CN105229842A

CN105229842A - Phosphonium ionic liquid, salt, composition, manufacture method and the device formed by it

Info

Publication number: CN105229842A
Application number: CN201380072290.4A
Authority: CN
Inventors: 本杰明·L·鲁珀特; 莱维·J·厄文; 利安娜·比尔; 什尔帕·A·沃利卡; 石志超
Original assignee: eSionic ES Inc
Current assignee: eSionic Corp
Priority date: 2012-12-05
Filing date: 2013-10-18
Publication date: 2016-01-06
Also published as: EP2929587A1; KR20150092270A; EP2929587A4; JP2014133734A; WO2014088710A1; JP2016507855A

Abstract

The present invention is Bao Kuo Phosphonium ionic liquid, salt, composition and their purposes in numerous applications generally, include but not limited to: as electronic installation as memory storage, comprise the electrolyte in static state, permanent and dynamic RAM, as energy storing device as the electrolyte in battery, electrochemical double layer capacitor (EDLC) or ultracapacitor or ultra-capacitor, electrolytic capacitor, as the electrolyte in DSSC (DSSC), as the electrolyte in fuel cell, as heat transfer medium, and other application.Particularly, She on this invention Zong body is Ji Phosphonium ionic liquid, salt, composition, and wherein, said composition shows the excellent combination of thermodynamic stability, low volatility, wide liquidus curve scope, ionic conductivity and electrochemical stability.The present invention comprises the method making Zhe Zhong Phosphonium ionic liquid, salt, composition further, comprises its operating means and system.

Description

Phosphonium ionic liquid, salt, composition, manufacture method and the device formed by it

Technical field

The present invention is Bao Kuo Phosphonium ionic liquid generally, salt, composition and their purposes in numerous applications, include but not limited to: as electronic installation as memory storage, comprise static state, electrolyte forever and in dynamic RAM, as energy storing device as battery, electrochemical double layer capacitor (EDLC) or ultracapacitor (supercapacitor) or ultra-capacitor (ultracapacitor), electrolyte in electrolytic capacitor, as the electrolyte in DSSC (DSSC), as the electrolyte in fuel cell, as heat transfer medium, pyroreaction and/or Extraction medium, and other application.Particularly, this invention She is Ji Phosphonium ionic liquid, salt, composition and have the molecule of architectural feature, wherein, these compositions table reveal following at least two or more expectation combination: thermodynamic stability, low volatility, wide liquidus curve scope and ionic conductivity.The present invention comprises the method making Zhe Zhong Phosphonium ionic liquid, salt, composition and molecule and the operating means and the system that comprise it further.

Background technology

Receive remarkable concern due to their potential uses widely and application to ion liquid section.Term " ionic liquid " is generally used for the salt of fusing point relatively low (below 100 DEG C and 100 DEG C).At room temperature that the salt of liquid is commonly referred to ionic liquid at room temperature.Early stage researcher adopts the ionic liquid based on dialkylimidazolium salt.Such as, the people such as Wilkes have developed the ionic liquid based on dialkylimidazolium salt used together with chlorine negative electrode with aluminum metal anode in the trial of setting up battery.J.Wilkes,J.Levisky,R.Wilson,C.Hussey,Inorg.Chem,21,1263(1982)。

The most extensively research and normally used ionic liquid in some be based on pyridiniujm, wherein N-alkyl pyridine and N, N '-dialkylimidazolium finds remarkable purposes.Pyridine ionic liquid (comprises N-alkyl-pyridine and N, N-dialkylimidazolium) and nitrogen class ionic liquid there is thermodynamic stability usually that be limited to less than 300 DEG C, be easy to distillation and remarkable lower than the temperature of 200 DEG C under often there is measurable vapour pressure.These character limit their serviceability and their application.Such as, this ionic liquid easily decomposes in rear end operation (backendofline) (BEOL) hot procedure.In addition, this ionic liquid also decomposes in other heat transfer procedure of processing processes often making ionic liquid stand to circulate more than the Continuous Heat of 300 DEG C of temperature.

Continue the multiple character having inquired into ionic liquid, and consider the other purposes of ionic liquid.Such as, electrochemical method and application need electrolyte to strengthen the conductivity in multiple device and application.Research in recent years is carried out in the electrolytical ionic liquid at room temperature field that may substitute of solvent based as routine.

Although research and develop, but it is evident that exist for ionic liquid, salt and electrolyte composition and electrolyte may be adopted to be used for the lasting needs of electrochemical double layer capacitor, lithium metal and lithium ion battery, fuel cell, DSSC and the material of molecular memory device and the new research and development of purposes.

Summary of the invention

The present invention is Bao Kuo Phosphonium ionic liquid widely, salt, composition and their purposes in numerous applications, include but not limited to: as electronic installation as memory storage, comprise static state, electrolyte forever and in dynamic RAM, as energy storing device as battery, electrochemical double layer capacitor (EDLC) or ultracapacitor or ultra-capacitor, electrolyte in electrolytic capacitor, as the electrolyte in DSSC (DSSC), as the electrolyte in fuel cell, as heat transfer medium, pyroreaction and/or Extraction medium, and other application.Particularly, this invention She is Ji Phosphonium ionic liquid, salt, composition and have the molecule of architectural feature, wherein, said composition show following at least two or more expectation combination: thermodynamic stability, low volatility, wide liquidus curve scope and ionic conductivity.

On the one hand, provide ionic liquid compositions, it comprises: the Yi kind of following general formula or Duo Zhong Phosphonium cationoid:

R ¹R ²R ³R ⁴P，

Wherein: wherein, R ¹, R ², R ³and R ⁴be optional and be substituting group independently of one another; With one or more anion.In some embodiments, R ¹, R ², R ³and R ⁴the different alkyl group be made up of 2 to 14 carbon atoms independently of one another.In some embodiments, R ¹, R ², R ³and R ⁴in at least one be aliphatic heterocycle part.Alternately, R ¹, R ², R ³and R ⁴in at least one be heteroaromatic part.In other embodiments, R ¹and R ²identical and be made up of following: tetramethylene phospholane (tetramethylenephospholane), pentamethylene phospha cyclohexane (pentamethylenephosphorinane), four methine Phospholes (tetramethinylphosphole), phospholane (phospholane) or phospha cyclohexane (phosphorinane).In another embodiment, R ², R ³and R ⁴identical and be made up of following: phospholane, phospha cyclohexane or Phospholes.

In another embodiment, provide ionic liquid compositions, comprise Yi kind or Duo Zhong Phosphonium cationoid and one or more anion, wherein, this ionic liquid compositions show be greater than 375 DEG C thermodynamic stability, be greater than the liquidus curve scope of 400 DEG C and room temperature under be up to the ionic conductivity of 10mS/cm.

On the other hand, the present invention includes the electrolyte composition be made up of Phosphonium cationoid and suitable anion.In some embodiments, employ term " electrolyte " or " electrolyte solution " or " electrolyte composition " or " ionic electrolytes " or " ionic conductivity electrolyte " or " ion conductive composition " or " ionic composition " and be defined as following any one or multiple in this article: (a) ionic liquid, (b) ionic liquid at room temperature, (c) is dissolved in one or more salt at least one solvent; (d) one or more salt forming gel electrolyte at least one solvent together with at least one polymer are dissolved in.In addition, one or more salt are defined as and comprise: (a) is one or more salt of solid under 100 DEG C and following temperature, and (b) is one or more salt of liquid under 100 DEG C and following temperature.

In another embodiment, provide electrolyte composition, and it is made up of following: dissolve one or more salt in a solvent, these one or more salt comprise one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P(1)，

With one or more anion, and wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another, such as but not limited to following described alkyl group.In some embodiments, R ¹, R ², R ³and R ⁴by 1 to 6 carbon atom independently of one another, the more commonly alkyl group of 1 to 4 carbon atom composition.Any one in salt or multiple can be liquid or solid under 100 DEG C and following temperature.In some embodiments, salt by a kind of cation and a kind of anion to forming.In other embodiments, salt is made up of a kind of cation and multiple anion.In other embodiments, salt is by a kind of anion and multiple cation composition.In further execution mode, salt is made up of multiple cation and multiple anion.

In another embodiment, electrolyte composition comprises one or more routine non-phosphonium salts further.In some embodiments, this electrolyte composition can be made up of the salt of routine, and wherein, this literary composition Gong Kai Phosphonium class ionic liquid or salt are additives.In some embodiments, electrolyte composition is made up of the salt of Phosphonium class ionic liquid or salt and one or more routines, with 1:100 to 1:1 Phosphonium class ionic liquid or salt: mole (or mole) within the scope of conventional salt is than existing.The example of conventional salt includes but not limited to the salt be made up of one or more cations and one or more anion, and this cation is selected from by the following group formed: tetra-allkylammonium, such as (CH ₃cH ₂) ₄n ⁺, (CH ₃cH ₂) ₃(CH ₃) N ⁺, (CH ₃cH ₂) ₂(CH ₃) ₂n ⁺, (CH ₃cH ₂) (CH ₃) ₃n ⁺, (CH ₃) ₄n ⁺, imidazoles, pyrazoles, pyridine, pyrazine, pyrimidine, pyridazine, pyrrolidines, this anion is selected from by the following group formed: ClO ₄ ^-, BF ₄ ^-, CF ₃sO ₃ ^-, PF ₆ ^-, AsF ₆ ^-, SbF ₆ ^-, (CF ₃sO ₂) ₂n ^-, (CF3CF ₂sO ₂) ₂n ^-, (CF ₃sO ₂) ₃c ^-.In some embodiments, the salt of one or more routines includes but not limited to: tetraethylammonium tetrafluoroborate (TEABF ₄), tetrafluoro boric acid triethyl methyl ammonium (TEMABF ₄), 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF ₄), 1-ethyl-1-picoline tetrafluoroborate (EMPBF ₄), 1-ethyl-3-methylimidazole two (trifyl) acid imide (EMIIm), 1-ethyl-3-methylimidazole hexafluorophosphate (EMIPF ₆).In some embodiments, the salt of one or more routines is lithium class salt, includes but not limited to: lithium hexafluoro phosphate (LiPF ₆), LiBF4 (LiBF ₄), lithium perchlorate (LiClO ₄), hexafluoroarsenate lithium (LiAsF ₆), three fluoromethanesulfonic lithiums or trifluoromethanesulfonic acid lithium (LiCF ₃sO ₃), two (trifyl) imide li (Li (CF ₃sO ₂) ₂n or LiIm) and two (five fluorine mesyls) imide li (Li (CF3CF ₂sO ₂) ₂n or LiBETI).

Further aspect of the present invention provides battery, comprising: positive pole, negative pole, barrier film between described positive pole and negative pole; And electrolyte.This electrolyte is made up of the ionic liquid compositions dissolved in a solvent or one or more salt, comprises: one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

Wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion.In another embodiment, electrolyte is characterized by has one kind or many kinds of Phosphonium cationoids and one or more anion, wherein, ionic liquid compositions shows and is up to the thermodynamic stability being greater than 375 DEG C of temperature, the ionic conductivity being greater than under the liquidus curve scope of 400 DEG C and room temperature at least 1mS/cm or at least 5mS/cm or at least 10mS/cm.In another embodiment, electrolyte is made up of one or more salt with dissolving in a solvent a kind or many kinds of Phosphonium cationoids and one or more anion, wherein, this electrolyte composition to show under room temperature the ionic conductivity of at least 5mS/cm or at least 10mS/cm or at least 15mS/cm or at least 20mS/cm or at least 30mS/cm or at least 40mS/cm or at least 50mS/cm or at least 60mS/cm.Further ， Phosphonium electrolyte meter reveals the combustibility of reduction compared with the electrolyte of routine, therefore improves battery-operated fail safe.In other, Phosphonium ionic liquid or salt are used as the formation that additive promotes alternate (SEI) layer of solid electrolyte or electrode protecting layer by Ke Yi.This SEI layer can widen electrochemical stability window, suppresses degraded or the decomposition reaction of battery, thus improves battery cycle life.

Further aspect of the present invention provides electrochemical double layer capacitor (EDLC), comprises: positive pole, negative pole, barrier film between described positive pole and negative pole; And electrolyte.This electrolyte is made up of the ionic liquid compositions dissolved in a solvent or one or more salt, comprises: one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

Wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion.In another embodiment, electrolyte is characterized by has one kind or many kinds of Phosphonium cationoids and one or more anion, wherein, ionic liquid compositions or salt show and are up to the thermodynamic stability being greater than 375 DEG C of temperature, the ionic conductivity being greater than under the liquidus curve scope of 400 DEG C and room temperature at least 1mS/cm or at least 5mS/cm or at least 10mS/cm.In another embodiment, electrolyte is made up of one or more salt with dissolving in a solvent a kind or many kinds of Phosphonium cationoids and one or more anion, wherein, this electrolyte composition to show under room temperature the ionic conductivity of at least 5mS/cm or at least 10mS/cm or at least 15mS/cm or at least 20mS/cm or at least 30mS/cm or at least 40mS/cm or at least 50mS/cm or at least 60mS/cm.Further ， Phosphonium electrolyte meter reveals the combustibility of reduction compared with the electrolyte of routine, therefore improves the fail safe of EDLC operation.In other, Phosphonium ionic liquid or salt are used as the formation that additive promotes alternate (SEI) layer of solid electrolyte or electrode protecting layer by Ke Yi.This is protective layer used in widening electrochemical stability windows, suppresses degraded or the decomposition reaction of EDLC, thus improves the cycle life of EDLC.

Embodiments of the present invention further provide heat transfer medium, comprise dissolving ionic liquid compositions in a solvent or one or more salt, comprise: Yi kind or Duo Zhong Phosphonium cationoid and one or more anion, wherein, this heat transfer medium shows and is being greater than the thermodynamic stability at 375 DEG C of temperature, is being greater than the liquidus curve scope of 400 DEG C.

Phosphonium ionic liquid compositions and salt can be used for forming multiple hybrid battery device of air.Such as, in one embodiment, provide a kind of device, the electrolyte comprising the first electrode, the second electrode and be made up of the ionic liquid compositions dissolved in a solvent or one or more salt, comprises: one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

Wherein, R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion, and wherein, described electrolyte is electrically coupled at least one in described first and second electrodes.In some embodiments, the first electrode is made up of redox active molecule (ReAM).

In another embodiment, provide molecular memory device, its comprise work electrode and and be configured to provide the counterelectrode of electric capacity; With the ion conductive composition comprising the following: the Yi kind of above general formula or Duo Zhong Phosphonium cationoid, and wherein, this ion conductive composition is electrically coupled at least one in work electrode and counterelectrode.

In another embodiment, the present invention includes comprise switching device, the molecular memory element of the bit line (bitline) that is coupled to switching device and wordline (wordline) and by the addressable molecular memory device of this switching device.This molecular memory device can be placed on two or more discrete states, wherein, by the signal that is applied to bit line and wordline this molecular memory device be placed in discrete state.This molecular memory device comprises the first electrode, the electrolyte of Phosphonium cationoid and suitable anion between the second electrode and described first and second electrodes.

Another execution mode comprises molecular memory array, and it comprises multiple molecular memory element, wherein, each molecular memory element can be placed on two or more discrete states.Each molecular memory element is made by multiple bit line and word line coupling to multiple molecular memory element to be coupled at least one bit line and at least one wordline and can by its addressing.

Accompanying drawing explanation

By reading detailed description of the present invention and the following appended claims that provide and by reference to accompanying drawing, other aspects of the present invention, execution mode and advantage will become apparent, wherein:

Fig. 1 depicts a kind of reaction scheme forming Phosphonium ionic liquid according to certain embodiments of the present invention;

Fig. 2 depicts the another kind of reaction scheme of other execution modes of the Phosphonium ionic liquid forming Ben Faming;

Fig. 3 depicts the another kind of reaction scheme formed according to other execution modes Phosphonium ionic liquid of the present invention;

Fig. 4 depicts the another kind of reaction scheme formed according to further execution mode Phosphonium ionic liquid of the present invention;

Fig. 5 is thermogravimetric analysis (TGA) figure carried out the illustrative embodiments preparing Phosphonium ionic liquid according to embodiment 1;

Fig. 6 A depicts reaction scheme, and Fig. 6 B and 6C respectively illustrates thermogravimetric analysis (TGA) and emergent gas analysis (evolvedgasanalysis) (EGA) figure of preparing the illustrative embodiments of Phosphonium ionic liquid according to embodiment 2;

Fig. 7 A and 7B shows respectively and prepares the thermogravimetric analysis (TGA) of the illustrative embodiments of Phosphonium ionic liquid and the figure of emergent gas analysis (EGA) according to embodiment 3;

Fig. 8 A depicts reaction scheme, and Fig. 8 B shows the illustrative embodiments of the preparation Phosphonium ionic liquid described by Fig. 2 and embodiment 4 ¹hNMR spectrogram;

Fig. 9 A is reaction scheme, and Fig. 9 B shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of Phosphonium ionic liquid according to embodiment 5;

Figure 10 shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of Phosphonium ionic liquid according to embodiment 6;

Figure 11 shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of Phosphonium ionic liquid according to embodiment 7;

Figure 12 A depicts reaction scheme, and Figure 12 B shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of Phosphonium ionic liquid according to embodiment 8;

Figure 13 A and Figure 13 B respectively illustrates and prepares the illustrative embodiments of phosphonium salt according to the description of embodiment 9 ¹h and ³¹pNMR spectrogram;

Figure 14 shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of phosphonium salt according to embodiment 9;

Figure 15 A and Figure 15 B respectively illustrates the illustrative embodiments of preparation phosphonium salt as described in Example 10 ¹h and ³¹pNMR spectrogram;

Figure 16 shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of phosphonium salt according to embodiment 10;

Figure 17 A and Figure 17 B respectively illustrates the illustrative embodiments of preparation phosphonium salt as described in Example 11 ¹h and ³¹pNMR spectrogram;

Figure 18 shows the figure of thermogravimetric analysis (TGA) result preparing the illustrative embodiments of phosphonium salt according to embodiment 11;

Figure 19 A and Figure 19 B shows the figure of differential scanning calorimetry (DSC) result preparing the illustrative embodiments of Phosphonium ionic liquid according to embodiment 12;

Figure 20 depict as described in Example 14 at acetonitrile (ACN) Zhong phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃as the ionic conductivity of the function of ACN/ salt volume ratio;

Figure 21 depicts as described in Example 15 at propylene carbonate (PC) Zhong phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃as the ionic conductivity of the function of PC/ salt volume ratio;

Figure 22 depict with such as described in embodiment 42-45 as be in propylene carbonate compared with ammonium salt, the ionic conductivity of the function of the molar concentration of phosphonium salt;

Figure 23 depict as described in Example 46 for acetonitrile, acetonitrile and 1M ammonium salt and acetonitrile and the 1M phosphonium salt vapour pressure as the function of temperature;

Figure 24 shows the phosphonium salt (CH under the different temperatures of-30 to 60 DEG C described by embodiment 51 ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃on the impact of the ionic conductivity of the 1.0MLiPF6 in EC:DEC1:1;

Figure 25 shows the phosphonium salt (CH under the different temperatures of 20 to 90 DEG C described by embodiment 52 ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃on the impact of the ionic conductivity of the 1.0MLiPF6 in EC:DEC1:1.

