13, 39.1, 1.75, 88, 16.6, 0.19, 0.48, 57, EC, 88.06, 1.41, 89.6, 1.85, 71, 16.4, 0.11, 0.14, 58, DME, 90.12, 0.87, 7.2, 0.46, 29, 20, 0.02, 0.10, 59, PC, 102.09, 1.21, 64.4, 2.53, 65, 15.1, 0.05, 0.02, 60, MF, 60.05, 0.974, 8.5, 0.33, 16, 16.5, 0.01, 0.01, 61, THF, 72.11, 0.889, 7.58, 0.46, 23, 20, 0.01, 0.01, 62, ACN, 41.05, 0.782, 37.5, 0.33, 19, 14.1, 0.02, 0.01, 63, TEP, 182.16, 1.072, 13.3, 2.147, 154, 26, 0.36, 0.35
Claims (31)
1. one kind demonstrates conductivity and is the highly fluorinated lithium ion exchange polymer dielectric film (FLIEPEM) of 0.1mS/cm at least, and this film comprises:
A kind of highly fluorinated lithium ion exchange polymer membrane (FLIEPM), this polymer have side chain Fluoroalkyloxy sulfonic acid lithium group, and wherein this polymer is fully or is cation exchange partly; With
At least a non-proton transitivity solvent that is absorbed in the described film, this FLIEPEM is characterised in that conductivity parameter value (CPV) is 0.3 or bigger.
2. highly fluorinated lithium ion exchange polymer dielectric film (FLIEPEM), this film comprises
A kind of highly fluorinated lithium ion exchange polymer membrane (FLIEPM), this polymer have side chain Fluoroalkyloxy sulfonic acid lithium group, and wherein this polymer is fully or is cation exchange partly; With
At least a non-proton transitivity solvent that is absorbed in the described film, this FLIEPEM is characterised in that conductivity is 0.1mS/cm at least, these one or more non-proton transitivity solvent is selected from a group of following composition: dimethyl formamide (DMF), dimethoxy-ethane (DME), ethylene carbonate (EC), propylene carbonate (PC), dimethyl sulfoxide (DMSO) (DMSO), gamma-butyrolacton (GBL), N, N '-dimethylpropylene urea (DMPU), 1-Methyl-2-Pyrrolidone (NMP), dimethylacetylamide (DMA), N, N '-amide dimethyl butyrate (DMB), triethyl phosphate (TEP), N, N '-di-n-butyl acetamide (DBA), and composition thereof; The perhaps mixture of PC and a kind of solvent of from DME, EC, GBL, dimethyl carbonate (DMC) and acrylonitrile (ACN) composition one group, selecting; Or the mixture of a kind of solvent of selecting EC and form from DME, GBL, DMSO, diethoxyethane (DEE) and DMC one group; Or the mixture of a kind of solvent of selecting NMP and form from DME, DMSO, GBL, DMF and DMA one group; Or the mixture of GBL and DEE or DME; Or the mixture of a kind of solvent of selecting EC and DME and form from diethyl carbonate (DEC), DMC and PC one group; Or DMF and from DMA, DMSO, NMP, methyl glycollate (MG), GBL, TEP, EC, DME, PC, methyl formate (MF), oxolane (THF), sulfolane (SULF), DMC, ACN, methyl acetate (MA), DEC, 1, the mixture of a kind of solvent of selecting in one group that 3-dioxolanes (DIOX), DEE, ethyl acrylate (EA) and dimethyl sulfite (DMSU) are formed; Or DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMSO and from NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or NMP and from MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or MG and from GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or GBL and from TEP, EC, DME, PC, MF, THF, ACN, MA, DEC, the mixture of a kind of solvent of selecting in one group that DIOX and EA form; Or the mixture of a kind of solvent of selecting TEP and form from EC, PC, SULF, ACN and DMSU one group; Or the mixture of EC and DME; Or the mixture of DME and ACN or DMSU; Or EC, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group of solvent that EA and DMSU form; Or EC, DMA and from DMSO, NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, DMSO and from NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, the mixture of a kind of solvent of selecting in one group that DMSU forms; Or EC, NMP and from MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, MG and from GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, GBL and from TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, TEP and from DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, DME and from MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of EC, MF and DEC or DIOX; Or the mixture of EC, THF and DEC or DIOX; Or the mixture of EC, DMC and DIOX; Or the mixture of EC, DEC and