Embodiment

general introduction

She on this invention Zong body is Ji Phosphonium ionic liquid, salt and composition and their purposes in numerous applications.

general description

The present invention includes Xin Xing Phosphonium ionic liquid, salt, composition and their purposes in numerous applications, include but not limited to: as electronic installation as memory storage, comprise the electrolyte in static state, permanent and dynamic RAM, as the electrolyte in battery, electrochemical double layer capacitor, electrolytic capacitor, fuel cell, DSSC and electrochromic device.Application in addition comprises as heat transfer medium, pyroreaction and/or Extraction medium, and other application.Particularly, this invention She is Ji Phosphonium ionic liquid, salt, composition and have the molecule of architectural feature, wherein, said composition shows following at least two or more expectation combination: thermodynamic stability, low volatility, wide liquidus curve scope, ionic conductivity and electrochemical stability.The present invention comprises the method making Zhe Zhong Phosphonium ionic liquid, composition and molecule and the operating means and the system that comprise it further.

On the other hand, embodiments of the present invention provide the electrolytical device having and be made up of the Phosphonium ionic liquid compositions dissolved in a solvent or one or more salt.On the other hand, embodiments of the present invention provide the electrolytical battery comprising and being made up of the Phosphonium ionic liquid compositions dissolved in a solvent or one or more salt.Further, embodiments of the present invention provide the electrolyte electrochemical double layer capacitor (EDLC) comprising and being made up of the Phosphonium ionic liquid compositions dissolved in a solvent or one or more salt.

The favourable character of this Phosphonium ionic liquid compositions makes them be specially adapted to as the electrolytical application in electronic installation, battery, EDLC, fuel cell, DSSC (DSSC) and electrochromic device.

Of the present invention further in, provide the heat transfer medium be made up of the Phosphonium ionic liquid compositions dissolved in a solvent or one or more salt.The favourable character of composition of the present invention is very suitable as heat transfer medium, and to adopt in the process of heat transfer medium and system (as heat extracts (heatextraction) process and pyroreaction) be wherein useful.

definition

As used herein and unless otherwise noted, otherwise use term " electrolyte " or " electrolyte solution " or " electrolyte composition " or " ionic electrolytes " or " ionic conductivity electrolyte " or " ion conductive composition " or " ionic composition " and be defined as following any one or multiple in this article: (a) ionic liquid, (b) ionic liquid at room temperature, c () is dissolved in one or more salt at least one solvent, (d) one or more salt forming gel electrolyte at least one solvent together with at least one polymer are dissolved in.In addition, one or more salt are defined as and comprise: (a) is one or more salt of solid under 100 DEG C and following temperature, and (b) is one or more salt of liquid under 100 DEG C and following temperature.

As used herein and unless otherwise noted, otherwise term " acyl group " refers to the OH of the wherein carboxylic group organic acid group that other substituting group (RCO-) (as being described as the substituting group of " R " herein) has been replaced by some.Example includes but not limited to halogen, acetyl group and benzoyl.

As used herein and unless otherwise noted, otherwise term " alkoxy base " means-O-alkyl group, and wherein, alkyl is as defined herein.Alkoxy base can be unsubstituted or by one, two or three suitable substituting groups replace.Preferably, the alkyl chain of alkoxy base is 1 to 6 carbon atom in length, such as, is referred to herein as " (C1-C6) alkoxyl ".

As used herein and unless otherwise noted, otherwise " alkyl " itself or refer to the monovalent hydrocarbon radical by removing saturated or unsaturated, side chain, straight chain or the ring-type that a hydrogen atom derives from the single carbon atom of parent alkane, alkene or alkynes as another substituent part.Also be included in the definition of alkyl group be group of naphthene base as C5, C6 or other rings, and there is the heterocycle (Heterocyclylalkyl) of nitrogen, oxygen, sulphur or phosphorus.Alkyl also comprises assorted alkyl, and wherein hetero-atom sulphur, oxygen, nitrogen, phosphorus and silicon find special purposes in some embodiments.Alkyl group can be replaced alternatively by R group, selects independently in following described each position.

The example of alkyl group includes but not limited to (C1-C6) alkyl group, as methyl, ethyl, propyl group, isopropyl, 2-methyl isophthalic acid-propyl group, 2-methyl-2-propyl, 2-methyl-1-butene base, 3-methyl isophthalic acid-butyl, 2-methyl-3-butyl, 2, 2-dimethyl-1-propyl group, 2-methyl-1-pentene base, 3-methyl-1-pentene base, 4-methyl-1-pentene base, 2-methyl-2-amyl group, 3-methyl-2-amyl group, 4-methyl-2-amyl group, 2, 2-dimethyl-1-butyl, 3, 3-dimethyl-1-butyl, 2-ethyl-1-butyl, butyl, isobutyl group, the tert-butyl group, amyl group, isopentyl, neopentyl and hexyl and longer alkyl group are as heptyl and octyl group.

Term " alkyl " is intended to the group comprising the saturation with any degree or level definitely, that is, the group only with carbon-to-carbon singly-bound, the group with one or more carbon-to-carbon double bond, there is the group of one or more carbon-to-carbon triple bond and there is the group of mixture of the single, double and triple bond of carbon-to-carbon.When being intended to the specified level referring to saturation, using and expressing " alkyl ", " alkylene " and " alkynes base ".

" alkyl " is own or refer to saturated side chain, straight chain or the cyclic alkyl radical that derive by removing a hydrogen atom from the single carbon atom of parent alkane as another substituent part.As described above, comprise " assorted alkyl ".

" alkylene " is own or refer to the undersaturated side chain with at least one carbon-to-carbon double bond, straight chain or the cyclic alkyl radical that derive by removing a hydrogen atom from the single carbon atom of parent alkene as another substituent part.This group can be cisoid conformation about double bond also can be anti conformation.Suitable alkylene group includes but not limited to (C2-C6) alkylene group, as vinyl, pi-allyl, cyclobutenyl, pentenyl, hexenyl, butadienyl, pentadienyl, hexadienyl, 2-ethyl hexyl thiazolinyl, 2-propyl group-2-cyclobutenyl, 4-(2-methyl-3-butylene)-pentenyl.Alkylene group can be unsubstituted or can be replaced by one or more independent R group selected.

" alkynes base " is own or refer to the undersaturated side chain with at least one carbon-to-carbon triple bond, straight chain or the cyclic alkyl radical that derive by removing a hydrogen atom from the single carbon atom of parent alcyne as another substituent part.

Also be included in the definition of " alkyl " is " alkyl of replacement "." replacement " refers in particular to " R " in this article usually, and refers to the group that wherein one or more hydrogen atoms have independently been replaced by identical or different substituting group.R substituent can independently selected from but be not limited to hydrogen, halogen, alkyl (comprises the alkyl (alkylthio group of replacement, alkylamino, alkoxyl etc.), cycloalkyl, the cycloalkyl replaced, the Heterocyclylalkyl of Heterocyclylalkyl and replacement), aryl (comprises the aryl of replacement, the heteroaryl of heteroaryl or replacement), carbonyl, alcohol, amino, amide groups (amido), nitro, ether, ester, aldehyde, sulfonyl, sulfoxide group (sulfoxyl), carbamoyl, acyl group, cyano group, thiocyanogen, silicon part, halogen, sulfur-bearing part, phosphorus-containing moieties etc.In some embodiments, as described herein, R substituent comprises redox-active moiety (ReAM).In some embodiments, alternatively, form cycloalkyl (comprising Heterocyclylalkyl) and/or cyclophane base (comprising heterocyclic aryl) together with the atom that R with R' is connected with them, it also can be further substituted according to expectation.In the structure described herein, when position is unsubstituted, R is hydrogen.It should be noted that two or three substituent R, R' and R can be allowed in some positions ", in this case, R, R' and R " group can be identical or different.

In some embodiments, R group (subelement) is for regulating the oxidation-reduction potential of host compound.Therefore, as what more fully describe in reference that is following and that quote herein, can by R group as redox active subelement be added into the large ring of large ring, particularly porphyrin to change its oxidation-reduction potential.Some preferred substituting group includes but not limited to 4-chlorphenyl, 3-acetamidophenyl, 2,4-dichlor-4-trifluoromethyls and ferrocene (comprising ferrocene derivatives).When substituting group is used for changing oxidation-reduction potential, preferred substituting group provide be less than about 5 volts, be preferably less than about 2 volts, be more preferably less than the redox potential range of about 1 volt.

In some embodiments, R group as U.S.Provisional serial number 60/687,464 accompanying drawing and text defined and described, be incorporated into this by reference.U.S. Patent number 6,212,093; 6,728,129; 6,451,942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484,394; With United States serial 10/040,059; 10/682,868; 10/445,977; 10/834,630; 10/135,220; 10/723,315; 10/456,321; 10/376, multiple suitable front part (proligand) and complex compound and suitable substituting group is outlined in 865, by reference clearly in conjunction with above-mentioned whole patent, their structure particularly wherein described and description, no matter it can be used as substituting group execution mode to combine thus clearly, be wherein depict substituent specific large ring or further substitutive derivative.

" aryl " herein or grammer equivalent mean usually to comprise the aromatic monocyclic of 5 to 14 carbon atoms or polycyclic hydrocarbon part (although can make larger multiring structure) and any carbocyclic ring ketone, imines or their 40 thione derivatives, wherein, the carbon atom with free valency is the member of aromatic ring.Aromatic group comprises the arylene group and aromatic group that eliminate more than two atoms.For purposes of this application, aryl comprises heteroaryl.Aromatic group that " heteroaryl " means wherein to specify 1 to 5 in carbon atom to be selected from the hetero-atom displacement of nitrogen, oxygen, sulphur, phosphorus, boron and silicon (atom wherein, with free valency is the member of aromatic ring) and any heterocyclic ketone and their 40 thione derivatives.Therefore, heterocycle comprises monocycle and multi-loop system, such as, and thienyl, furyl, pyrrole radicals, pyrimidine radicals, indyl, purine radicals, quinolyl, isoquinolyl, thiazolyl, imidazole radicals, naphthalene, phenanthroline etc.Also being included in the definition of aryl is the aryl replaced, and has one or more substituting groups " R " that are defined herein and above and that summarize herein.Such as, " perfiuoroaryl " is comprised and it refers to the aromatic yl group that wherein each hydrogen atom has been replaced by fluorine atom.What also comprise is oxalyl group.

As used herein, term " halogen " refers to the one (fluorine, chlorine, bromine, iodine and astatine) in the electronegative element of the VIIA race of the periodic table of elements.

Term " nitro " refers to-NO ₂group.

" amino group " herein or grammer equivalent mean-NH2 ,-NHR and-NRR' group, R and R' independently as defined herein.

As used herein, term " pyridine radicals " refers to the aromatic yl group that one of them CH unit has been replaced by nitrogen-atoms.

As used herein, term " cyano group " refers to-CN group.

As used herein, term " thiocyanogen " refers to-SCN group.

Term " sulfoxide group " refer to consist of RS (O)-group, wherein, R is substituting group as herein defined, comprises alkyl (cycloalkyl, perfluoroalkyl etc.) or aryl (such as, perfiuoroaryl group).Example includes but not limited to methyl sulfoxide base, phenylsulfone base etc.

Term " sulfonyl " refers to the group consisting of RSO2-, and wherein, R is the substituting group as herein defined with alkyl, aryl (comprising cycloalkyl, perfluoroalkyl or perfiuoroaryl group).Example includes but not limited to methyl sulphonyl, phenyl sulfonyl, ptoluene-sulfonyl etc.

Term " carbamoyl " refer to consist of R (R') NC (O)-group, wherein, as defined herein, example includes but not limited to N-ethylaminocarbonyl, N, N-formyl-dimethylamino etc. to R and R'.

Term " amide groups " refers to and consists of R ₁cONR ₂-group, wherein, R ₁and R ₂it is substituting group as herein defined.Example includes but not limited to acetamido, N-ethylbenzoyl amido etc.

Term " imines " refers to=NR.

In some embodiments, when such as refering in particular to metal by " M " or " Mn ", wherein, n is integer, thinks that this metal can combine with counter ion.

As used herein and unless otherwise noted, otherwise term " current-flow test set " is the device can measuring the electric current (result as application particular field current potential (" voltage ")) produced in electrochemical cell.

As used herein and unless otherwise noted, otherwise term " aryloxy group " means-O-aromatic yl group, and wherein, aryl is as defined herein.Aryloxy group can be unsubstituted or can be replaced by one or two suitable substituting group.Preferably, the aromatic ring of aryloxy group is monocycle, and wherein, this ring comprises 6 carbon atoms, is referred to herein as " (C6) aryloxy group ".

As used herein and unless otherwise noted, otherwise term " benzyl " means-CH2-phenyl.

As used herein and unless otherwise noted, otherwise term " carbonyl " group be formula-C (O)-divalent group.

As used herein and unless otherwise noted, otherwise term " coulomb measurement mechanism " is the device can measuring the net charge produced in application electric potential field (potentialfield) (" voltage ") to the process of electrochemical cell.

As used herein and unless otherwise noted, otherwise term " cyano group " refers to-CN group.

As used herein and unless otherwise noted, otherwise term " different with differentiable " is when relating to two or more oxidation state, meaning net charge on entity (atom, molecule, aggregation, subelement etc.) can exist with two kinds of different states.When difference between state is greater than the heat energy under room temperature, then these states are " differentiable ".

As used herein and unless otherwise noted, otherwise term " E _1/2" refer to and pass through E=E ₀+ (RT/nF) ln (D _ox/ D _red) formal potential (the formalpotential) (E of oxidation-reduction process that defines ₀) actual definition, wherein, R is gas constant, and T is in the temperature of K (Kelvin), and n is the electron number related in this process, and F is Faraday constant (96,485 coulomb/mole), D _oxdiffusion coefficient and the D of oxidation material _redit is the diffusion coefficient of reducing substances.

As used herein and unless otherwise noted, otherwise when being used for mentioning storage molecule and/or storage medium and electrode, term " electric coupling " refers to that this storage medium or the combination between molecule and electrode make electronics move to electrode from storage medium/molecule or move to storage medium/molecule from electrode, thus changes the oxidation state of storage medium/molecule.Electric coupling can comprise directly covalently bound, the indirect covalent coupling of storage medium/between molecule and electrode (such as, by connecting base), the direct or indirect ionic bonding of storage medium/between molecule and electrode or other bondings (such as, hydrophobic bonding).In addition, the bonding on realistic border may do not wanted, and can simply storage medium/molecule be contacted with electrode surface.Also there is no need to there is any contact between electrode and storage medium/molecule, wherein electrode fully close to storage medium/molecule to allow the electron tunneling effect (electrontunneling) of medium/between molecule and electrode.

As used herein and unless otherwise noted, otherwise term " electrochemical cell " minimally by reference electrode, work electrode, redox reaction medium (such as, storage medium) and if need, form for providing some devices (such as, dielectric) of the conductivity between electrode and/or between electrode and medium.In some embodiments, dielectric is the component of storage medium.

As used herein and unless otherwise noted, otherwise term " electrode " refer to can delivered charge (such as, electronics) to storage molecule and/or any medium by storage molecule delivered charge (such as, electronics).Preferred electrode is metal or conductive organic molecule.Electrode can be fabricated to any 2 dimensions or 3 dimensions shape (such as, discrete line, liner, plane, spheroid, cylinder etc.) practically.

As used herein and unless otherwise noted, otherwise term " fixed electrode " to be intended to reflection electrode substantially stable and relative to the immovable fact of storage medium.That is, electrode and storage medium is arranged with the geometrical relationship be substantially fixed to one another.Certainly it is to be appreciated that because medium is with the expansion of thermal change and contraction or the conformation change due to the molecule that comprises electrode and/or storage medium, relation changes a little.But overall space is arranged and is substantially remained unchanged.

As used herein and unless otherwise noted, otherwise term " connection base " is to the molecule of substrate for two subelements of the two kinds of different molecules that are coupled, molecule or coupled molecule.

Chemical compound lot described herein utilizes the substituting group being usually depicted as " R " herein.Suitable R group includes but not limited to hydrogen, alkyl, alcohol, aryl, amino, amide groups, nitro, ether, ester, aldehyde, sulfonyl, silicon part, halogen, cyano group, acyl group, sulfur-bearing part, phosphorus-containing moieties, Sb, sub-amide groups, carbamoyl, connection base, coupling part, ReAM and other subelements.It should be noted that some positions can allow two substituent R and R', in this case, R and R' group can be identical or different, and usually preferably in substituting group one is hydrogen.In some embodiments, R group as the U.S. accompanying drawing and text defined and described.U.S. Patent number 6,212,093; 6,728,129; 6,451,942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484,394; With United States serial 10/040,059; 10/682,868; 10/445,977; 10/834,630; 10/135,220; 10/723,315; 10/456,321; 10/376, multiple suitable front part and complex compound and suitable substituting group is outlined in 865, whole in conjunction with it clearly by reference, their structure particularly wherein described and description, no matter it can be used as substituting group execution mode to combine thus clearly, be wherein depict substituent specific large ring or further substitutive derivative.

As used herein and unless otherwise noted, otherwise term " subelement (subunit) " refers to the redox active component of molecule.

the Phosphonium ionic liquid of Ben Faming, salt and composition

As described in detail herein, the execution mode of Xin Xing Phosphonium ionic liquid of the present invention, salt and composition shows the character of expectation, and following particularly at least two or more combination: high thermodynamic stability, low volatility, wide liquidus curve scope, high ionic conductivity and wide electrochemical stability windows.Most as many as, and in some embodiments, all these character are unexpected with the combination of aspiration level in a kind of composition and do not predict, and provide the significant advantage exceeding known ionic composition.The execution mode showing the Phosphonium composition of the Ben Faming of these character makes it front unavailable application and device becomes possibility.

In some embodiments, the Phosphonium ionic liquid of Ben Faming comprises the phosphonium cation of selected molecular weight and substitute mode, be coupled with selected anion, to form the ionic liquid of the Combined adjustable with thermodynamic stability, ionic conductivity, liquidus curve scope and low volatility character.

In some embodiments, " ionic liquid " herein mean 100 DEG C and following be the salt of liquid condition.Herein " room temperature " ionic liquid is further defined as its room temperature and following be liquid condition.

In other embodiments, employ term " electrolyte " or " electrolyte solution " or " electrolyte composition " or " ionic electrolytes " or " ionic conductivity electrolyte " or " ion conductive composition " or " ionic composition " and be defined as in this article following in any one or multiple: (a) ionic liquid, (b) ionic liquid at room temperature, c () is dissolved in one or more salt at least one solvent, be dissolved in (d) one or more salt forming gel electrolyte at least one solvent together with at least one polymer.In addition, one or more salt are defined as and comprise: (a) is one or more salt of solid under 100 DEG C and following temperature, and (b) is one or more salt of liquid under 100 DEG C and following temperature.

In some embodiments, the present invention includes the temperature showing and be up to about 400 DEG C and be more commonly up to the thermodynamic stability Phosphonium ionic liquid of temperature of about 375 DEG C with Phosphonium electrolyte.Showing the thermal stability being up to so high-temperature is major progress, and allows the Phosphonium ionic liquid using Ben Faming in the application of wide region.The Phosphonium ionic liquid of Ben Faming and the electrolytical execution mode of Phosphonium to show under room temperature the ionic conductivity of at least 1mS/cm or at least 5mS/cm or at least 10mS/cm or at least 15mS/cm or at least 20mS/cm or at least 30mS/cm or at least 40mS/cm or at least 50mS/cm or at least 60mS/cm further.The Phosphonium ionic liquid of Ben Faming and the electrolytical execution mode of Phosphonium show the volatility of about 20% lower than their nitrogen class analog.This combination of high thermal stability, high ionic conductivity, wide liquidus curve scope and low volatility be highly make us wishing with beat all.Usually, in the prior art, find that the thermal stability of ionic liquid and ionic conductivity show contrary relation.

Some execution modes of Zhong ， Phosphonium ionic liquid is with Phosphonium electrolyte is by having the cation composition being up to 500 daltonian molecular weight.， Phosphonium ionic liquid is with Phosphonium electrolyte is by having in the cation composition compared with the molecular weight within the scope of 200 to 500 dalton of the ionic liquid under low thermal stability scope in other embodiments.

The Phosphonium ionic composition of Ben Faming is made up of the Phosphonium cationoid of following general formula:

R ¹R ²R ³R ⁴P(1)，

Wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another.In some embodiments, wherein, cation is made up of open chain.

In some embodiments, R ¹, R ², R ³and R ⁴alkyl group independently of one another.In one embodiment, at least one in alkyl group from other two kinds different.In one embodiment, alkyl group is not methyl.In some embodiments, alkyl group is by 2 to 7 carbon atoms, and more commonly 1 to 6 carbon atom forms.In some embodiments, R ¹, R ², R ³and R ⁴the different alkyl group be made up of 2 to 14 carbon atoms independently of one another.In some embodiments, alkyl group does not comprise side chain.In one embodiment, R ¹=R ²it is aliphatic heterocycle part.Alternately, R ¹=R ²it is heteroaromatic part.

In some embodiments, R ¹or R ²be made up of the alkyl phenyl of phenyl or replacement.In some embodiments, R ¹and R ²identical and be made up of tetramethylene (phospholane) or pentamethylene (phospha cyclohexane).Alternately, R ¹and R ²identical and be made up of four methines (Phospholes).In further execution mode, R ¹and R ²identical and be made up of phospholane or phospha cyclohexane.In addition, in another embodiment, R ², R ³and R ⁴identical and be made up of phospholane, phospha cyclohexane or Phospholes.

In some embodiments, R is selected ¹, R ², R ³and R ⁴in at least one, multiple or all make each not comprise the functional group of reacting with redox active molecule (ReAM) described below.In some embodiments, R ¹, R ², R ³and R ⁴in at least one, multiple or all do not comprise halide, metal or O, N, P or Sb.

In some embodiments, alkyl group comprises 1 to 7 carbon atom.In other embodiments, the entire carbon atom of all alkyl groups is less than 12.In other implementations, alkyl group is independently of one another by 1 to 6 carbon atom, and more generally 1 to 5 carbon atom forms.

In another embodiment, carries and supplied Phosphonium ionic composition, and it is made up of following: dissolve one or more salt in a solvent, these one or more salt comprise one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P(1)，

With one or more anion, and wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another, such as but not limited to following described alkyl group.In some embodiments, R ¹, R ², R ³and R ⁴by 1 to 6 carbon atom independently of one another, the more commonly alkyl group of 1 to 4 carbon atom composition.In some embodiments, the one or more hydrogen atoms in one or more R group replaced by fluorine.Any one in salt or multiple can be liquid or solid under 100 DEG C and following temperature.In some embodiments, salt is made up of a kind of cation and a kind of anion.In other embodiments, salt is made up of a kind of cation and multiple anion.In other embodiments, salt is by a kind of anion and multiple cation composition.In further execution mode, salt is made up of multiple cation and multiple anion.The illustrative embodiments of suitable solvent includes but not limited to following one or more: acetonitrile, carbonic acid ethylidene ester (EC), propylene carbonate (PC), butylene carbonate base ester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoro carbonic acid ethylidene ester (FEC), fluorobenzene (FB), vinylene carbonate base ester (VC), ethylene thiazolinyl ethylidene ester (VEC), phenyl-carbonic acid ethylidene ester (PhEC), hydroxypropyl methyl carbonic ester (PMC), diethoxyethane (DEE), dimethoxy-ethane (DME), oxolane (THF), gamma-butyrolacton (GBL) and gamma-valerolactone (GVL).

Be made up of following formula at an exemplary execution mode Zhong ， phosphonium cation:

The execution mode Zhong ， phosphonium cation exemplary at another is made up of following formula:

Be made up of following formula at the execution mode Zhong ， phosphonium cation of Still another example:

Be made up of following formula at other illustrative embodiments Zhong ， phosphonium cation:

Be made up of following formula at further illustrative embodiments Zhong ， phosphonium cation:

Another embodiment provides for by following formula Zu Cheng phosphonium cation:

Provide by following formula Zu Cheng phosphonium cation further:

In some embodiments, the example of He Shi phosphonium cation includes but not limited to: two-n-pro-pyl Yi Ji Phosphonium; Normal-butyl n-pro-pyl Yi Ji Phosphonium; N-hexyl normal-butyl Yi Ji Phosphonium etc.

In other embodiments, the example of He Shi phosphonium cation includes but not limited to: ethyl phospholane; N-pro-pyl phospholane; Normal-butyl phospholane; N-hexyl phospholane; With phenyl phospholane.

In further execution mode, the example of He Shi phosphonium cation includes but not limited to: ethyl Phospholes; N-pro-pyl Phospholes; Normal-butyl Phospholes; N-hexyl Phospholes; With phenyl Phospholes.

In yet another embodiment, the example of He Shi phosphonium cation includes but not limited to: 1-ethyl phospha cyclohexane; N-pro-pyl phospha cyclohexane; Normal-butyl phospha cyclohexane; N-hexyl phospha cyclohexane; With phenyl phospha cyclohexane.

The Phosphonium ionic liquid of Ben Faming or salt are made up of cation and anion.Those skilled in the art by it is to be understood that exist various possible cation and anion combination.The Phosphonium ionic liquid of Ben Faming or salt comprise cation described above and are usually selected from the anion being easy to the compound exchanged with the reagent of following general formula or lyate ion:

C ⁺A ^-，

Wherein, C ⁺cation and A ⁺it is anion.When organic solvent, C ⁺preferably Li ⁺, K ⁺, Na ⁺, NH ₄ ⁺or Ag ⁺.When aqueous solvent, C+ is preferably Ag ⁺.

Many anion can be selected.In one preferred embodiment, anion is two-perfiuoromethylsulfonyl acid imide.The illustrative examples of suitable anion includes but not limited to following any one or multiple: NO ₃ ^-, O ₃sCF ₃ ^-, N (SO ₂cF ₃) ₂ ^-, PF ₆ ^-, O ₃sC ₆h ₄cH ₃ ^-, O ₃sCF ₂cF ₂cF ₃ ^-, O ₃sCH ₃ ^-, I ^-, C (CN) ₃ ^-, ^-o ₃sCF ₃, ^-n (SO ₂) ₂cF ₃, CF ₃bF ₃ ^-, ^-o ₃sCF ₂cF ₂cF ₃, SO ₄ ^2-, ^-o ₂cCF ₃, ^-o ₂cCF ₂cF ₂cF ₃or ^-n (CN) ₂.

In some embodiments, the Phosphonium ionic liquid of Ben Faming or salt by single anionic-cationic to forming.Alternately, Liang kind or more Zhong Phosphonium ionic liquid or salt can be used to form the ternary system etc. of common binary system (binary), the binary system mixed, common ternary system (ternary), mixing.For often kind of component cation and often kind of component anion, the compositing range of binary system, ternary system etc. comprises 1ppm to maximum 999,999ppm.In another embodiment, Phosphonium electrolyte is made up of one or more salt dissolved in a solvent, and this salt can be liquid or solid at the temperature of 100 DEG C.In some embodiments, salt by single anionic-cationic to forming.In other embodiments, salt is made up of a kind of cation and multiple anion.In other embodiments, salt is by a kind of anion and multiple cation composition.In other execution mode again, salt is made up of multiple cation and multiple anion.

In one preferred embodiment, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 1A and 1B and anionic group.Another preferred embodiment in, Phosphonium electrolyte is combined into by with the cation shown in following table 1C, 1D, 1E and 1F and anionic group.For purpose of brevity, the electric charge mark in formula has been eliminated.

Table 1 shows the example of the anion binary system with Common Cations:

Table 1A

Table 1B shows the example of cation and anion combination:

Table 1B

In another embodiment, Phosphonium electrolyte forms with the cationic salt shown in following table 1C-1 to 1C-3 by having:

Table 1C-1:

Table 1C-2:

Table 1C-3:

In another embodiment, Phosphonium electrolyte forms with the salt of the anion shown in following table 1D-1 to 1D-4 by having:

Table 1D-1:

Table 1D-2:

Table 1D-3:

Table 1D-4:

In another embodiment, Phosphonium electrolyte composition forms with the salt of the cation shown in following table 1E-1 to 1E-4 and anion combination by having:

Table 1E-1

Table 1E-2

Table 1E-3

Table 1E-4

In some execution modes, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: one or more cations in following formula:

P (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _4-x-y(x, y=0 to 4; X+y≤4),

P (CF ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _4-x-y(x, y=0 to 4; X+y≤4),

P (-CH ₂cH ₂cH ₂cH ₂-) (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _2-x-y(x, y=0 to 2; X+y≤2),

P (-CH ₂cH ₂cH ₂cH ₂cH ₂-) (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _2-x-y(x, y=0 to 2; X+y≤2),

With one or more anion in following formula:

(CF ₃) _xbF _4-x(x=0 to 4),

(CF ₃(CF ₂) _n) _xpF _6-x(n=0 to 2; X=0 to 4),

(-OCO (CH ₂) _ncOO-) (CF ₃) _xbF _2-x(n=0 to 2; X=0 to 2),

(-OCO (CF ₂) _ncOO-) (CF ₃) _xbF _2-x(n=0 or 2; X=0 to 2),

(-OCO (CH ₂) _ncOO-) ₂b (n=0 to 2),

(-OCO (CF ₂) _ncOO-) ₂b (n=0 to 2),

(-OOR) _x(CF ₃) BF _3-x(x=0 to 3),

(-OCOCOCOO-) (CF ₃) _xbF _2-x(x=0 to 2),

(-OCOCOCOO-) ₂B、

(-OSOCH ₂sOO-) (CF ₃) _xbF _2-x(x=0 to 2),

(-OSOCF ₂sOO-) (CF ₃) _xbF _2-x(x=0 to 2),

(-OCOCOO-) _x(CF ₃) _ypF _6-2x-y(x=1 to 3; Y=0 to 4; 2x+y≤6).

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: one or more cations in following formula:

P (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _4-x-y(wherein, x, y=0 to 4; X+y≤4);

With

One or more anion in following formula:

(CF ₃) _xbF _4-x(wherein, x=0 to 4),

(CF ₃(CF ₂) _n) _xpF _6-x(wherein, n=0 to 2; X=0 to 4),

(-OCO (CH ₂) _ncOO-) (CF ₃) _xbF _2-x(wherein, n=0 to 2; X=0 to 2),

(-OCO (CH ₂) _ncOO-) ₂b (wherein, n=0 to 2),

(-OSOCH ₂sOO-) (CF ₃) _xbF _2-x(wherein, x=0 to 2),

(-OCOCOO-) _x(CF ₃) _ypF _6-2x-y(x=1 to 3; Y=0 to 4; 2x+y≤6).

P (-CH ₂cH ₂cH ₂cH ₂-) (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _2-x-y(wherein, x, y=0 to 2; X+y≤2),

P (-CH ₂cH ₂cH ₂cH ₂cH ₂-) (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _2-x-y(wherein, x, y=0 to 2; X+y≤2);

With

One or more anion in following formula:

(CF ₃) _xbF _4-x(wherein, x=0 to 4),

(CF ₃(CF ₂) _n) _xpF _6-x(wherein, n=0 to 2; X=0 to 4),

(-OCO (CH ₂) _ncOO-) (CF ₃) _xbF _2-x(wherein, n=0 to 2; X=0 to 2),

(-OCO (CH ₂) _ncOO-) ₂b (wherein, n=0 to 2),

(-OSOCH ₂sOO-) (CF ₃) _xbF _2-x(wherein, x=0 to 2),

(-OCOCOO-) _x(CF ₃) _ypF _6-2x-y(x=1 to 3; Y=0 to 4; 2x+y≤6).

In one embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of one or more anion be selected from by the following group formed: PF ₆, (CF ₃) ₃pF ₃, (CF ₃) ₄pF ₂, (CF ₃cF ₂) ₄pF ₂, (CF ₃cF ₂cF ₂) ₄pF ₂, (-OCOCOO-) PF ₄, (-OCOCOO-) (CF ₃) ₃pF, (-OCOCOO-) ₃p, BF ₄, CF ₃bF ₃, (CF ₃) ₂bF ₂, (CF ₃) ₃bF, (CF ₃) ₄b, (-OCOCOO-) BF ₂, (-OCOCOO-) BF (CF ₃), (-OCOCOO-) (CF ₃) ₂b, (-OSOCH ₂sOO-) BF ₂, (-OSOCF ₂sOO-) BF ₂, (-OSOCH ₂sOO-) BF (CF ₃), (-OSOCF ₂sOO-) BF (CF ₃), (-OSOCH ₂sOO-) B (CF ₃) ₂, (-OSOCF ₂sOO-) B (CF ₃) ₂, CF ₃sO ₃, (CF ₃sO ₂) ₂n, (-OCOCOO-) ₂pF ₂, (CF ₃cF ₂) ₃pF ₃, (CF ₃cF ₂cF ₂) ₃pF ₃, (-OCOCOO-) ₂b, (-OCO (CH ₂) _ncOO-) BF (CF ₃), (-OCOCR ₂cOO-) BF (CF ₃), (-OCOCR ₂cOO-) B (CF ₃) ₂, (-OCOCR ₂cOO-) ₂b, CF ₃bF (-OOR) ₂, CF ₃b (-OOR) ₃, CF ₃b (-OOR) F ₂, (-OCOCOCOO-) BF (CF ₃), (-OCOCOCOO-) B (CF ₃) ₂, (-OCOCOCOO-) ₂b, (-OCOCR ¹r ²cR ¹r ²cOO-) BF (CF ₃) and (-OCOCR ¹r ²cR ¹r ²cOO-) B (CF ₃) ₂; And wherein, R, R ¹and R ²h or F independently of one another.

In one embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: the cation of following formula: (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂p ⁺with any one in following formula or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: formula (CH ₃) (CH ₃cH ₂) ₃p ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: formula (CH ₃cH ₂cH ₂) (CH ₃cH ₂) ₃p ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: formula (CH ₃cH ₂cH ₂) ₃(CH ₃) P ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: formula (CH ₃cH ₂cH ₂) ₃(CH ₃cH ₂) P ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: formula (CH ₃cH ₂cH ₂) ₂(CH ₃cH ₂) (CH ₃) P ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In another embodiment, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: formula (CH ₃cH ₂) ₄p ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^- _,(-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In further execution mode, Phosphonium electrolyte is made up of the salt dissolved in a solvent, and wherein, this salt is made up of following: the formula (CH of 1:3:1 mol ratio ₃cH ₂cH ₂) (CH ₃) ₃p/ (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂p/ (CH ₃cH ₂cH ₂) (CH ₃cH ₂) ₂(CH ₃) any one in the cation of P and following formula or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^- _,(-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

In some embodiments, anion is by [the BF in 100/1 to 1/1 scope ₄ ^-]: [CF ₃bF ₃ ^-] BF of concentration of mol ratio ₄ ^-and CF ₃bF ₃ ^-mixture composition.In other embodiments, anion is by [the PF in 100/1 to 1/1 scope ₆ ^-]: [CF ₃bF ₃ ^-] PF of concentration of mol ratio ₆ ^-and CF ₃bF ₃ ^-mixture composition.Also wanting in further execution mode, anion is by [the PF in 100/1 to 1/1 scope ₆ ^-]: [BF ₄ ^-] PF of concentration of mol ratio ₆ ^-and BF ₄ ^-mixture composition.

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 2 and anionic group:

Table 2

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 3 and anionic group:

Table 3

In further preferred embodiment, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 4 and anionic group:

Table 4

In further preferred embodiment again, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 5 and anionic group:

Table 5

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 6 and anionic group:

Table 6

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 7 and anionic group:

Table 7

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 8 and anionic group:

Table 8

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 9 and anionic group:

Table 9

Another preferred embodiment in, Phosphonium ionic liquid compositions is combined into by with the cation shown in following table 10 and anionic group:

Table 10

Preferred embodiment comprise by the Phosphonium ionic liquid compositions be combined into the cation shown in following table 11 and anionic group in addition:

Table 11

Provide by the further preferred embodiment of the Phosphonium ionic liquid compositions be combined into the cation shown in following table 12 and anionic group:

Table 12

Another preferred illustrative embodiments comprises by the Phosphonium ionic liquid compositions be combined into the cation shown in following table 13 and anionic group:

Table 13

In some embodiments, the further example of He Shi Phosphonium ionic liquid compositions includes but not limited to: two-n-pro-pyl Yi base Jia Ji Phosphonium is two-and (trifluoromethyl sulfonyl) acid imide; Normal-butyl n-pro-pyl Yi base Jia Ji Phosphonium is two-(trifluoromethyl sulfonyl) acid imide; N-hexyl normal-butyl Yi base Jia Ji Phosphonium is two-(trifluoromethyl sulfonyl) acid imide etc.

The illustrating property example closing suitable Phosphonium ionic liquid compositions includes but not limited to further: 1-ethyl-1-first base Phosphonium heterocycle pentane is two-and (trifluoromethyl sulfonyl) acid imide; N-pro-pyl first base Phosphonium heterocycle pentane is two-(trifluoromethyl sulfonyl) acid imide; Normal-butyl first base Phosphonium heterocycle pentane is two-(trifluoromethyl sulfonyl) acid imide; N-hexyl first base Phosphonium heterocycle pentane is two-(trifluoromethyl sulfonyl) acid imide; With benzene base first base Phosphonium heterocycle pentane two-(trifluoromethyl sulfonyl) acid imide.

In another embodiment, the example closing suitable Phosphonium ionic liquid compositions includes but not limited to: 1-ethyl-1-first base Phosphonium heterocycle pentane is two-and (trifluoromethyl sulfonyl) acid imide; N-pro-pyl first base Phosphonium heterocycle pentane is two-(trifluoromethyl sulfonyl) acid imide; Normal-butyl first base Phosphonium heterocycle pentane is two-(trifluoromethyl sulfonyl) acid imide; N-hexyl first base Phosphonium heterocycle pentane is two-(trifluoromethyl sulfonyl) acid imide; With benzene base first base Phosphonium heterocycle pentane two-(trifluoromethyl sulfonyl) acid imide.

The further illustrative embodiments of He Shi Phosphonium ionic liquid compositions includes but not limited to: 1-ethyl-1-methyl phospha cyclohexane is two-and (trifluoromethyl sulfonyl) acid imide; N-pro-pyl methyl phospha cyclohexane is two-(trifluoromethyl sulfonyl) acid imide; Normal-butyl methyl phospha cyclohexane is two-(trifluoromethyl sulfonyl) acid imide; N-hexyl methyl phospha cyclohexane is two-(trifluoromethyl sulfonyl) acid imide; With phenyl methyl phospha cyclohexane two-(trifluoromethyl sulfonyl) acid imide.