DIOX; Or PC, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, DMSO and from NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, NMP and from MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, MG and from GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, GBL and from TEP, EC, DME, MF, THF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, TEP and from EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of a kind of solvent of selecting PC, DME and form from THF, DEC and DIOX one group; Or DMC, DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, DMSO and from NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, NMP and from MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, MG and from GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, GBL and from TEP, EC, DME, PC, MF, THF, ACN, MA, DEC, the mixture of a kind of solvent of selecting in one group that DIOX and EA form; Or the mixture of a kind of solvent of selecting DMC, TEP and form from EC, PC, SULF and ACN one group; Or the mixture of DMC, EC and DME or DIOX; Or the mixture of DMC, DME and ACN; Or DME, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, DMA and from DMSO, NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, DMSO and from NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, NMP and from MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, MG and from GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, GBL and from TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, TEP and from EC, PC, SULF, the mixture of a kind of solvent of selecting in one group that ACN and DMSU form; Or DME, EC and from MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of a kind of solvent of selecting DME, PC and form from THF, DEC and DIOX one group; Or the mixture of DME, MF and SULF or ACN; Or the mixture of DME, THF and SULF or ACN; Or the mixture of DME, SULF and DEC or DIOX; Or the mixture of DME, DMC and ACN; Or the mixture of a kind of solvent of selecting DME, ACN and form from MA, DEC, DIOX, DEE, EA and DMSU one group.
3. the FLIEPEM of claim 2, wherein one or more solvents are selected from a group of following composition: DMF, DME, EC, PC, DMSO, GBL, DMPU, NMP, DMA, DMB, TEP, DBA, and composition thereof form one group; Or the mixture of a kind of solvent of selecting PC and form from DME, EC, GBL, DMC and ACN one group; Or the mixture of a kind of solvent of selecting EC and form from DME, GBL, DMSO, DEE and DMC one group; Or the mixture of a kind of solvent of selecting NMP and form from DME, DMSO, GBL, DMF and DMA one group; Or the mixture of GBL and DEE or DME; Or the mixture of a kind of solvent of selecting EC and DME and form from DEC, DMC and PC one group.
4. the FLIEPEM of claim 3, wherein one or more solvents are selected from a group of following composition: DMSO, DMF, PC, EC, NMP, GBL, and composition thereof and they and form from DMC, DME and DEC one group the mixture of at least a solvent selected.
5. the FLIEPEM of claim 4, wherein, this solvent mixture comprises EC and DMC, or the mixture of the another kind of at least solvent of selecting they and form from GBL, PC, DEC, DMSO and DME a group.
6. the FLIEPEM of claim 1 or claim 2, wherein, this polymer is a kind of perfluoroolefine homopolymers or copolymer that pendant sulfonic acid lithium group is arranged.
7. the FLIEPEM of claim 6, wherein, this side-chain radical is a Fluoroalkyloxy sulfonate.
8. the FLIEPEM of claim 6, wherein, this polymer is a kind of copolymer that comprises a kind of nonionic perfluoroolefin comonomer of at least 50% (mole).
9. the FLIEPEM of claim 8, wherein, this copolymer comprises a kind of nonionic perfluoroolefin comonomer of at least 70% (mole).
10. the FLIEPEM of claim 9, wherein, this copolymer comprises a kind of nonionic perfluoroolefine comonomer of at least 80% (mole).
11.FLIEPEM formation technology, this technology comprises: a kind of FLIEPM is contacted in-40~200 ℃ temperature range in a kind of dry environment with at least a non-proton transitivity solvent, the combination of this solvent and polymer has CPV at least O.3mS/cm, forms a kind of conductivity and is the FLIEPEM of 0.1mS/cm at least.