According to some execution modes, the Phosphonium ionic liquid of Ben Faming can also be formed by one or more solids or form eutectic (eutectic) by solid and liquid.In this case, term " ionic liquid " is further defined as and comprises as by ion solid or eutectiferous ionic liquid of being formed by ionic liquid and ion solid (as binary system, ternary system etc.).

redox active molecule

Electric hybrid module and/or the device of the Phosphonium ionic liquid synthesis wide region of Ben Faming described herein can be adopted, as such as memory storage and element.In an exemplary execution mode, this Wen Phosphonium ionic liquid is for the formation of wherein by the molecular memory device of information storage in redox active information storage molecule.

Term " redox active molecule (ReAM) " be herein intended to finger can, such as, by applying the component of molecule that suitable voltage is oxidated or reduced or molecule.As described below, ReAM can include but not limited to large ring (comprising porphyrin and derivatives of porphyrin) and non-macrocyclic compound, and comprises lamellar compound (sandwichcompound), such as, as described herein.In some embodiments, ReAM can comprise multiple subelement, such as, when two tuples (dyad) or tlv triple (triad).ReAM can comprise ferrocene, Bipys, PAH, purple alkali (viologen) etc.In general, as described below, there is the ReAM used in the present invention of several types, all based on part (polydentateproligand) before polygamy position, comprise large ring and non-large loop section.U.S. Patent number 6,212,093; 6,728,129; 6,451,942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484,394; And U.S.S.N10/040,059; 10/682,868; 10/445,977; 10/834,630; 10/135,220; 10/723,315; 10/456,321; 10/376, outline multiple suitable front part and complex compound and suitable substituting group in 865; Whole in conjunction with it clearly by reference, its structure particularly wherein described and description.

Suitable front part is divided into two classifications: use nitrogen, oxygen, sulphur, carbon or phosphorus atoms (depending on metal ion) as the part of coordination atom (being usually called sigma (σ) donor in the literature) and organometallic ligand as metallocene ligand (be usually called pi (π) donor in the literature, and be depicted as Lm herein).

In addition, single ReAM can have two or more redox actives.Such as, Figure 13 A of US publication 2007/0108438 show two kinds of redox active subelements, porphyrin (metal not in the presence of illustrate) and ferrocene.Similarly, intercalation coordination compound is considered as single ReAM.This distinguishes as the situation of monomer polymerization with wherein these ReAM.In addition, metal ion/complex compound of the present invention can be combined with the counter ion usually do not described herein.

macrocyclic ligand

In one embodiment, ReAM is macrocyclic ligand, and it comprises macrocyclic proligand and large ring complex compound." macrocyclic proligand " herein means cyclic compound, and it comprises directed donor atom (being sometimes referred to herein as " coordination atom "), makes them to be bonded to metal ion and it is enough large with around metallic atom.In general, donor atom is hetero-atom, includes but not limited to nitrogen, oxygen and sulphur, and the former is especially preferred.But those skilled in the art is by it is to be understood that different metal ions is preferentially bonded to different hetero-atoms, and the hetero-atom therefore used can depend on the metal ion of needs.In addition, in some embodiments, single large ring can comprise dissimilar hetero-atom.

" large ring complex compound " is the macrocyclic proligand with at least one metal ion; In some embodiments, large ring complex compound comprises single metal ion, although as described below, have also contemplated that polynuclear complex, comprises the large ring complex compound of multinuclear.

Find the purposes of various macrocyclic ligand in the present invention, comprise electron conjugated those and may those of non-electronic conjugation; But macrocyclic ligand of the present invention preferably has at least one, and preferably two or more oxidation state, wherein 4,6 and 8 oxidation state have special meaning.

Figure 11 and 14 of US publication 2007/0108438 illustrate and describes the extensive schematic diagram of suitable macrocyclic ligand, except Figure 11 and 14, by reference it is all incorporated into this.In this embodiment, roughly based on porphyrin, consider 16 all ring (Dang – X-parts and comprise single atom, carbon or hetero-atom time), 17 rings (wherein in – X-part comprises two skeletal atoms), 18 rings (two wherein in – X-part comprise two skeletal atoms), 19 rings (three wherein in – X-part comprise two skeletal atoms) or 20 rings (all four wherein in ， – X-part comprise two skeletal atoms).Select Mei – X-group independently.For 5 or 6 rings,-Q-part, together with Gu Jia – C-hetero-atom-C (wherein singly-bound or double bond connect carbon and hetero-atom independently), replaced by the R2 group 1 or 2 (when 5 ring) independently selected or 1,2 or 3 (in 6 rings) alternatively.In some embodiments, select ring, key and substituting group to obtain the compound that electron conjugated and bottom line has at least two kinds of oxidation state.

In some embodiments, macrocyclic ligand of the present invention is selected from the group be made up of porphyrin (particularly the following derivatives of porphyrin defined) and cycleanine (cyclen) derivative.

porphyrin

The particularly preferred subset being applicable to large ring of the present invention is porphyrin, comprises derivatives of porphyrin.These derivatives comprise the porphyrin having and condense the extra loop of (perifused) with porphyrin core ortho-condensed or ortho position-periphery, there are one or more carbon atoms of porphyrin ring by the porphyrin of the displacement of the atom of another kind of element (skeleton displacement), there is the nitrogen-atoms of porphyrin ring by the derivative of the atomic substitutions of another kind of element (the skeleton displacement of nitrogen), have except being positioned at periphery (porphyrin m-, the 3-of porphyrin or core atom) the substituent derivative of hydrogen, derivative that one or more keys of porphyrin are saturated (hydrogenation porphyrin, such as, chlorin, bacteriochlorin, different bacteriochlorin, decahydro porphyrin, corphins, pyrrocorphins etc.), there is one or more atom, comprise pyrrole radicals and pyrroles's methine unit is inserted into derivative in porphyrin ring (porphyrin of extension), there is the combination (such as phthalocyanine, sub-phthalocyanine and porphyrin isomers) of derivative (porphyrin of contraction, such as, corrin, click is coughed up (corrole)) and the said derivative removing one or more group from porphyrin ring.Derivatives of porphyrin suitable in addition includes but not limited to chlorophyll group, comprise etiophyllin, pyrroporphyrin, rhodoporphyrin, phylloporphyrin, phylloerythin, chlorophyll a and b, and hemoglobin group, comprise deuteroporphyrin, deuterohemin, hemin, hematin, protoporphyrin, mesohemin, haematoporphyrin, mesoporphyrin, coproporphyrin, uruporphyrin and turacin and a series of four aryl azepine two pyrroles methines.

Be correct for the compound summarized herein, and those skilled in the art will be appreciated that, each unsaturated position, no matter be carbon or hetero-atom, need chemical valence according to system, one or more substituting group described herein can be comprised.

In one preferred embodiment, redox active molecule can be metallocene, and use the independent R group selected herein, it can be substituted in any suitable position.Find have the metallocene of special purposes to comprise ferrocene and its derivative in the present invention.In this embodiment, preferred substituting group includes but not limited to 4-chlorphenyl, 3-acetamidophenyl, 2,4-dichlor-4-trifluoromethyls.Preferred substituting group provides the redox potential range being less than about 2 volts.

Will it is to be understood that the oxidizing potential of this serial member can be changed routinely by change metal (M) or substituting group.

Figure 12 H of US publication 2007/018438 shows another example of the redox active molecule be made up of porphyrin, wherein, F is that redox active subelement is (as ferrocene, the ferrocene replaced, metalloporphyrin or metal dihydride porphines etc.), JI connects base, M is that metal is (as Zn, Mg, Cd, Hg, Cu, Ag, Au, Ni, Pd, Pt, Co, Rh, Ir, Mn, B, Al, Ga, Pb and Sn), S1 and S2 is independently selected from the group of the following: aryl, phenyl, cycloalkyl, alkyl, halogen, alkoxyl, alkylthio group, perfluoroalkyl, perfiuoroaryl, pyridine radicals, cyano group, thiocyano, nitro, amino, alkyl amino, acyl group, sulfoxide group, sulfonyl, imido grpup, amide groups and carbamoyl, wherein, described substituting group provides the redox potential range being less than about 2 volts, K1, K2, K3 and K4 is independently selected from the group of the following: N, O, S, Se, Te and CH, L connects base, X is selected from the group of the following: substrate, with the attachment of substrate with can be coupled to the reactivity site of substrate by ion.In a preferred embodiment, X or L-X can be alcohol or mercaptan.In some embodiments, can L-X be eliminated and can replace with the substituting group independently selected from the group identical with SlorS2.

The structure controlling this memory storage is well allowed to the hole-storage of the redox active unit of the redox active molecule used in memory storage of the present invention and the control of hole-jump character.

This control is undertaken by compounding design.Hole-storage properties depends on.Can by selecting base molecule, the metal of combination and the substituting group fine adjustment hole-storage properties of surrounding and oxidation-reduction potential (Yangetal. (1999) J.PorphyrinsPhthalocyanines, 3:117-147), by reference it is openly incorporated into this.

Such as, when porphyrin, Mg porphyrin is easier than Zn porphyrin oxidized, and electrophilic or push away electron-rich aryl group and can regulate oxidizing property in foreseeable mode.Hole-jump appears at waiting of nanostructure can in porphyrin and via covalently bound base mediation (Sethetal. (1994) J.Am.Chem.Soc. engaging porphyrin, 116:10578-10592, Sethetal (1996) J.Am.Chem.Soc., 118:11194-11207, Strachanetal. (1997) J.Am.Chem.Soc., 119:11191-11201; Lietal. (1997) J.Mater.Chem., 7:1245-1262, Strachanetal. (1998) Inorg.Chem., 37:1191-1201, Yangetal. (1999) J.Am.Chem.Soc., 121:4008-4018), quote by this it is all openly incorporated into this clearly.

The design with the compound of the oxidation-reduction potential of prediction is that those of ordinary skill in the art know.In general, the oxidizing potential of redox active unit or subelement is well known to those skilled in the art and can be found (such as, see HandbookofElectrochemistryoftheElements).In addition, in general, multiple substituting group is to the effect of the oxidation-reduction potential of molecule normally additive property.Therefore, the theoretical oxidation current potential of any potential data storage molecule can easily be predicted.Actual oxidizing potential, particularly information storage molecule or the oxidizing potential of information storage medium, can measure according to standard method.Typically, the oxidizing potential of the base molecule determined by comparative experiments and the oxidizing potential prediction oxidizing potential of a band substituent base molecule, to determine the potential drifting because specified substituent causes.Then, the summation of the potential shift of each substituent these substituting groups dependence obtains the oxidizing potential of prediction.

Easily can determine the applicability of the specific redox active molecule of method of the present invention.According to method of the present invention, be polymerized interesting molecule simply and couple it to surface (such as, the surface of hydrogen passivation).Then can carry out sinusoidal voltammetry (such as, as herein or at United States Patent (USP) 6,272,038; 6,212,093; With 6,208, in 553, in the open WO01/03126 of PCT, or by (Rothetal. (2000) Vac.Sci.Technol.B18:2359-2364; Rothetal. (2003) J.Am.Chem.Soc.125:505-517) described by), to assess 1) whether these molecules be coupled to surface, 2) level of coverage (coupling); 3) whether these molecules degrade in coupling step, and 4) stability of these molecules repeatedly read/write operation.

In addition, being included in " porphyrin " definition is porphyrin complex, and it comprises part and at least one metal ion before porphyrin.For the hetero-atom that the suitable metal of porphyrin compound will depend on as coordination atom, but be in general selected from transition metal ions.Term as used herein " transition metal " typically refers to the 38 kind elements of the 3rd race to the 12nd race of periodic table.Typical transition metal to be present in more than one shell for the electronics be combined with other elements by their valence electron or they and the fact therefore often showing several frequently seen oxidation state characterizes.In some embodiments, transition metal of the present invention includes but not limited to following one or more: scandium, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold, mercury, Lu Jin (rutherfordium) and/or their oxide and/or nitride and/or alloy and/or mixture.

other large rings

There is many large rings based on cycleanine (cyclen) derivative.Figure 17 and 13C of US publication 2007/0108438 shows many looselys draw amine (cyclam) derivative macrocyclic proligand based on cycleanine/ring, and it can comprise skeleton by the carbon or hetero-atom comprising independent selection and extend.In some embodiments, at least one R group is the subelement of redox active, and it is preferably electron conjugated to metal.In some embodiments, when at least one R group is the subelement of redox active, comprises two or more R2 group closed on and form ring or aromatic yl group.

In addition, in some embodiments, the large ring complex compound depending on organometallic ligand is employed.Except the pure organic compound as redox moiety with containing there is the δ-key organic ligand of donor atom as outside multiple transition metal coordination complexes substituent except heterocycle or ring, the transition metal organometallic compound of the various π of having-key organic ligand is also obtainable (see AdvancedInorganicChemistry, 5thEd., Cotton & Wilkinson, JohnWiley & Sons, 1988, chapter26; Organometallics, AConciseIntroduction, Elschenbroichetal., 2ndEd., 1992, VCH; And ComprehensiveOrganometallicChemistryII, AReviewoftheLiterature1982-1994, Abeletal.Ed., Vol.7, chapters7,8,10 & 11, PergamonPress, are incorporated into this by reference clearly).This organometallic ligand comprises cyclic nonaromatics if cyclopentadienyl (cyclopentadienideion) [C5H5 (-1)] and the multiple cyclosubstituted derivative condensed with ring are as indenes (-1) anion (indenylideion), it produces two (cyclopentadienyl group) metallic compound (that is, metallocene) of a class; Such as, see Robinsetal., J.Am.Chem.Soc.104:1882-1893 (1982); And Gassmanetal., J.Am.Chem.Soc.108:4228-4229 (1986), combine by reference.In these, ferrocene [(C5H5) 2Fe] and its derivative are prototypic example, it is for various chemistry (Connellyetal., Chem.Rev.96:877-910 (1996), combine by reference) and electrochemistry (Geigeretal., AdvancesinOrganometallicChemistry23:1-93; And Geigeretal., AdvancesinOrganometallicChemistry24:87, by reference combine) electro transfer or " redox " reaction.The metallocene derivative of multiple first, second, and third row transition metal can be used as redox moiety (with redox subelement).Other may comprise ring-type virtue alkene as benzene by suitable organometallic ligand, to produce the derivative that two (fragrant alkene) metallic compound condenses with their cyclosubstituted and ring, wherein, two (benzene) chromium is prototypic example, other non-annularity π-key part such as pi-allyl (-1) ion or butadiene produce the suitable organo-metallic compound of possibility, with all these parts, the general type of organo-metallic compound is formed with other π-key and δ-key ligand binding, wherein, there is metal-carbon key.These have bridging organic ligand and other non-bridged part and have and do not have the multiple dimer of compound of Metal-Metal bond and the electrochemical research of oligomer is all useful.

When one or more in common part are organometallic ligand, part, can by other atom of heterocyclic ligand although connect usually by a connection in the carbon atom of organometallic ligand.Preferred organometallic ligand comprises metallocene ligands, comprises the derivative of replacement and metalloceneophanes (the 1174th page see CottonandWilkenson above).Such as, the derivative of metallocene ligands, as methyl cyclopentadienyl (wherein multiple methyl group is preferred, as pentamethylcyclopentadiene base), can be used for the stability increasing metallocene.In some embodiments, metallocene by herein one or more substituting groups of summarizing derive, particularly change the oxidation-reduction potential of subelement or part.

As described herein, any combination of part can be used.Preferred combination comprises: a) all parts are nitrogen supply parts; B) all parts are organometallic ligand.

sandwich coordination complex compound

In some embodiments, ReAM is Sandwich coordination complex compound.Term " intercalation coordination compound " or " Sandwich coordination complex compound " refer to the compound of formula L-Mn-L, wherein, each L is heterocyclic ligand (as described below), each M is metal, n is 2 or more, is most preferably 2 or 3, and each metal between a pair part and with the one or more hetero-atoms in each part (and typically, multiple hetero-atom, such as 2,3,4,5) connect (depending on the oxidation state of metal).Therefore, intercalation coordination compound is not that wherein metal is connected to the organo-metallic compound of carbon atom, as ferrocene.Part in intercalation coordination compound usually with stacking direction arrangement (namely, normally coplanar orientation with to be axially in alignment with each other, although they can or cannot around axle rotation respect to one another) (such as, see NgandJiang (1997) ChemicalSocietyReviews26:433-442), combine by reference.Sandwich coordination complex compound includes but not limited to " double-layer interlayer complex " and " three layer interlayer complexes ".United States Patent (USP) 6,212,093; 6,451,942; 6,777, describe synthesis and the purposes of intercalation coordination compound in 516 in detail; And in US publication 2007/0123618, describing the polymerization of these molecules, it is all included in herein, in sandwich complex and " single " " large ring " complex compound, particularly find the independent substituting group of purposes.

Term " double-layer interlayer complex " refers to that wherein n described above is the intercalation coordination compound of 2, therefore there is formula L'-M'-LZ, wherein, in L1 and LZ each can identical or different (such as, see Jiangetal. (1999) J.PorphyrinsPhthalocyanines3:322-328) and U.S. Patent number 6,212,093; 6,451,942; 6,777,516; And in US publication 2007/0123618, describe the polymerization of these molecules, by reference it is all incorporated into this.

Term " three layer interlayer complexes " refers to that wherein n described above is the intercalation coordination compound of 3, therefore there is formula L'-M'LZ-MZ-L3, wherein, each in L1, LZ and L3 can be identical or different, and Ml and MZ can identical or different (such as, see Arnoldetal. (1999) ChemistryLetters483-484) and U.S. Patent number 6,212,093; 6,451,942; 6,777,516; And in US publication 2007/0123618, describe the polymerization of these molecules, by reference it is all incorporated into this.

In addition, the polymer of these lamellar compounds is also useful; It comprises U.S.S.N6, and 212,093; 6,451,942; 6,777, " diploid (dyad) " and " triplet (triad) " described in 516; And in US publication 2007/0123618, describe the polymerization of these molecules, combine by reference.

non-macrocyclic proligand and complex compound

According to general rule, the existence due to metal allows multiple front ligand binding to produce multiple oxidation state, so the ReAM comprising non-macrocyclic chelants is bonded to metal ion to form non-macrocyclic chelate compound together.

In some embodiments, the front part of nitrogen supply is employed.Before suitable nitrogen supply, part is well known in the art, and includes but not limited to NH2; NHR; NRR '; Pyridine; Pyrazine; Pyrazinamide; Imidazoles; The substitutive derivative of two pyridines and two pyridines; Three pyridines and substitutive derivative; The substitutive derivative of phenanthroline, particularly 1,10-phenanthroline (referred to as phen) and phenanthroline is as 4,7-dimethyl phenanthroline and two pyridols [3,2-a:2 ', 3 '-c] azophenlyene (referred to as dppz); Two pyrido azophenlyene; Isosorbide-5-Nitrae, 5,8,9,12-six azepine Sanya phenyl (referred to as hat); 9,10-phenanthrenequione diimine (referred to as phi); Isosorbide-5-Nitrae, 5,8-naphthisotetrazine (referred to as tap); Isosorbide-5-Nitrae, 8,11-tetraazacyclododecane tetradecane (drawing amine (cyclam) referred to as ring) and isocyanide.The derivative of replacement can also be used, comprise fused derivative.It should be noted that think there is no coordination saturation metal ion and need to add another kind of before the macrocyclic ligand of part for the large ring of these object right and wrong.Those skilled in the art will it is to be understood that can covalently bound multiple " non-large ring " part to form the compound of coordination saturation, but it lacks cyclic skeleton.

The suitable Sigma's supply part using carbon, oxygen, sulphur and phosphorus is known in the art.Such as, at CottonandWilkenson, AdvancedOrganicChemistry, 5thEdition, JohnWiley & Sons, in 1988, have found suitable Sigma's carbon donor, such as, see the 38th page, incorporated herein by reference.Similarly, suitable oxygen part comprises crown ether known in the art, water and other materials.The phosphine of phosphine and replacement is also suitable; See the 38th page of CottonandWilkenson..

Oxygen, sulphur, phosphorus and nitrogen supply part is connected in the mode allowing hetero-atom to be used as coordination atom.

part and complex compound before multinuclear

In addition, many ligands that some execution modes utilize are multinuclear parts, and such as, they can in conjunction with more than one metal ion.These can be large ring or non-large ring.

U.S. Patent number 6,212,093; 6,728,129; 6,451,942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484,394; With U.S. Serial No 10/040,059; 10/682,868; 10/445,977; 10/834,630; 10/135,220; 10/723,315; 10/456,321; 10/376, outline multiple suitable front part and complex compound and suitable substituting group in 865; Whole in conjunction with it clearly by reference, their structure particularly wherein described and description.

the application of Phosphonium ionic liquid or salt and purposes

As used herein and unless otherwise noted, otherwise term " memory cell ", " mnemon " or " memory cell " refer to the electrochemical cell that can be used for storage information.Preferably " memory cell " is the zone of dispersion by least one and the storage medium preferably by two electrodes (such as, work electrode and reference electrode) addressing.Can addressable memory cell (such as, unique electrode is combined with each memory cell) separately, or particularly when the oxidation state of different memory cell is diacritic, can by the multiple memory cell of single electrode addressing.This memory cell can comprise dielectric (such as, with the dielectric of counter ion dipping) alternatively.

As used herein, term " electrode " refer to can delivered charge (such as, electronics) to storage molecule and/or any medium by storage molecule delivered charge (such as, electronics).Preferred electrode is metal and conductive organic molecule, includes but not limited to iii group element (that comprise doping with iii group element that is oxidation), IV race element (that comprise doping with IV race element that is oxidation), V group element (that comprise doping with V group element that is oxidation) and transition metal (comprising transition metal oxide and transition metal nitride).Electrode can be fabricated to actual tieing up with 2 or 3 shapes (such as, discrete line, liner (pad), plane, spheroid, cylinder) tieed up.

As used herein and unless otherwise noted, otherwise term " multiple oxidation state " means more than a kind of oxidation state.In a preferred embodiment, oxidation state can reflect to obtain electronics (reduction) or betatopic (oxidation).

As used herein and unless otherwise noted, otherwise term " many porphyrin arrays " refers to the discrete number of the large ring of two or more covalently bound porphyrins.Many porphyrin arrays can be straight chain, ring-type or side chain.

As used herein and unless otherwise noted, otherwise term " output of integrated circuit " refers to the voltage or signal that are produced by one or more assemblies of one or more integrated circuit and/or integrated circuit.

As used herein and unless otherwise noted, otherwise when being used for mentioning memory storage of the present invention, term " is present in single plane " and refers to the assembly of discussion (such as, storage medium, electrode etc.) be present in the fact that the same physical plane of device (such as, is present on single thin layer).Typically simultaneously, such as, in single operation, the assembly on same level can be manufactured on.Therefore, such as, all electrodes (supposing that they all have same material) in single plane typically can be applied in single (such as, sputtering) step.

As used herein and unless otherwise noted, otherwise potentiometer device is the device of the current potential can measured between the interface that caused by the difference of the equilibrium concentration of the Redox molecules in electrochemical cell.

As used herein and unless otherwise noted, otherwise term " oxidation " refers to the one or more electronics lost in element, compound or chemical substituents/subelement.In the oxidation reaction, the atom of the element related in reaction loses electronics.So these atomic charges must become more positive.The material of experience oxidation loses electronics, thus electronics occurs as the product of oxidation reaction.Because oxidized material Fe ²⁺(aqueous solution) loses electronics, so at reaction Fe ²⁺(aqueous solution) → Fe ³⁺(aqueous solution)+e ^-in, be oxidized, although apparent generation is as the electronics of " dissociating " entity in the oxidation reaction.On the contrary, term reduction refers to that element, compound or chemical substituents/subelement obtain one or more electronics.

As used herein and unless otherwise noted, otherwise term " oxidation state " refers to electric neutrality state or is obtained or lose the state that electronics produces by element, compound or chemical substituents/subelement.In one preferred embodiment, term " oxidation state " refers to and comprises neutral state and by the state obtaining or lose any state except neutral state that electronics (reduction or oxidation) causes.

As used herein and unless otherwise noted, otherwise term " reading " or " inquiry " refer to the oxidation state determining one or more molecules (such as, comprising the molecule of storage medium).

As used herein and unless otherwise noted, otherwise term " redox active unit " or " redox active subelement " refer to the component of molecule or the molecule that can be oxidated or reduced by the suitable voltage of application.

As used herein and unless otherwise noted, otherwise term " renewal ", when for mentioning storage molecule or storage medium, refer to applied voltage to storage molecule or storage medium the oxidation state of this storage molecule or storage medium to be reset to predetermined state (such as, storage molecule or the oxidation state of storage medium before adjacent reading).

As used herein and unless otherwise noted, otherwise term " reference electrode " is used in reference to the one or more electrodes be provided for by the reference of the measurement of work electrode record (such as, specific reference voltage).In a preferred embodiment, the reference electrode in memory storage of the present invention, at identical current potential, although in some embodiments, needs not be this situation.

As used herein and unless otherwise noted, otherwise " sinusoidal volt ampere meter " is the volt-ampere device of the Frequency Domain Properties can determining electrochemical cell.

As used herein and unless otherwise noted, otherwise term " storage density " refers to every volume bit number and/or per molecule bit number that can store.When saying that storage medium has the storage density being greater than per molecule 1 bit, it refers to that storage medium preferably comprises wherein individual molecule and can store the fact of the molecule of at least one bit information.

As used herein and unless otherwise noted, otherwise term " memory location " refers to the discrete domain or region of wherein arranging storage medium.When with one or more electrode addressing, memory location can form memory cell.But, make them have substantially identical oxidation state if two memory locations comprise identical storage medium, and jointly addressing two memory locations, so they can form the memory cell of a function.

As used herein and unless otherwise noted, otherwise term " storage medium " refers to and comprises storage molecule of the present invention, is preferably bonded to the composition of substrate.

Substrate is preferably applicable to the solid material connecting one or more molecules.Substrate can be formed by following material: include but not limited to glass, plastics, silicon, mineral matter (such as, quartz), semi-conducting material, pottery, metal etc.

As used herein and unless otherwise noted, otherwise the device as the resultant electric current of applied voltage or change in voltage in electrochemical cell to be measured in term " voltammertry device ".

As used herein and unless otherwise noted, otherwise voltage source be can applied voltage to any source (such as, molecule, device, circuit etc.) of target (such as, electrode).

As used herein and unless otherwise noted, otherwise term " work electrode " is used in reference to one or more electrode of the state for setting or read storage medium and/or storage molecule.

device

Some execution modes of the Phosphonium ionic liquid compositions of Ben Faming can be used for forming multiple mixed type electric device.Such as, in one embodiment, provide device, comprise: the first electrode, the second electrode and the electrolyte be made up of ionic liquid compositions, this ionic liquid compositions comprises: the Yi kind of following general formula or Duo Zhong Phosphonium cationoid:

R ¹R ²R ³R ⁴P，

Wherein, R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion, and wherein, described electrolyte is electrically coupled at least one in described first and second electrodes.In some embodiments, the first electrode is made up of redox active molecule (ReAM) described above in detail.

In another embodiment, provide molecular memory device, its counterelectrode comprising work electrode and be configured to provide electric capacity; With comprise following ion conductive composition: the Yi kind of above general formula or Duo Zhong Phosphonium cationoid, and wherein, this ion conductive composition is electrically coupled at least work electrode and counterelectrode.

In another embodiment, the present invention includes molecular memory element, it comprises switching device, is coupled to bit line (bitline) and the wordline (wordline) of switching device and passes through the addressable molecular memory device of this switching device.This molecular memory device can be placed on two or more discrete states, wherein, by the signal that is applied to bit line and wordline this molecular memory device be placed in discrete state.This molecular memory device comprises the first electrode, the electrolyte of Phosphonium cationoid and suitable anion between the second electrode and described first and second electrodes.Another execution mode comprises molecular memory array, and it comprises multiple molecular memory element, wherein, each molecular memory element can be placed on two or more discrete states.Each molecular memory element is made by multiple bit line and word line coupling to multiple molecular memory element to be coupled at least one bit line and at least one wordline and can by its addressing.

Molecular memory device can comprise the addressable array of molecular memory element.Address decoder received code address also generates the word-line signal corresponding to coded address.Word line driver is coupled to address decoder and produces the word-line signal amplified.The word-line signal control switch amplified, the member of molecular memory element array is optionally coupled to bit line by this switch.The read/write logic determination molecular memory device being coupled to bit line is reading mode or WriteMode.In reading mode, the sense amplifier being coupled to every bit lines detects the electronic state of selectively coupled molecular memory element and on bit line, produces the data-signal of the electronic state of the selectively coupled molecular memory element of instruction.In WriteMode, read/write logical drive data-signal is to bit line and selectively coupled molecular memory element.

Another execution mode comprises device, and it comprises the logic element as integrated in application-specific integrated circuit (ASIC) (applicationspecificintergratedcircuit) (ASIC) and system on chip (systermonchip) (SOC) device etc. with the molecular memory device embedded.This execution comprises formed and interconnective one or more functional unit overall with molecular memory device.This functional unit can comprise solid-state electronic devices and/or molecular electronic device.

In a particular embodiment, complete molecular memory device as formed after the semiconductor substrate wherein forming active device and laminated construction thereon.In other embodiments, as the micron wherein formed in the semiconductor substrate of active device or nano-pore, molecular memory device is completed.Molecular memory device use with semiconductor substrate and semiconductor substrate in before the process technology manufacture of the active device that formed compatibility mutually.Molecular memory device comprises, such as, have the electrochemical cell of two or more electrode surfaces separated by electrolyte (such as, pottery or solid electrolyte).Storage molecule (such as, having the molecule of one or more oxidation state that can be used for storage information) is coupled to the electrode surface in electrochemical cell.

Other execution modes of the present invention comprise the purposes independently selected from following assembly: transistor switching device, comprises field-effect transistor, be coupled to the row decoder of wordline, be coupled to the column decoder of bit line, be connected to the galvo-preamplifier of bit line, be connected to the sense amplifier of bit line, received code address also generates the address decoder of the word-line signal corresponding to coded address, be coupled to the line drive of address decoder, wherein, line drive produces the word-line signal of amplification (alternatively, wherein, the word-line signal control switch amplified, the member of switch optionally coupled molecule memory element array is to bit line), be coupled to the read/write logic element of bit line, wherein, read/write logic element determination molecular memory device is reading mode or WriteMode, be coupled to the sense amplifier of every bit lines, wherein, when device is at reading mode, the sense amplifier being coupled to every bit lines detects the electronic state of selectively coupled molecular memory element and on bit line, produces the selectively coupled molecular memory element of instruction (make when device is at WriteMode, read/write logical drive data-signal is to bit line and selectively coupled molecular memory element) data-signal of the electronic state of dielectric substrate, with their combination.

Further execution mode comprises the second electrode of coupling grounding, and perpendicular or parallel bit line and wordline.

Other execution mode has memory array of the present invention, comprises volatile storage as DRAM or SRAM, or non-volatility memorizer is as flash memory or ferroelectric memory.

Further embodiment provides array, wherein, molecular memory device comprises formation attachment layer on the first electrode, wherein, this attachment layer comprises opening, and wherein, and molecular material in the opening and be electrically coupled to the second electrode lay and be formed in the dielectric substrate in attachment layer.

Another execution mode comprises the device of over all Integration, and it comprises the molecular memory device of the present invention of the logic device being configured to perform specific function and the embedding being coupled to logic device.This device can comprise application-specific integrated circuit (ASIC) (ASIC), system on chip (SOC), solid-state electronic devices or molecular electronic device alternatively.

Standard method well known to those skilled in the art can be used to manufacture memory storage of the present invention.In one preferred embodiment, according to the standard method known (such as, see Rai-Choudhury (1997) TheHandbookofMicrolithography, Micromachining, andMicrofabrication, SPIEOpticalEngineeringPress; Bard & Faulkner (1997) FundamentalsofMicrofabrication) electrode layer is applied to suitable substrate (such as, silicon dioxide, glass, plastics, pottery etc.).At following and other U.S. Patent number 6,212,093; 6,728,129; 6,451,942; 6,777,516; 6,381,169; 6,208,553; 6,657,884; 6,272,038; 6,484,394; With United States serial 10/040,059; 10/682,868; 10/445,977; 10/834,630; 10/135,220; 10/723,315; 10/456,321; 10/376,865; Describe multiple technologies with US publication 20070123618, by reference it is all combined clearly, the manufacturing technology particularly wherein summarized.

There is the various device and system construction that have benefited from using molecular memory.

By row address reception in N position is received to column address decoder operative memory device to row-address decoder and M bit column address.Row-address decoder is created on the signal in a wordline.Wordline can be included in and drive high current signal to the word line driver circuit in wordline.Because the length that wordline extends across many chip surfaces often, thin conductor, so it needs significant electric current and powerful switch to drive word-line signal.As a result, line driver circuit is often provided with except power supply circuit (not shown) as other logic elements provide the electric power of electrical power for operation to supply.Therefore, word line driver often comprises large assembly, and the speed-sensitive switch of big current often causes noise, increases the weight of the restriction to electric power supply and power governor, and increases the weight of isolating construction.

In a kind of memory array of routine, there are the row (bit line) more than row (wordline), because in renewal rewards theory process, activate every bar wordline and upgrade all memory elements being coupled to this wordline.Therefore, the number of row is fewer, and the time upgrading the cost of all row is fewer.A feature of the present invention be can configure molecular memory element with show tens of, hundreds of, thousands of or effectively, the data hold time significantly grown of the typical capacitor of ratio of the grade of unrestricted second.Therefore, can renewal circulation be performed with more low-frequency order of magnitude or all omit.Therefore, the renewal of the physical layout of the actual influence memory array that can relax is considered, and can realize the array of multiple geometry.Such as, easily can manufacture memory array by more substantial wordline, this will make every bar wordline shorter.As a result, can word line driver circuit be made as less or be eliminated, because need lower electric current to carry out the every bar wordline of high-speed driving.Alternately or additionally, shorter wordline can be driven quickly to improve the read/write access time.Substitute as another, the often row of memory location can be provided with many wordline, to be provided for the mechanism of the various states storing information in each memory location.

Sense amplifier is coupled to every bit lines and operation is coupled to the signal of the state of the memory cell of this bit line to detect instruction on bit line 109, and amplifies this state to suitable logic level signals.In one embodiment, sense amplifier can realize with substantially conventional design, and design conventional like this will operate to detect and to amplify the signal from molecular memory element.Alternately, different from the capacitor of routine, some molecular memory element provide the very different signal of their state of instruction.These different signals can reduce the needs of the sense amplifier logic to routine, because can than the signal be stored in conventional capacitor more easily and be reliably latched into the buffering area of read/write logic from the status signal of molecular memory device.That is, the present invention can provide enough large device to eliminate the needs to sense amplifier.

Read/write logic comprises the circuit for memory storage being placed in read/write status.In read states, the data from molecular array are placed on bit line and (are with or without the operation of sense amplifier), and are caught by buffering area/breech lock (latch) in read/write logic.Which bit lines of selection is active by column address decoder in specific read operation.In write operation, data-signal is urged on the bit line of selection by read/write logic, makes when wordline is activated, and these data will rewrite any data be stored in addressing memory cell.

Renewal rewards theory is substantially similar to read operation; But, the address driving that wordline is driven by refresh circuit (not shown) instead of applied by outside.In renewal rewards theory, sense amplifier, if you are using, drive bit line to the signal level of the current status of instruction memory cell, and this value is automatically written back to memory cell.Different from read operation, at no point in the update process, the state of bit line is not coupled to read/write logic.If the charge retention time of molecule used is less than the operation lifetime of the device of use, such as, for flash memory during the order of magnitude of 10 years, this is just needed to operate.

In one that comprises central processing unit and molecular memory exemplary embedded system, memory bus coupling CPU and molecular memory device are with IA interchange address, data and control signal.Alternatively, embedded system can also comprise the memory of the routine be coupled with memory bus.Conventional memory can comprise random access storage device (such as, DRAM, SRAM, SDRAM etc.) or read-only memory (such as, ROM, EPROM, EEPROM etc.).The memory of these other types can be used for cached data molecular memory device, storage operation system or BIOS file etc.Embedded system can comprise one or more I/O (I/O) interface, and this interface can make CPU and external device (ED) and system communication.I/O interface can by realizations such as serial port, parallel port, prevention at radio-frequency port, optical port, infrared ports.Further, communication can be carried out to use any obtainable agreement (comprising the agreement based on packet) by configuration interface.

battery

Phosphonium ionic liquid, salt and composition are suitable for the electrolyte done in battery applications very much according to the embodiment of the present invention.In one embodiment, provide battery, it comprises: positive pole (negative electrode), negative pole (anode), barrier film between described positive pole and negative pole; And electrolyte.Electrolyte is made up of the ionic liquid compositions dissolved in a solvent or one or more ionic liquids or salt, comprises: one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

Wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion.In some embodiments, R ¹, R ², R ³and R ⁴by 1 to 6 carbon atom independently of one another, the more commonly alkyl group of 1 to 4 carbon atom composition.Any one in salt or multiple can be liquid or solid under 100 DEG C and following temperature.In some embodiments, salt by a kind of cation and a kind of anion to forming.In other embodiments, salt is made up of a kind of cation and multiple anion.In other embodiments, salt is by a kind of anion and multiple cation composition.In further execution mode, salt is made up of multiple cation and multiple anion.In one embodiment, electrolyte forms by having Yi kind or Duo Zhong Phosphonium cationoid and one or more anion ion liquids, wherein, ionic liquid compositions shows the thermodynamic stability being up to 375 DEG C, the ionic conductivity being greater than under the liquidus curve scope of 400 DEG C and room temperature at least 1mS/cm or at least 5mS/cm or at least 10mS/cm.In another embodiment, electrolyte is made up of one or more salt with dissolving in a solvent a kind or many kinds of Phosphonium cationoids and one or more anion, wherein, this electrolyte composition to show under room temperature the ionic conductivity of at least 5mS/cm or at least 10mS/cm or at least 15mS/cm or at least 20mS/cm or at least 30mS/cm or at least 40mS/cm or at least 50mS/cm or at least 60mS/cm.