12.FLIEPEM formation technology, this technology comprises:
A kind of FLIEPM is contacted with at least a non-proton transitivity solvent, form the FLIEPEM that a kind of conductivity is 0.1mS/cm; These one or more solvents are selected from a group of following composition: dimethyl formamide (DMF), dimethoxy-ethane (DME), ethylene carbonate (EC), propylene carbonate (PC), dimethyl sulfoxide (DMSO) (DMSO), gamma-butyrolacton (GBL), N, N '-dimethylpropylene urea (DMPU), 1-Methyl-2-Pyrrolidone (NMP), dimethylacetylamide (DMA), N, N '-amide dimethyl butyrate (DMB), triethyl phosphate (TEP), N, N '-di-n-butyl acetamide (DBA), and composition thereof; The perhaps mixture of PC and a kind of solvent of from DME, EC, GBL, dimethyl carbonate (DMC) and acrylonitrile (ACN) composition one group, selecting; Or the mixture of a kind of solvent of selecting EC and form from DME, GBL, DMSO, diethoxyethane (DEE) and DMC one group; Or the mixture of a kind of solvent of selecting NMP and form from DME, DMSO, GBL, DMF and DMA one group; Or the mixture of GBL and DEE or DME; Or the mixture of a kind of solvent of selecting EC and DME and form from diethyl carbonate (DEC), DMC and PC one group; Or DMF and from DMA, DMSO, NMP, methyl glycollate (MG), GBL, TEP, EC, DME, PC, methyl formate (MF), oxolane (THF), sulfolane (SULF), DMC, ACN, methyl acetate (MA), DEC, 1, the mixture of a kind of solvent of selecting in one group that 3-dioxolanes (DIOX), DEE, ethyl acrylate (EA) and dimethyl sulfite (DMSU) are formed; Or DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMSO and from NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or NMP and from MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or MG and from GBL, TFP, EC, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or GBL and from TEP, EC, DME, PC, MF, THF, ACN, MA, DEC, the mixture of a kind of solvent of selecting in one group that DIOX and EA form; Or the mixture of a kind of solvent of selecting TEP and form from EC, PC, SULF, ACN and DMSU one group; Or the mixture of EC and DME; Or the mixture of DME and ACN or DMSU; Or EC, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group of solvent that EA and DMSU form; Or EC, DMA and from DMSO, NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, DMSO and from NMP, MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, EA, the mixture of a kind of solvent of selecting in one group that DMSU forms; Or EC, NMP and from MG, GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, MG and from GBL, TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, GBL and from TEP, DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, TEP and from DME, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or EC, DME and from MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of EC, MF and DEC or DIOX; Or the mixture of EC, THF and DEC or DIOX; Or the mixture of EC, DMC and DIOX; Or the mixture of EC, DEC and DIOX; Or PC, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, DMSO and from NMP, MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, NMP and from MG, GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, MG and from GBL, TEP, EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, GBL and from TEP, EC, DME, MF, THF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or PC, TEP and from EC, DME, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of a kind of solvent of selecting PC, DME and form from THF, DEC and DIOX one group; Or DMC, DMA and from DMSO, NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, DMSO and from NMP, MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, NMP and from MG, GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, MG and from GBL, TEP, EC, DME, PC, MF, THF, SULF, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DMC, GBL and from TEP, EC, DME, PC, MF, THF, ACN, MA, DEC, the mixture of a kind of solvent of selecting in one group that DIOX and EA form; Or the mixture of a kind of solvent of selecting DMC, TEP and form from EC, PC, SULF and ACN one group; Or the mixture of DMC, EC and DME or DIOX; Or the mixture of DMC, DME and ACN; Or DME, DMF and from DMA, DMSO, NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, DMA and from DMSO, NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, DMSO and from NMP, MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, NMP and from MG, GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, MG and from GBL, TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, GBL and from TEP, EC, PC, MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or DME, TEP and from EC, PC, SULF, the mixture of a kind of solvent of selecting in one group that ACN and DMSU form; Or DME, EC and from MF, THF, SULF, DMC, ACN, MA, DEC, DIOX, DEE, the mixture of a kind of solvent of selecting in one group that EA and DMSU form; Or the mixture of a kind of solvent of selecting DME, PC and form from THF, DEC and DIOX one group; Or the mixture of DME, MF and SULF or ACN; Or the mixture of DME, THF and SULF or ACN; Or the mixture of DME, SULF and DEC or DIOX; Or the mixture of DME, DMC and ACN; Or the mixture of a kind of solvent of selecting DME, ACN and form from MA, DEC, DIOX, DEE, EA and DMSU one group.
13. the technology of claim 12, these one or more solvents are selected from a group of following composition: DMF, DME, EC, PC, DMSO, GBL, DMPU, NMP, DMA, DMB, TEP, DBA, and composition thereof form one group; Or the mixture of a kind of solvent of selecting PC and form from DME, EC, GBL, DMC and ACN one group; Or the mixture of a kind of solvent of selecting EC and form from DME, GBL, DMSO, DEE and DMC one group; Or the mixture of a kind of solvent of selecting NMP and form from DME, DMSO, GBL, DMF and DMA one group; Or the mixture of GBL and DEE or DME; Or the mixture of a kind of solvent of selecting EC and DME and form from DEC, DMC and PC one group.