Further describe the battery of the electrolyte composition comprised according to the embodiment of the present invention in the co-pending U.S. Patent patent application serial numbers (attorney 057472-060) simultaneously submitted to it, by reference it is all openly incorporated into this.

In some embodiments, electrolyte composition is made up of one or more in following solvent, but be not limited thereto: acetonitrile, carbonic acid ethylidene ester (EC), propylene carbonate (PC), butylene carbonate base ester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoro carbonic acid ethylidene ester (FEC), fluorobenzene (FB), vinylene carbonate base ester (VC), ethylene thiazolinyl ethylidene ester (VEC), carbonate ethylidene ester (PhEC), third methyl carbonic (PMC), diethoxyethane (DEE), dimethoxy-ethane (DME), oxolane (THF), gamma-butyrolacton (GBL) and gamma-valerolactone (GVL).

In some embodiments, electrolyte composition is made up of one or more lithium salts, and this lithium salts has one or more anion be selected from by the following group formed: PF ₆, (CF ₃) ₃pF ₃, (CF ₃) ₄pF ₂, (CF ₃cF ₂) ₄pF ₂, (CF ₃cF ₂cF ₂) ₄pF ₂, (-OCOCOO-) PF ₄, (-OCOCOO-) (CF ₃) ₃pF, (-OCOCOO-) ₃p, BF ₄, CF ₃bF ₃, (CF ₃) ₂bF ₂, (CF ₃) ₃bF, (CF ₃) ₄b, (-OCOCOO-) BF ₂, (-OCOCOO-) BF (CF ₃), (-OCOCOO-) (CF ₃) ₂b, (-OSOCH ₂sOO-) BF ₂, (-OSOCF ₂sOO-) BF ₂, (-OSOCH ₂sOO-) BF (CF ₃), (-OSOCF ₂sOO-) BF (CF ₃), (-OSOCH ₂sOO-) B (CF ₃) ₂, (-OSOCF ₂sOO-) B (CF ₃) ₂, CF ₃sO ₃, (CF ₃sO ₂) ₂n, (-OCOCOO-) ₂pF ₂, (CF ₃cF ₂) ₃pF ₃, (CF ₃cF ₂cF ₂) ₃pF ₃, (-OCOCOO-) ₂b, (-OCO (CH ₂) _ncOO-) BF (CF ₃), (-OCOCR ₂cOO-) BF (CF ₃), (-OCOCR ₂cOO-) B (CF ₃) ₂, (-OCOCR ₂cOO-) ₂b, CF ₃bF (-OOR) ₂, CF ₃b (-OOR) ₃, CF ₃b (-OOR) F ₂, (-OCOCOCOO-) BF (CF ₃), (-OCOCOCOO-) B (CF ₃) ₂, (-OCOCOCOO-) ₂b, (-OCOCR ¹r ²cR ¹r ²cOO-) BF (CF ₃) and (-OCOCR ¹r ²cR ¹r ²cOO-) B (CF ₃) ₂; And wherein, R, R ¹and R ²h or F independently of one another.

In further execution mode, electrolyte composition is made up of one or more in following lithium salts, but is not limited thereto: lithium hexafluoro phosphate (LiPF ₆), LiBF4 (LiBF ₄), lithium perchlorate (LiClO ₄), hexafluoroarsenate lithium (LiAsF ₆), three fluoromethanesulfonic lithiums or trifluoromethanesulfonic acid lithium (LiCF ₃sO ₃), two (trifyl) imide li (Li (CF ₃sO ₂) ₂n or LiIm) and two (five fluorine mesyls) imide li (Li (CF3CF ₂sO ₂) ₂n or LiBETI).

Low battery equivalent series resistance (ESR) for the energy circulation efficiency strengthened and the key request of sending maximum power.Therefore, it has high ionic transfer conductivity to cell electrolyte is useful.Unexpectedly, when this literary composition described above Gong Kai Phosphonium electrolyte composition replaces conventional electrolyte or when phosphonium salt being used as together with the electrolyte of routine additive, ionic conductivity significantly raises, and the stability of cell apparatus is significantly improved, can find out below in an example.

In an exemplary execution mode, there is no solvent Chun Phosphonium ionic liquid (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃show the ionic conductivity of 15.2mS/cm.

At the execution mode Zhong ， Phosphonium ionic liquid (CH that another is exemplary ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃when mixing in acetonitrile (ACN) solvent, under the ACN/ ionic liquid volume ratio between 1.5 and 2.0, show the ionic conductivity of 75mS/cm.

At the execution mode Zhong ， Phosphonium ionic liquid (CH that another is exemplary ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃when mixing in propylene carbonate (PC) solvent, under the PC/ ionic liquid volume ratio between 0.75 and 1.25, show the ionic conductivity of 22mS/cm.

In the execution mode that other are exemplary, with the concentration of 1.0M, Duo Zhong phosphonium salt is dissolved in acetonitrile (ACN) solvent.The electrolyte obtained at room temperature shows and is greater than about 28mS/cm or is greater than about 34mS/cm or is greater than about 41mS/cm or is greater than about 55mS/cm or is greater than the ionic conductivity of about 61mS/cm.

In the execution mode that another is exemplary, the 1.0MLiPF in the mixed solvent of the EC (carbonic acid ethylidene ester) and DEC (diethyl carbonate) (being recorded as EC:DEC=1:1) that are in 1:1 weight ratio ₆in conventional electrolyte solution, with 10w% Tian Jia phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃.By Tian Jia Phosphonium additive, this electrolytical ionic conductivity raises 109% at-30 DEG C, and raises about 25% at+20 DEG C and+60 DEG C.In general, make the result into Phosphonium additive, the ionic conductivity of conventional electrolyte solution raises at least 25%.

In execution mode exemplary further, the 1.0MLiPF in the mixed solvent of EC (carbonic acid ethylidene ester), the DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) (being recorded as EC:DEC:EMC=1:1:1) that are in 1:1:1 weight ratio ₆in conventional electrolyte solution, with 10w% Tian Jia phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃.By Tian Jia Phosphonium additive, electrolytical ionic conductivity raises 36% at 20 DEG C, at 60 DEG C, raise 26%, and raises 38% at 90 DEG C.In general, make the result into Phosphonium additive, the ionic conductivity of conventional electrolyte solution raises at least 25%.

No matter be used as the additive in conventional electrolyte as displacement or Jiang phosphonium salt, another considerable advantage of Xin Xing Phosphonium electrolyte composition disclosed herein is, they show the electrochemical voltage stability window wider than the electrolyte of routine.

In the execution mode that some are exemplary, Duo Zhong phosphonium salt is dissolved in acetonitrile (ACN) solvent to form the electrolyte solution of 1.0M concentration.In the battery with Pt work electrode and Pt counterelectrode and Ag/Ag+ reference electrode, determine electrochemical voltage window.In one embodiment, stable voltage window is about between-3.0V and+2.4V.In another embodiment, voltage window is about between-3.2V and+2.4V.In another is arranged, between voltage window Yue – 2.4V and+2.5V.In another is arranged, voltage window is about between-1.9V and+3.0V.

No matter be used as the additive in conventional electrolyte as displacement or Jiang phosphonium salt, another considerable advantage of this literary composition Gong Kai Phosphonium electrolyte composition is used to be, the vapour pressure that they show reduction compared with the electrolyte of routine and the combustibility therefore reduced, thus improve battery-operated fail safe.In one aspect of the invention, be present in electrolyte Dang salt phosphonium salt being used as together with conventional electrolyte (it comprises conventional non-phosphonium salt) additive Shi ， phosphonium salt and routine with the mol ratio within the scope of the salt of 1/100 to 1/1 phosphonium salt/routine.

In an exemplary execution mode, Tong Guo is Jiang phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃be dissolved in acetonitrile (ACN) solvent with the concentration of 1.0M and form electrolyte.The vapour pressure of ACN reduces about 39% at 25 DEG C, and reduces by 38% at 105 DEG C.The remarkable suppression of phosphonium salt to vapour pressure is the flammable advantage reducing electrolyte solution, thus the fail safe of improving device operation.

In the execution mode that another is exemplary, the 1.0MLiPF in the mixed solvent of the EC (carbonic acid ethylidene ester) and DEC (diethyl carbonate) that are in 1:1 weight ratio ₆conventional electrolyte solution in, with 20w% Tian Jia Phosphonium additive (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃.By Tian Jia Phosphonium additive to conventional electrolyte, flame self-extinguishing time reduces 53%.Phosphonium salt is used as the additive in conventional electrolyte by this instruction Tong Guo, significantly can improve the safety and reliability of lithium ion battery.

Further ， Phosphonium electrolyte has the combustibility of reduction, therefore improves battery-operated fail safe.In other, Phosphonium ionic liquid or salt are used as the formation that additive promotes alternate (SEI) layer of solid electrolyte or electrode protecting layer by Ke Yi.This SEI layer contributes to widening electrochemical stability windows, suppresses degraded or the decomposition reaction of battery, thus improves battery cycle life.

Phosphonium ionic liquid, salt and composition are suitable for and make multiple battery as lithium primary cell and lithium secondary battery very much according to the embodiment of the present invention, comprise the electrolyte in lithium ion battery and chargeable lithium metal battery.The example of lithium primary cell includes but not limited to: lithium/manganese dioxide (Li/MnO ₂), lithium/mono-fluorocarbons (Li/CFx), lithium/silver-vanadium oxide (Li/Ag ₂v ₄o ₁₁), Li-(CF) _x, lithium/iron disulfide (Li/FeS ₂) and lithium/cupric oxide (Li/CuO).The example of lithium ion battery (LIB) includes but not limited to that the carbon that carbon, graphite, Graphene, silicon (Si), tin (Sn), Si/Co adulterate and metal oxide are as the anode of lithium metatitanic acid oxide (LTO) and lithium and cobalt oxides (LCO) (LiCoO ₂), lithium manganese oxide (LMO) (LiMn ₂o ₄), iron lithium phosphate (LFP) (LiFePO ₄), lithium nickel cobalt manganese oxide (NMC) (Li (NiMnCo) O ₂), lithium nickel cobalt aluminum oxide (NCA) (Li (NiCoAl) O ₂), Li, Ni, Mn oxide (LNMO) (Li ₂niMn ₃o ₈) and the negative electrode of lithium-barium oxide (LVO).The example of chargeable lithium metal battery includes but not limited to: lithium anodes and lithium and cobalt oxides ((LCO) (LiCoO ₂), lithium manganese oxide (LMO) (Li/Mn ₂o ₄) iron lithium phosphate ((LFP) (LiFePO ₄), lithium-nickel-manganese-cobalt (NMC) (Li (NiMnCo) O ₂), lithium nickel cobalt aluminium (NCA) (Li (NiCoAl) O ₂), Li, Ni, Mn oxide (LNMO) (Li ₂niMn ₃o ₈) negative electrode, lithium/sulphur battery and lithium/air cell.

In further execution mode, above stored energy method and electrochemical double layer capacitor (EDLC) can be combined to form the hybrid energy storage system comprising battery unit and EDLC array.

electrochemical double layer capacitor

Phosphonium ionic liquid, salt and composition are suitable for the electrolyte done in electrochemical double layer capacitor (EDLC) very much according to the embodiment of the present invention.In one embodiment, provide EDLC, it comprises: positive pole, negative pole, barrier film between described positive pole and negative pole; And electrolyte.Described electrolyte is made up of ionic liquid compositions or one or more ionic liquids or salt (dissolving in a solvent), comprises a kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

And wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion.In some embodiments, R ¹, R ², R ³and R ⁴by 1 to 6 carbon atom independently of one another, the more commonly alkyl group of 1 to 4 carbon atom composition.Any one in salt or multiple can be liquid or solid under 100 DEG C and following temperature.In some embodiments, salt by a kind of cation and a kind of anion to forming.In other embodiments, salt is made up of a kind of cation and multiple anion.In other embodiments, salt is by a kind of anion and multiple cation composition.In further execution mode, salt is made up of multiple cation and multiple anion.

In one embodiment, electrolyte forms by having Yi kind or Duo Zhong Phosphonium cationoid and one or more anion ion liquids, wherein, ionic liquid compositions shows the thermodynamic stability being up to 375 DEG C, the ionic conductivity being greater than under the liquidus curve scope of 400 DEG C and room temperature at least 1mS/cm or at least 5mS/cm or at least 10mS/cm.In another embodiment, electrolyte is made up of one or more salt with dissolving in a solvent a kind or many kinds of Phosphonium cationoids and one or more anion, wherein, this electrolyte composition to show under room temperature the ionic conductivity of at least 5mS/cm or at least 10mS/cm or at least 15mS/cm or at least 20mS/cm or at least 30mS/cm or at least 40mS/cm or at least 50mS/cm or at least 60mS/cm.

Further describe the EDLC device of the electrolyte composition comprised according to certain embodiments of the present invention in the co-pending U.S. Patent patent application serial numbers (attorney 057472-059) simultaneously submitted to it, by reference it is all openly incorporated into this.

In some embodiments, electrolyte composition is made up of one or more in following solvent, but be not limited thereto: acetonitrile, carbonic acid ethylidene ester (EC), propylene carbonate (PC), butylene carbonate base ester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoro carbonic acid ethylidene ester (FEC), fluorobenzene (FB), vinylene carbonate base ester (VC), vinyl ethylene carbonate (VEC), carbonate ethylidene ester (PhEC), third methyl carbonic (PMC), diethoxyethane (DEE), dimethoxy-ethane (DME), oxolane (THF), gamma-butyrolacton (GBL) and gamma-valerolactone (GVL).

Lower battery equivalent series resistance (ESR) for the energy circulation efficiency strengthened and the key request of sending maximum power.Therefore, it has high ionic transfer conductivity to cell electrolyte is useful.Unexpectedly, when this literary composition described above Gong Kai Phosphonium electrolyte composition replaces conventional electrolyte or when phosphonium salt being used as together with the electrolyte of routine additive, ionic conductivity significantly raises; And the stability of cell apparatus is significantly improved, can find out below in an example.

At execution mode Zhong ， Phosphonium the ionic liquid ((CH that another is exemplary ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃when mixing in propylene carbonate (PC) solvent, under the PC/ ionic liquid volume ratio between 0.75 and 1.25, show the ionic conductivity of 22mS/cm.

In the execution mode that another is exemplary, the 1.0MLiPF in the mixed solvent of the EC (carbonic acid ethylidene ester) and DEC (diethyl carbonate) (being recorded as EC:DEC=1:1) that are in 1:1 weight ratio ₆conventional electrolyte solution in, with 10w% Tian Jia phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃.By Tian Jia Phosphonium additive, this electrolytical ionic conductivity raises 109% at-30 DEG C, and raises about 25% at+20 DEG C and+60 DEG C.In general, make the result into Phosphonium additive, the ionic conductivity of conventional electrolyte solution raises at least 25%.

In execution mode exemplary further, the 1.0MLiPF in the mixed solvent of EC (carbonic acid ethylidene ester), the DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) (being recorded as EC:DEC:EMC1:1:1) that are in 1:1:1 weight ratio ₆conventional electrolyte solution in, with 10w% Tian Jia phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃.By Tian Jia Phosphonium additive, electrolytical ionic conductivity raises 36% at 20 DEG C, at 60 DEG C, raise 26%, and raises 38% at 90 DEG C.In general, make the result into Phosphonium additive, the ionic conductivity of conventional electrolyte solution raises at least 25%.

In the execution mode that some are exemplary, Duo Zhong phosphonium salt is dissolved in acetonitrile (ACN) solvent to form the electrolyte solution of 1.0M concentration.In the battery with Pt work electrode and Pt counterelectrode and Ag/Ag+ reference electrode, determine electrochemical voltage window.In arranging at one, stable voltage window is about between-3.0V and+2.4V.In another is arranged, voltage window is about between-3.2V and+2.4V.In another is arranged, between voltage window Yue – 2.4V and+2.5V.In another is arranged, voltage window is about between-1.9V and+3.0V.

In an exemplary execution mode, Tong Guo is Jiang phosphonium salt-(CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃be dissolved in (concentration of 1.0M) in acetonitrile (ACN) solvent and form electrolyte.The vapour pressure of ACN reduces about 39% at 25 DEG C, and reduces by 38% at 105 DEG C.The remarkable suppression of phosphonium salt to vapour pressure is the flammable advantage reducing electrolyte solution, thus the fail safe of improving device operation.

Further, Phosphonium ionic liquid or salt are used as the formation that additive promotes alternate (SEI) layer of solid electrolyte or electrode protecting layer by Ke Yi.This protective layer contributes to widening electrochemical stability windows, suppresses degraded or the decomposition reaction of EDLC, thus improves the cycle life of EDLC.

Phosphonium ionic liquid, salt and composition are suitable for the electrolyte done in multiple EDLC very much according to the embodiment of the present invention, wherein, electrode active material is selected from by any one or multiple in the following group formed: carbon black, graphite, Graphene, carbon-metal compound; Polyaniline, polypyrrole, polythiophene; The oxide of lithium, ruthenium, tantalum, rhodium, iridium, cobalt, nickel, molybdenum, tungsten or vanadium, chloride, bromide, sulfate, nitrate, sulfide, hydride, nitride, phosphide, or selenides and their combination.

In further execution mode, the negative electrode (positive pole) that the Phosphonium electrolyte composition that can use this Wen Gongkai, the carbon activated by high surface are made and the anode (negative pole) be made up of the graphite inserting lithium ion set up EDLC device.The EDLC formed is asymmetric mixed capacitor, is called lithium-ion capacitor (LIC).

In other execution mode, can by EDLC and battery combination to form the capacitor-battery mixed tensor storage system comprising battery unit and EDLC array.

electrolytic capacitor

Phosphonium ionic liquid, salt and composition are suitable for the electrolyte done in electrolytic capacitor very much according to the embodiment of the present invention.In one embodiment, provide electrolytic capacitor, it comprises: positive pole, negative pole, barrier film between described positive pole and negative pole; And electrolyte.Electrolyte is made up of the ionic liquid compositions dissolved in a solvent or one or more ionic liquids or salt, comprises a kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

Wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion.In one embodiment, electrolyte forms by having Yi kind or Duo Zhong Phosphonium cationoid and one or more anion ion liquids, wherein, ionic liquid compositions shows the thermodynamic stability being up to 375 DEG C, the ionic conductivity being greater than under the liquidus curve scope of 400 DEG C and room temperature at least 1mS/cm or at least 5mS/cm or at least 10mS/cm.In another embodiment, electrolyte is made up of one or more salt with dissolving in a solvent a kind or many kinds of Phosphonium cationoids and one or more anion, wherein, this electrolyte composition to show under room temperature the ionic conductivity of at least 5mS/cm or at least 10mS/cm or at least 15mS/cm or at least 20mS/cm or at least 30mS/cm or at least 40mS/cm or at least 50mS/cm or at least 60mS/cm.In some embodiments, electrolyte composition is made up of one or more in following solvent, but be not limited thereto: acetonitrile, carbonic acid ethylidene ester (EC), propylene carbonate (PC), butylene carbonate base ester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoro carbonic acid ethylidene ester (FEC), fluorobenzene (FB), vinylene carbonate base ester (VC), ethylene thiazolinyl ethylidene ester (VEC), carbonate ethylidene ester (PhEC), third methyl carbonic (PMC), diethoxyethane (DEE), dimethoxy-ethane (DME), oxolane (THF), gamma-butyrolacton (GBL) and gamma-valerolactone (GVL).In one embodiment, positive pole-anode has the aluminium foil of the thin-oxide film formed by electrolytic oxidation or anodization typically.Although aluminium is the preferable alloy for anode, other metals can be used as tantalum, magnesium, titanium, niobium, zirconium and zinc.Negative pole-negative electrode is the aluminium foil of etching commonly.Further ， Phosphonium electrolyte meter reveals the combustibility of reduction compared with the electrolyte of routine, therefore improves the fail safe of electrolytic capacitor operation.

dSSC

Phosphonium ionic liquid, salt and composition are suitable for the electrolyte done in DSSC (DSSC) very much according to the embodiment of the present invention.In one embodiment, provide DSSC, it comprises: the anode of dye molecule attachment, the electrolyte comprising oxidation-reduction system and negative electrode.Electrolyte is made up of the ionic liquid compositions dissolved in a solvent or one or more ionic liquids or salt, comprises: one kind or many kinds of Phosphonium cationoids of following general formula:

R ¹R ²R ³R ⁴P，

Wherein: R ¹, R ², R ³and R ⁴substituting group independently of one another; With one or more anion.In another embodiment, electrolyte characterizes by having one kind or many kinds of Phosphonium cationoids and one or more anion, wherein, this electrolyte composition show following at least two or more: thermodynamic stability, low volatility, wide liquidus curve scope, ionic conductivity, chemical stability and electrochemical stability.In another embodiment, this electrolyte characterizes by having one kind or many kinds of Phosphonium cationoids and one or more anion, wherein, electrolyte composition shows the thermodynamic stability being up to about 375 DEG C or higher temperature and the ionic conductivity being up to 10mS/cm.

electrolytic film

Phosphonium ionic liquid, salt and composition are suitable for and make electrolytic film or dielectric film very much according to the embodiment of the present invention.In one embodiment, provide electrolytic film, comprise: be applied to substrate Phosphonium ionic liquid compositions.In another embodiment, provide electrolytic film, comprise: the dissolving being applied to substrate in a solvent a kind or many kinds of Phosphonium ionic liquids or salt.In one embodiment, one kind or many kinds of Phosphonium ionic liquids or salt dissolve in a solvent, to form coating solution.By any suitable mode, as by spraying, spin coating etc., solution is applied to substrate.Then heated substrates is with partially or completely except desolventizing, forms electrolyte or ion-conducting membrane.In other embodiments, the solution dissolving ionic liquid, salt and polymer is in a suitable solvent coated on substrate, as by spraying or spin coating, then partially or completely evaporating solvent.This causes the formation of ionic conductive polymer gel/film.This film particularly suitable acts on the electrolyte of battery, EDLC and DSSC, and is used as fuel cell membrane.

heat transfer medium

The desirable properties of the high thermodynamic stability of the Phosphonium ionic liquid of Ben Faming, low volatility and wide liquidus curve scope is highly suitable for heat transfer medium.Some embodiments of the present invention provide heat transfer medium, comprise dissolving ionic liquid compositions in a solvent or one or more salt, comprise: Yi kind or Duo Zhong Phosphonium cationoid and one or more anion, wherein, this heat transfer medium show be up to about 375 DEG C of temperature thermodynamic stability, be greater than the liquidus curve scope of 400 DEG C.In some embodiments, heat transfer medium of the present invention is pyroreaction medium.In another embodiment, heat transfer medium of the present invention is high Extraction medium.

other application

The Phosphonium ionic liquid of Ben Faming has found purposes in other application.In an exemplary execution mode, examine embedded capacitor device.In one embodiment, embedded capacitor device is made up of the dielectric arranged between two electrodes, and wherein, dielectric is made up of the electrolytic film of Phosphonium ionic composition described above.Embedded capacitor device of the present invention can be embedded in integrated circuit packaging.Capacitor arrangement that further execution mode comprises " on plate (on-board) ".

embodiment

With reference now to specific embodiment, in more detail embodiments of the present invention are described.The embodiment below provided only is intended to presented for purposes of illustration, and and limits the scope of the invention never in any form and/or instruct.

In general, by suitably replacing the metathesis reaction of phosphonium salt and the suitable slaine replaced, or by the phosphine precursor of suitably replacement and the reaction of the suitable anionic pre-cursors replaced, Bei Phosphonium ionic liquid processed.Fig. 1 to 4 shows the reaction scheme of four illustrative embodiments of the Phosphonium ionic liquid carrying out Ben Faming.

embodiment 1

Prepare Phosphonium ionic liquid.By AgSO ₃cF ₃be added to round bottom (Rb) flask of 50ml and be assembled to 3cm rotary glass material (swivelfrit).Emptying flask also puts it in glove box.In glove box, add two-n-pro-pyl second base first base Phosphonium iodide, and re-assembly flask, put it into vacuum pipeline, emptying, and vacuum moves into anhydrous THF.Allow flask is warming up to room temperature, be then heated to 40 DEG C 2 hours.This causes the formation of light green pearl solid.This solid is filtered by crossing.This produces perlarious milky white solution.Volatile material is removed under a high vacuum by using 30 DEG C of hot bath heating.This obtains the white crystalline material that productive rate is 0.470g.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 5.

embodiment 2

Prepare Jin mono-Bu Phosphonium ionic liquid.In glove box, two-n-pro-pyl Yi base Jia Ji Phosphonium iodide are added in the Rb flask of 100ml, then remove and be dissolved in the DIH of 50ml ₂in O.Add AgO ₂cCF ₃to this solution, produce yellow pearl sediment immediately.Stirring after 2 hours, filtering AgI by crossing, and with the DIH of each 5ml ₂o washing leaching cake 3 times.By rotary evaporator removing main body water.This produces clarification, low viscous liquid, then in a vacuum by heat and stirring is dried.This causes the solidification of material.In tepidarium, mildly heat white solid obtain seeming just at the liquid of the above melting of room temperature.This experiment produces the material of 0.410g.Fig. 6 A depicts reaction scheme.Thermogravimetric analysis (TGA) and emergent gas analysis (evolvedgasanalysis) (EGA) test are carried out to material, and result is shown in Fig. 6 B and Fig. 6 C.

embodiment 3

In this embodiment, in glove box, two-n-pro-pyl Yi base Jia Ji Phosphonium iodide are added in the Rb flask of 100ml, then take out from fume hood and be dissolved in 70mlMeOH.Next, AgO is added ₂cCF ₂cF ₂cF ₃, produce yellow slurry immediately.Stirring after 3 hours, removing solid by filtering, by rotary evaporation removing main body MeOH, and dry remaining residue under a high vacuum.This produces yellow gel mud materials.Observe " liquid " type Crystallization in the side of Rb flask, then when scraping flask, its " melting " is fallen.This experiment produces the material of 0.618g.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Fig. 7 A.Also carry out emergent gas analysis (EGA), and result is shown in Fig. 7 B.

embodiment 4

Pressure flask is put into glove box, and adds the P (CH of 0.100g ₂oH) ₃, add the THF-d8 of 5mL subsequently.Once dissolution of solid, then add Me ₂sO ₄.Then sealed flask it is taken out from glove box.In the oil bath of 110 DEG C, be heated 10 minutes, then cool, then be returned to glove box, and take out 1mL aliquot and be used for ¹hNMR.Fig. 8 A shows reaction scheme.Fig. 8 B shows ¹hNMR spectrogram.

embodiment 5

In this experiment, in glove box, 1-ethyl-1-first base Phosphonium heterocycle pentane (phospholanium) nitrate is added in the 14/20Rb flask of 100ml.By KC (CN) ₃be added into wherein, then Rb be assembled to the rotary glass material of 3cm.This frit is taken out to pipeline, and vacuum moves into CHCl ₃.Allow stirred flask 12 hours.The brown material of gluing is observed at drag.Filtering solution obtains pearl shape, milky filtrate, isolates brown oil by it.With the CHCl of recirculation ₃wash 2 these brown materials, cause it to become more in vain and more granular.Remove all volatile components under a high vacuum, produce low viscous brown oil.This experiment produces the material of 1.52g.Reaction scheme is shown in Fig. 9 A.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Fig. 9 B.

embodiment 6

In this experiment, in glove box, 1-ethyl-1-Jia Ji Phosphonium azacyclohexane (phosphorinanium) iodide are added in the Rb flask of 100ml, then it are taken out (being dissolved in 70mlMeOH in fume hood) from fume hood.Next, AgO is added ₂cCF ₂cF ₂cF ₃, produce yellow precipitation immediately.Stirred flask 18 hours, then passes through solids removed by filtration.By rotary evaporation removing main body MeOH, and dried residue under a high vacuum.This step produces canescence, faint yellow solid.This experiment produces the material of 0.620g.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 10.

embodiment 7

In another experiment, in fume hood, 1-butyl-1-second base Phosphonium heterocycle pentane (phospholanium) iodide are added in Rb flask, are then dissolved in water and stir.Add AgO ₃sCF ₃, and form yellow mercury oxide immediately.Stirred flask 2 hours, then vacuum filtration.Solution foams during filtering, and observes milky substance after filtering.This material of rotary evaporation, and dried residue in the oil bath of molten solids under vacuo.This experiment produces the material of 0.490g.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 11.

embodiment 8

In further testing, in fume hood, 1-butyl-1-Yi Ji Phosphonium azacyclohexane iodide are added in flask.Add MeOH, then stirred flask 15 minutes.Add p-toluenesulfonic acid silver.Stirred flask 4 hours.Form yellow mercury oxide.This material of gravity filtration, then rotary evaporation.Drying material under vacuo, obtains liquid.This experiment produces the material of 0.253g.Reaction scheme is shown in Figure 12 A.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 12 B.

embodiment 9

Another experiment in, 250mg (0.96mmol) triethyl group Jia Ji Phosphonium iodide are added in the deionized water of 15mL, subsequently by the predissolve of 163mg (0.96mmol) silver nitrate in the deionized water of 5.0mL.Stirring reaction 10 minutes, now filters out white yellow mercury oxide.Then with 5.0mL deionized water washing solid, and merge containing water section.On the rotary evaporator under vacuo except anhydrating, to remain white solid residue, by its 3:1 mixture recrystallization by ethyl acetate and acetonitrile, produce triethyl group first base Phosphonium nitrate.Productive rate: 176mg, 94%.Phosphonium nitrate (176mg, 0.90mmol) is dissolved in the anhydrous acetonitrile of 5mL.By 113mg (0.90mmol) the potassium tetrafluoroborate Tian Jia that is dissolved in 5mL anhydrous acetonitrile Zhi phosphonium salt, and after stirring for 5 minutes, pass through solids removed by filtration.On the rotary evaporator except desolventizing, and the pale solid obtained is by the 2-propyl alcohol recrystallization of heat, produces analytically pure triethyl group first base Phosphonium tetrafluoroborate.Productive rate: 161mg, 81%.By shown in Figure 13 A ¹shown in HNMR spectrogram and Figure 13 B ³¹pNMR spectrogram confirms composition.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 14.

embodiment 10

In another experiment, the triethyl group Bing Ji Phosphonium bromide of 250mg (1.04mmol) and the potassium tetrafluoroborate of 135mg (1.06mmol) are incorporated in 10mL acetonitrile.Meticulous white KBr precipitation starts to be formed immediately.Stir the mixture 1 hour, filter, and on the rotary evaporator except desolventizing is to provide white solid.Productive rate: 218mg, 85%.This crude product can by 2-propyl alcohol recrystallization to provide analytically pure material.By shown in Figure 15 A ¹shown in HNMR spectrogram and Figure 15 B ³¹pNMR spectrogram confirms composition.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 16.

embodiment 11

In further testing, react in the glove box of nitrogen atmosphere.Triethyl group Bing Ji Phosphonium iodide (1.00g, 3.47mmol) is dissolved in the anhydrous acetonitrile of 20mL.With continuous stirring hexafluorophosphoric acid silver 877mg (3.47mmol) is added in this solution.Silver iodide white precipitate is formed at once, and stirring reaction 5 minutes.Filter and use anhydrous CH ₃cN many washing precipitations.Filtrate is taken out from glove box, and evaporation is to obtain white solid.Roughage is dissolved in the isopropyl alcohol of heat, and makes it pass 0.2 μm of PTFE film.Cooled screening, to obtain white crystal, is collected by filtering.Productive rate: 744mg, 70%.By shown in Figure 17 A ¹shown in HNMR spectrogram and Figure 17 B ³¹pNMR spectrogram confirms composition.Thermogravimetric analysis (TGA) is carried out to this material, and result is shown in Figure 18.

embodiment 12

In this embodiment, (the CH of 1:3:1 mol ratio will be comprised ₃cH ₂cH ₂) (CH ₃) ₃pCF ₃bF ₃/ (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃/ (CH ₃cH ₂cH ₂) (CH ₃cH ₂) ₂(CH ₃) PCF ₃bF ₃san Yuan Phosphonium ionic liquid compositions with comprise (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃single-component composition compare.Differential scanning calorimetry (DSC) is carried out to this material, and the result of single-component composition is shown in Figure 21 A and the result of ternary composition is shown in Figure 21 B.As illustrated in fig. 19 a and fig. 19b, compared with single-component composition, ternary composition illustrates the advantage of lower cryogenic temperature and therefore wider liquidus curve scope.

embodiment 13

In another experiment, prepare phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃.This salt shows the low viscosity of 19.5cP at 25 DEG C, the fusing point of-10.0 DEG C, the initial decomposition temperature of 396.1 DEG C, the liquid scope of 407 DEG C, the ionic conductivity of 15.2mS/cm and when having Pt work electrode and Pt counterelectrode and Ag/Ag ⁺the electrochemical voltage window of-1.5V to+1.5V when measuring in the electrochemical cell of reference electrode.Result is summarised in in following table 14.

Table 14

embodiment 14

In another experiment, prepare phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃.With the ACN/ salt volume ratio in 0 to 4 scope, salt is dissolved in acetonitrile (ACN) solvent.At room temperature measure the ionic conductivity of the electrolyte solution obtained, and result is shown in Figure 20.As shown in figure 20, ionic conductivity than raising, is increased to the peak value of the 75mS/cm between 1.5 to 2.0 under ratio with ACN/ salt from the 13.9mS/cm 0 ratio (pure ionic liquid).

embodiment 15

In another experiment, prepare phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃.With the PC/ salt volume ratio in 0 to 2.3 scope, salt is dissolved in propylene carbonate (PC) solvent.At room temperature measure the ionic conductivity of the electrolyte solution obtained, and result is shown in Figure 21.As shown in figure 21, ionic conductivity raises with PC/ salt ratio, is increased to the peak value of the 22mS/cm between 0.75 to 1.25 under ratio from the 13.9mS/cm 0 ratio (pure ionic liquid).

embodiment 16-35

In further testing, prepare Duo Zhong phosphonium salt.Salt is dissolved in acetonitrile (ACN) solvent to form the electrolyte solution of 1.0M concentration.At room temperature measure the ionic conductivity of the electrolyte solution obtained.Electrochemical voltage window (electrochemical window) is determined in the electrochemical cell with Pt work electrode and Pt counterelectrode and Ag/Ag+ reference electrode.The results are summarized in table 15.This electrolyte at room temperature shows and is greater than about 28mS/cm or is greater than about 34mS/cm or is greater than about 41mS/cm or is greater than about 55mS/cm or is greater than the ionic conductivity of about 61mS/cm.In arranging at one, electrochemical window is about between-3.2V and+3.2V.In another kind is arranged, electrochemical window is between about-2.0 and+2.4V.In another is arranged, electrochemical window is about between-1.5V and+1.5V.In another arranges, electrochemical window is about between-1.0V and+1.0V.

Table 15

Embodiment	Cation	Anion	Conductivity (mS/cm)	Electrochemical window (V)
					16	(CH ₃CH ₂CH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	C(CN) ₃ ^-	69.0	-1.7 to+1.1
17	(CH ₃CH ₂CH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	CF ₃BF ₃ ^-	64.0	-3.0 to+2.4
					18	(CH ₃CH ₂CH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	CF ₃SO ₃ ^-	43.7	-2.0 to+1.9
19	(CH ₃CH ₂CH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	BF ₄ ^-	55.5	-2.0 to+1.9
					20	(CH ₃CH ₂CH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	(CF ₃CO) ₂N ^-	41.5	-1.6 to+2.0
21	(CH ₃CH ₂CH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	(CF ₃) ₂PO ₂ ^-	45.6	-1.8 to+1.8
					22	(CH ₃CH ₂CH ₂) ₂(CH ₃) ₂P ⁺	CF ₃SO ₃ ^-	38.7	-2.0 to+2.4
23	(CH ₃CH ₂CH ₂) ₂(CH ₃) ₂P ⁺	CH ₃C ₆H ₄SO ₃ ^-	28.6	N/A
					24	(CH ₃CH ₂CH ₂) ₂(CH ₃) ₂P ⁺	C(CN) ₃ ^-	61.5	-1.8 to+1.1
25	(CH ₃CH ₂CH ₂) ₂(CH ₃) ₂P ⁺	(CF ₃SO ₂) ₂N ^-	43.1	-3.2 to+2.4
					27	(CH ₃CH ₂CH ₂) ₂(CH ₃) ₂P ⁺	CH ₂CHBF ₃ ^-	41.0	-1.0 to+1.0
28	((CH ₃) ₂CH)(CH ₃CH ₂)(CH ₃) ₂P ⁺	C ₄H ₄SO ₄N	32.5	N/A
					29	((CH ₃) ₂CH)(CH ₃CH ₂)(CH ₃) ₂P ⁺	C ₆H ₅BF ₃ ^-	37.6	N/A
30	((CH ₃) ₂CH)(CH ₃CH ₂)(CH ₃) ₂P ⁺	C ₆H ₃F ₂BF ₃ ^-	37.1	N/A
					31	((CH ₃) ₂CHCH ₂)(CH ₃CH ₂)(CH ₃) ₂P ⁺	CH ₂CHBF ₃ ^-	45.7	-1.8 to+1.8
32	((CH ₃) ₂CHCH ₂) ₂(CH ₃CH ₂)(CH ₃)P ⁺	CF ₃SO ₃ ^-	46.8	N/A
					33	((CH ₃) ₂CHCH ₂) ₂(CH ₃CH ₂)(CH ₃)P ⁺	(CF ₃SO ₂) ₂N ^-	37.5	N/A
34	((CH ₃) ₂CHCH ₂) ₂(CH ₃CH ₂)(CH ₃)P ⁺	CH ₃CH ₂BF ₃ ^-	34.3	N/A
					35	((CH ₃) ₂CHCH ₂) ₂(CH ₃CH ₂)(CH ₃)P ⁺	BF ₄ ^-	33.9	N/A

embodiment 36-41

In further experiment, prepared Duo Zhong phosphonium salt and by its with contrast ammonium salt and compare.Salt is dissolved in propylene carbonate (PC) solvent to form the electrolyte solution of 1.0M concentration.At room temperature measure the ionic conductivity of the electrolyte solution obtained.Electrochemical voltage window (electrochemical window, EchemWindow) is determined in the electrochemical cell with Pt work electrode and Pt counterelectrode and Ag/Ag+ reference electrode.Result is summarised in table 16, demonstrate,proves real phosphonium salt and shows the conductivity higher than contrast-ammonium analog and wider electrochemical voltage stability window.