14. the technology of claim 13, these one or more solvents are selected from a group of following composition: DMSO, DMF, PC, EC, NMP, GBL, and composition thereof and they and form from DMC, DME and DEC one group the mixture of at least a solvent selected.
15. the technology of claim 14, wherein, this solvent comprises the mixture of EC and DMC, or the mixture of the another kind of at least solvent of selecting they and form from GBL, PC, DEC, DMSO and DME a group.
16. lithium ion battery group, comprise one or more electrochemical cells, wherein comprise a positive pole, negative pole and one and be disposed between positive pole and the negative pole and be in the FLIEPEM that contacts with its ionic conduction, with a kind of means that these electrodes are connected with external electrical load or power supply of being used to.
17. the battery pack of claim 16, wherein, this battery pack is rechargeable.
18. a porous electrode wherein comprises a kind of particle of electrode active material, a kind of highly fluorinated lithium ion exchange polymer and at least a non-proton transitivity solvent that is selected from this group of claim 2.
19. the battery pack of claim 17, wherein, this electrode is the electrode of claim 18.
20. an electrode forms technology, this technology comprises
Prepare a kind of solution or dispersion liquid that the highly fluorinated polymers of side chain Fluoroalkyloxy sulfonic acid lithium or sulfuryl fluoride group is arranged;
In this solution or dispersion liquid, sneak into a kind of electrode active material of a granular form, form a kind of coating paste;
Form a kind of film from this coating paste;
By heating, make the polymer coagulation in this film;
With, if this side-chain radical is a kind of sulfuryl fluoride, then make this polymer hydrolysis become a kind of lithium ionomer.
21. the technology of claim 20, wherein, this polymer has a kind of side chain Fluoroalkyloxy sulfonic acid lithium group, and this solvent is the mixture of propylene carbonate and a kind of alcohol.
22. the FLIEPEM of claim 8, wherein, this nonionic perfluoroolefine monomer is selected from a group of following composition: tetrafluoroethene (TFE), hexafluoropropylene, PVF, vinylidene fluoride, trifluoro-ethylene, one chlorotrifluoroethylene, perfluor (alkyl vinyl ether), and composition thereof.
23. the FLIEPEM of claim 8, wherein, this copolymer is to form from TFE and a kind of perfluorovinyl sulfide monomer that side-chain radical shown in the following formula arranged:
-(O-CF
2CFR)
aO-CF
2CFR ' SO
3Li, R and R ' are independently selected from F, Cl or a kind of perfluorinated alkyl that 1~10 carbon atom is arranged, a=0,1 or 2 in the formula.
24. the FLIEPEM of claim 23, wherein R is CF
3, R ' is F, and a=0 or 1.
25. the FLIEPEM of claim 24, wherein a=1.
26. the FLIEPEM of claim 8 has 600~1500 gram/equivalent weights in weight range.
27. the FLIEPEM of claim 26 has 900~1200 gram/equivalent weights in weight range.
28. the technology of claim 11 or 12, wherein, this polymer is a kind of copolymer that comprises a kind of nonionic perfluoroolefine monomer of at least 50% (mole).
29. the technology of claim 28, wherein, this nonionic perfluoroolefine monomer is selected from a group of following composition: tetrafluoroethene (TFE), hexafluoropropylene, PVF, vinylidene fluoride, trifluoro-ethylene, one chlorotrifluoroethylene, perfluor (alkyl vinyl ether), and composition thereof.
30. the technology of claim 28, wherein, this copolymer is to form from TFE and a kind of perfluorovinyl sulfide monomer that side-chain radical shown in the following formula arranged:
-(O-CF
2CFR)
aO-CF
2CFR ' SO
3Li, R is CF in the formula
3, R ' is F, and a=0 or 1.
31. the technology of claim 11 or claim 12, wherein this FLIEPM contacts with at least two kinds of non-proton transitivity solvents, and this further comprises first solvent contact procedure, also has at least one solvent contact procedure subsequently.
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CN 97181163 CN1242877A (en) | 1996-11-01 | 1997-10-31 | Highly conductive ion exchange polymer and process |
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1997
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