Table 16

embodiment 42-45

In further experiment, prepared Duo Zhong phosphonium salt and by its with contrast ammonium salt and compare.Salt is dissolved in propylene carbonate (PC) solvent to form the electrolyte solution of concentration within the scope of 0.6M to maximum 5.4M.At room temperature measure the ionic conductivity of the electrolyte solution obtained, and result is presented in Figure 22.Under 2.0M concentration, the numerical value of conductivity is shown in Table 17, and shows that phosphonium salt shows the conductivity higher than contrast-ammonium analog.

Table 17

embodiment 46

In another experiment, prepare phosphonium salt-(CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃, and by its with contrast ammonium salt (CH ₃cH ₂) ₃(CH ₃) NBF ₄relatively.Salt is dissolved in acetonitrile (ACN) solvent to form the electrolyte solution of 1.0M concentration.Measured the vapour pressure of solution by pressure differential scanning calorimetry (DSC) at the temperature of 25 to 105 DEG C.As shown in figure 23, at 25 DEG C compared with 27% of ammonium salt, the vapour pressure of ACN is reduced by 39% by phosphonium salt, and at 105 DEG C compared with 13% of ammonium salt, phosphonium salt is 38%.Tong Guo phosphonium salt to the remarkable suppression of vapour pressure reduce electrolyte solution flammable in be advantage, therefore improve utilizing the device of this electrolyte composition as the fail safe of battery, EDLC device etc.

embodiment 47-50

In another experiment, phosphonium salt is used as the additive in lithium battery standard electrolyte solution by ，.In an embodiment of the invention, 1.0MLiPF ₆standard electrolyte solution in the EC (carbonic acid ethylidene ester) and DEC (diethyl carbonate) (being recorded as EC:DEC1:1) mixed solvent of 1:1 weight ratio is provided by NovolyteTechnologies (branch of BASFGroup).Jiang phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃be added into the standard electrolyte solution of 20w%.In yet another embodiment of the present invention, 1.0MLiPF ₆standard electrolyte solution in EC (carbonic acid ethylidene ester), the DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) (being recorded as EC:DEC:EMC1:1:1) mixed solvent of 1:1:1 weight ratio is provided by NovolyteTechnologies (branch of BASFGroup).Jiang phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃be added into the standard electrolyte solution of 10w%.By the 1g sample of electrolyte solution is put into glass dish, lighting sample, and record the time needed for fray-out of flame, carrying out flame from putting out test.Result is summarised in in following table 18.Between 10w% and 20w%, concentration Phosphonium additive reduces flame self-extinguishing time (second/gram) 33% to 53%.Phosphonium salt is used as the additive in conventional lithium-ion electrolyte by this instruction Tong Guo, significantly can improve the safety and reliability of lithium ion battery.

Table 18

Embodiment	Solvent	Conventional salt	Phosphonium additive (w%)	SET(s/g)
					47	EC∶DEC 1∶1	1.0M LiPF ₆	0	67
48	EC∶DEC 1∶1	1.0M LiPF ₆	20	31
					49	EC∶DEC∶EMC	1.0M LiPF ₆	0	75
5	EC∶DEC∶EMC	1.0M LiPF ₆	10	51

embodiment 51

In another experiment, phosphonium salt is used as the additive in lithium battery standard electrolyte solution by ，.In an embodiment of the invention, 1.0MLiPF ₆standard electrolyte solution in the EC (carbonic acid ethylidene ester) and DEC (diethyl carbonate) (being recorded as EC:DEC1:1) mixed solvent of 1:1 weight ratio is provided by NovolyteTechnologies (branch of BASFGroup).Jiang phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pC (CN) ₃be added into the standard electrolyte solution of 10w%.The ionic conductivity of the solution of measurement standard electrolyte solution and Ju You Phosphonium additive under the different temperatures of-30 to+60 DEG C.， Phosphonium additive improves the ionic conductivity of electrolyte solution at wide temperature range as shown in figure 24.At-30 DEG C, Zuo is the result of Phosphonium additive, and ionic conductivity raises 109%.At+20 DEG C, Zuo is the result of Phosphonium additive, and ionic conductivity raises 23%.At+60 DEG C, Zuo is the result of Phosphonium additive, and ionic conductivity raises about 25%.In general, make the result into Phosphonium additive, the ionic conductivity of standard electrolyte solution raises at least 25%.

embodiment 52

In another experiment, phosphonium salt is used as the additive in lithium battery standard electrolyte solution by ，.In an embodiment of the invention, 1.0MLiPF ₆standard electrolyte solution in EC (carbonic acid ethylidene ester), the DEC (diethyl carbonate) and EMC (ethyl methyl carbonate) (being recorded as EC:DEC:EMC1:1:1) mixed solvent of 1:1:1 weight ratio is provided by NovolyteTechnologies (branch of BASFGroup).Jiang phosphonium salt (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂pCF ₃bF ₃be added into the standard electrolyte solution of 10w%.The ionic conductivity of the solution of measurement standard electrolyte solution and Ju You Phosphonium additive under the different temperatures of 20 to 90 DEG C.， Phosphonium additive improves the ionic conductivity of electrolyte solution at wide temperature range (especially at high temperature) as shown in figure 25.At 20 DEG C, Zuo is the result of Phosphonium additive, and ionic conductivity raises about 36%.At 60 DEG C, Zuo is the result of Phosphonium additive, and ionic conductivity raises about 26%.At 90 DEG C, Zuo is the result of Phosphonium additive, and ionic conductivity raises about 38%.In general, make the result into Phosphonium additive, the ionic conductivity of standard electrolyte solution raises at least 25%.

The present invention is not limited to the scope of embodiment disclosed in embodiment, these embodiments be intended to illustrate invention several aspect and any execution mode of function equivalent within the scope of the invention.In fact, except illustrate herein and describe those except multiple amendment of the present invention it will be apparent to those skilled in the art that and be intended to drop in claims.

Refer to multiple reference, by reference it is all openly incorporated into this.

Claims

1. an electrolyte composition, comprises:

Dissolve in a solvent one kind or many kinds of Phosphonium ionic liquids or one kind or many kinds of phosphonium salts, described one kind or many kinds of Phosphonium ionic liquids or phosphonium salt comprise one kind or many kinds of Phosphonium cationoids of following formula:

R ¹R ²R ³R ⁴P，

Wherein, R ¹, R ², R ³and R ⁴alkyl group independently of one another; With one or more anion.

2. electrolyte composition according to claim 1, wherein, R ¹, R ², R ³and R ⁴the alkyl group be made up of 1 to 4 carbon atom independently of one another.

3. electrolyte composition according to claim 1, wherein, R ¹, R ², R ³and R ⁴the alkyl group be made up of 1 to 4 carbon atom independently of one another, and in described R group at least two are identical, and described R group does not comprise oxygen.

4. electrolyte composition according to claim 1, wherein, the one or more hydrogen atoms in one or more described R group replaced by fluorine.

5. electrolyte composition according to claim 1 wherein, can be liquid or solid at any one in Suo Shu phosphonium salt or multiple temperature below 100 DEG C.

6. electrolyte composition according to claim 1, wherein, at least one in Suo Shu Phosphonium ionic liquid or salt by a kind of cation and a kind of anion to forming.

7. electrolyte composition according to claim 1, at least one wherein in ， Phosphonium ionic liquid Huo phosphonium salt is by a kind of anion and multiple cation composition.

8. electrolyte composition according to claim 1, wherein, at least one stated in Phosphonium ionic liquid or phosphonium salt be made up of a kind of cation and multiple anion.

9. electrolyte composition according to claim 1, wherein, at least one stated in Phosphonium ionic liquid or phosphonium salt be made up of multiple cation and multiple anion.

10. electrolyte composition according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂cH ₂) ₂(CH ₃cH ₂) (CH ₃) P ⁺.

11. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂p ⁺.

12. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂) ₃(CH ₃) P ⁺.

13. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂cH ₂) (CH ₃cH ₂) ₃p ⁺.

14. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂) ₄p ⁺.

15. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂cH ₂) ₃(CH ₃) P ⁺.

16. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CH ₃cH ₂cH ₂) ₃(CH ₃cH ₂) P ⁺.

17. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CF ₃cH ₂cH ₂) (CH ₃cH ₂) ₃p ⁺.

18. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CF ₃cH ₂cH ₂) ₃(CH ₃cH ₂) P ⁺.

19. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CF ₃cH ₂cH ₂) ₃(CH ₃) P ⁺.

20. electrolyte compositions according to claim 1, wherein, Suo Shu Phosphonium cationoid is made up of following formula: (CF ₃cH ₂cH ₂) ₄p ⁺.

21. electrolyte compositions according to claim 1, wherein, state Phosphonium ionic liquid or phosphonium salt is made up of one or more anion be selected from by the following group formed: PF ₆, (CF ₃) ₃pF ₃, (CF ₃) ₄pF ₂, (CF ₃cF ₂) ₄pF ₂, (CF ₃cF ₂cF ₂) ₄pF ₂, (-OCOCOO-) PF ₄, (-OCOCOO-) (CF ₃) ₃pF, (-OCOCOO-) ₃p, BF ₄, CF ₃bF ₃, (CF ₃) ₂bF ₂, (CF ₃) ₃bF, (CF ₃) ₄b, (-OCOCOO-) BF ₂, (-OCOCOO-) BF (CF ₃), (-OCOCOO-) (CF ₃) ₂b, (-OSOCH ₂sOO-) BF ₂, (-OSOCF ₂sOO-) BF ₂, (-OSOCH ₂sOO-) BF (CF ₃), (-OSOCF ₂sOO-) BF (CF ₃), (-OSOCH ₂sOO-) B (CF ₃) ₂, (-OSOCF ₂sOO-) B (CF ₃) ₂, CF ₃sO ₃, (CF ₃sO ₂) ₂n, (-OCOCOO-) ₂pF ₂, (CF ₃cF ₂) ₃pF ₃, (CF ₃cF ₂cF ₂) ₃pF ₃, (-OCOCOO-) ₂b, (-OCO (CH ₂) _ncOO-) BF (CF ₃), (-OCOCR ₂cOO-) BF (CF ₃), (-OCOCR ₂cOO-) B (CF ₃) ₂, (-OCOCR ₂cOO-) ₂b, CF ₃bF (-OOR) ₂, CF ₃b (-OOR) ₃, CF ₃b (-OOR) F ₂, (-OCOCOCOO-) BF (CF ₃), (-OCOCOCOO-) B (CF ₃) ₂, (-OCOCOCOO-) ₂b, (-OCOCR ¹r ²cR ¹r ²cOO-) BF (CF ₃) and (-OCOCR ¹r ²cR ¹r ²cOO-) B (CF ₃) ₂; And wherein, R, R ¹and R ²h or F independently of one another.

22. electrolyte compositions according to claim 1, wherein, one or more anion described are by following any one or multiplely form: ^-o ₃sCF ₃, ^-o ₂cCF ₃, ^-o ₂cCF ₂cF ₂cF ₃, CF ₃bF ₃ ^-, C (CN) ₃ ^-, PF ₆ ^-, NO ₃ ^-, ^-o ₃sCH ₃, BF ₄ ^-, ^-o ₃sCF ₂cF ₂cF ₃, ^-o ₂cCF ₂cF ₃, ^-o ₂cH, ^-o ₂cC ₆h ₅, ^-oCN, CO ₃ ^2-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, (CF ₃sO ₂) ₂n ^-, (CF ₃) ₂bF ₂ ^-, (CF ₃) ₃bF ^-, CF ₃cF ₂bF ₃ ^-or ^-n (CN) ₂.

23. electrolyte compositions according to claim 1, wherein, described solvent is made up of following one or more: acetonitrile, carbonic acid ethylidene ester (EC), propylene carbonate (PC), butylene carbonate base ester (BC), dimethyl carbonate (DMC), diethyl carbonate (DEC), ethyl methyl carbonate (EMC) or methyl ethyl carbonate (MEC), methyl propionate (MP), fluoro carbonic acid ethylidene ester (FEC), fluorobenzene (FB), vinylene carbonate base ester (VC), ethylene thiazolinyl ethylidene ester (VEC), carbonate ethylidene ester (PhEC), carbonic acid hydroxypropyl methyl ester (PMC), diethoxyethane (DEE), dimethoxy-ethane (DME), oxolane (THF), gamma-butyrolacton (GBL), gamma-valerolactone (GVL), or their mixture.

24. electrolyte compositions according to claim 1, wherein, Suo Shu phosphonium salt is made up of following: formula (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂p ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

25. electrolyte compositions according to claim 1, wherein, Suo Shu phosphonium salt is made up of following: formula (CH ₃) (CH ₃cH ₂) ₃any one in the cation of P and following formula or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

26. electrolyte compositions according to claim 1, wherein, Suo Shu phosphonium salt is made up of following: formula (CH ₃cH ₂cH ₂) (CH ₃cH ₂) ₃p ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) ₂b ^-, (-OCOCOO-) (CF ₃) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

27. electrolyte compositions according to claim 1, wherein, Suo Shu phosphonium salt is made up of following: formula (CH ₃cH ₂) ₄p ⁺cation and following formula in any one or multiple anion: BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or their combination.

28. electrolyte compositions according to claim 1, comprise further: one or more routine non-phosphonium salts.

29. electrolyte compositions according to claim 28, wherein, Suo Shu Phosphonium ionic liquid Huo phosphonium salt is additive.

30. electrolyte compositions according to claim 28, wherein, the salt of Suo Shu Phosphonium ionic liquid Huo phosphonium salt and described routine is with 1:100 to 1:1 Phosphonium ionic liquid or salt: the mol ratio within the scope of conventional salt is present in described electrolyte composition.

31. electrolyte compositions according to claim 28, wherein, the salt of one or more routines described is selected from the group of the following: tetraethylammonium tetrafluoroborate (TEABF ₄), tetrafluoro boric acid triethyl methyl ammonium (TEMABF ₄), 1-ethyl-3-methylimidazole tetrafluoroborate (EMIBF ₄), two (trifyl) acid imide (EMIIm) of 1-ethyl-3-methylimidazole or 1-ethyl-3-methylimidazole hexafluorophosphate (EMIPF ₆) and their mixture.

32. electrolyte compositions according to claim 28, wherein, the salt of one or more routines described is lithium class salt.

33. electrolyte compositions according to claim 28, wherein, the salt of one or more routines described is selected from the group of the following: lithium hexafluoro phosphate (LiPF ₆), LiBF4 (LiBF ₄), lithium perchlorate (LiClO ₄), hexafluoroarsenate lithium (LiAsF ₆), trifluoromethanesulfonic acid lithium (LiCF ₃sO ₃), two (trifyl) imide li (Li (CF ₃sO ₂) ₂and two (five fluorine mesyls) imide li (Li (CF N) ₃cF ₂sO ₂) ₂and their mixture N).

34. 1 kinds of electrolyte compositions, comprise:

Dissolve in a solvent one kind or many kinds of Phosphonium ionic liquids or one kind or many kinds of phosphonium salts, one or more ionic liquids described or salt comprise one or more cations in following formula:

P (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _4-x-y(wherein, x, y=0 to 4; X+y≤4), and one or more anion in following formula:

(CF ₃) _xbF _4-x(wherein, x=0 to 4),

(CF ₃(CF ₂) _n) _xpF _6-x(wherein, n=0 to 2; X=0 to 4),

(-OCO (CH ₂) _ncOO-) (CF ₃) _xbF _2-x(wherein, n=0 to 2; X=0 to 2),

(-OCO (CH ₂) _ncOO-) ₂b (wherein, n=0 to 2),

(-OSOCH ₂sOO-) (CF ₃) _xbF _2-x(wherein, x=0 to 2),

(-OCOCOO-) _x(CF ₃) _ypF _6-2x-y(x=1 to 3; Y=0 to 4; 2x+y≤6).

35. 1 kinds of electrolyte compositions, comprise:

P (-CH ₂cH ₂cH ₂cH ₂cH ₂-) (CH ₃cH ₂cH ₂) _y(CH ₃cH ₂) _x(CH ₃) _2-x-y(wherein, x, y=0 to 2; X+y≤2),

With one or more anion in following formula:

(CF ₃) _xbF _4-x(wherein, x=0 to 4),

(CF ₃(CF ₂) _n) _xpF _6-x(wherein, n=0 to 2; X=0 to 4),

(-OCO (CH ₂) _ncOO-) (CF ₃) _xbF _2-x(wherein, n=0 to 2; X=0 to 2),

(-OCO (CH ₂) _ncOO-) ₂b (wherein, n=0 to 2),

(-OSOCH ₂sOO-) (CF ₃) _xbF _2-x(wherein, x=0 to 2),

(-OCOCOO-) _x(CF ₃) _ypF _6-2x-y(x=1 to 3; Y=0 to 4; 2x+y≤6).

36. electrolyte compositions according to claim 34, wherein, the one or more hydrogen atoms in one or more cations described or anion replaced by fluorine.

37. electrolyte compositions according to claim 35, wherein, the one or more hydrogen atoms in one or more cations described or anion replaced by fluorine.

38. 1 kinds of electrolyte compositions, comprise: dissolve phosphonium salt in a solvent, wherein, phosphonium salt of stating is made up of following:

By (the CH of 1:3:1 mol ratio ₃cH ₂cH ₂) (CH ₃) ₃p/ (CH ₃cH ₂cH ₂) (CH ₃cH ₂) (CH ₃) ₂p/ (CH ₃cH ₂cH ₂) (CH ₃cH ₂) ₂(CH ₃) P composition cation;

With

Formula BF ₄ ^-, PF ₆ ^-, CF ₃bF ₃ ^-, (-OCOCOO-) BF ₂ ^-, (-OCOCOO-) (CF ₃) ₂b ^-, (-OCOCOO-) ₂b ^-, CF ₃sO ₃ ^-, C (CN) ₃ ^-, (CF ₃sO ₂) ₂n ^-or one or more anion in their combination.

39. according to electrolyte according to claim 38, and wherein, described anion is with [the BF in 100/1 to 1/1 scope ₄ ^-]: [CF ₃bF ₃ ^-] concentration of mol ratio is by BF ₄ ^-and CF ₃bF ₃ ^-mixture composition.

40. according to electrolyte according to claim 38, and wherein, described anion is with [the PF in 100/1 to 1/1 scope ₆ ^-]: [CF ₃bF ₃ ^-] concentration of mol ratio is by PF ₆ ^-and CF ₃bF ₃ ^-mixture composition.

41. according to electrolyte according to claim 38, and wherein, described anion is with [the PF in 100/1 to 1/1 scope ₆ ^-]: [BF ₄ ^-] concentration of mol ratio is by PF ₆ ^-and BF ₄ ^-mixture composition.

42. 1 kinds of electrolyte compositions, comprise: dissolve phosphonium salt in a solvent, wherein, phosphonium salt of stating is made up of following:

With

By CF ₃bF ₃ ^-the anion of composition.

43. 1 kinds of electrolyte compositions, comprise: dissolve phosphonium salt in a solvent, wherein, phosphonium salt of stating is made up of following:

With

By BF ₄ ^-the anion of composition.

44. 1 kinds of electrolyte compositions, comprise: dissolve phosphonium salt in a solvent, wherein, phosphonium salt of stating is made up of following:

With

By PF ₆ ^-the anion of composition.