CN107437467A - The hybrid super capacitor of service life with growth - Google Patents
The hybrid super capacitor of service life with growth Download PDFInfo
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- CN107437467A CN107437467A CN201710397316.2A CN201710397316A CN107437467A CN 107437467 A CN107437467 A CN 107437467A CN 201710397316 A CN201710397316 A CN 201710397316A CN 107437467 A CN107437467 A CN 107437467A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/04—Hybrid capacitors
- H01G11/06—Hybrid capacitors with one of the electrodes allowing ions to be reversibly doped thereinto, e.g. lithium ion capacitors [LIC]
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/02—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof using combined reduction-oxidation reactions, e.g. redox arrangement or solion
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/64—Liquid electrolytes characterised by additives
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/60—Liquid electrolytes characterised by the solvent
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/54—Electrolytes
- H01G11/58—Liquid electrolytes
- H01G11/62—Liquid electrolytes characterised by the solute, e.g. salts, anions or cations therein
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
Hybrid super capacitor (2),It includes at least one negative electrode (21),It includes direct capacitance active material,Electrochemical redox active material or its mixture,At least one positive electrode (22),It includes direct capacitance active material,Electrochemical redox active material or its mixture,At least one barrier film (18) being arranged between at least one negative electrode (21) and at least one positive electrode (22),With electrolyte composition (15),Condition is,At least one electrode (21),(22) direct capacitance active material and at least one electrode (21) are included,(22) electrochemical redox active material is included,Wherein described electrolyte composition (15) is the electrolyte composition of liquid and includes the non-proton organic solvent of at least one liquid,At least one conducting salt and at least one polymerizable additive agent electrolyte,The additive agent electrolyte the hybrid super capacitor just and/or negative electrode (22),(21) just and/or negative electrode (22) when applying voltage on,(21) oligomer and/or polymer architecture are formed on surface and is consequently formed coat,The coat has the solubility for being less than 1 g/L under the service condition of hybrid super capacitor in electrolyte composition (15).
Description
Prior art
Electric energy by electrochemical energy storage system such as electrochemical capacitor (ultracapacitor) or electrochemistry once-it is or secondary
Being stored in for battery pack is for many years known.The difference of the energy storage system is the original based on energy storage
Reason.
Ultracapacitor generally includes negative electrode and positive electrode, and they are separated from each other by barrier film (Separator).Institute
State the electrolyte that ionic conductivity between electrode in addition be present.The storage of electric energy is based on, and is applied on the electrode of ultracapacitor
Electrochemical double layer is formed during voltage in its surface.The charge carrier for the solvation that the bilayer is made up of electrolyte and formed, its
It is arranged on the surface of the electrode with opposite charges.It is anti-redox is not related in the case of such energy storage
Should.Therefore, ultracapacitor arbitrarily can in multiple times charge and thus have very high service life in theory.It is described super
The power density of capacitor is also high, but energy density is relatively low compared to such as Li-ion batteries piles.
Differently, once-and secondary battery in energy storage carried out by redox reaction.These batteries herein
Group also generally includes negative electrode and positive electrode, and they are separated from each other by barrier film.Electric conductivity is equally existed between said electrodes
Electrolyte.In Li-ion batteries piles（One of most widely used secondary cell set type）In, energy storage by by lithium from
Son is embedded in electrode active material and carried out.When battery assembly module is run, i.e., in discharge process, electronics is in external circuit
In from negative electrode flow to positive electrode.In the inside of battery assembly module, lithium ion moves to positive electricity in discharge process from negative electrode
Pole.Here, lithium ion reversibly deintercalation from the active material of negative electrode, this also referred to as de- lithiumation.In filling for battery assembly module
In electric process, lithium ion moves to negative electrode from positive electrode.Here, lithium ion is embedded in the active material of negative electrode again, this
Also referred to as lithiumation.
Li-ion batteries piles are characterised by that they have high energy density, i.e., they can store every quality or body
The substantial amounts of energy of product.But relatively, they only have limited power density and service life.This is not for many applications
Profit, so that Li-ion batteries piles can not or can only use in small scope in these areas.
Hybrid super capacitor represents the combination of these technologies, and is suitable for filling up with Li-ion batteries piles skill
Breach in art and the use range of supercapacitor technologies.
Hybrid super capacitor generally equally has two electrodes, and they respectively include a collector
(Stromableiter) and by barrier film it is separated from each other.Electric charge between said electrodes transport through electrolyte or electrolysis
Matter composition and ensured.The electrode generally comprises (to be also referred hereinafter as traditional super capacitor material of active material
For direct capacitance active material) and the redox reaction with the charge carrier of electrolyte can be subjected to and be consequently formed
The material (hereinafter also referred to electrochemical redox active material) of inlaid scheme.Therefore, the energy of hybrid super capacitor
Amount stores principle and is, the formation of electrochemical double layer and the formation of faraday's lithium-inlaid scheme.Thus obtained energy storage
Deposit system has high energy density, while with high power density and high service life.
However, thus the service life of hybrid super capacitor is often restricted, i.e., the active material of electrode due to
Reaction with the composition or the impurity wherein optionally contained of electrolyte composition and change its chemical composition and property.The worst
In the case of, this may cause the premature failure of electrode.
Additive agent electrolyte is used in electrolyte composition to improve the performance of Li-ion batteries piles existing
Described in technology, such as in (2006) 1379-1394 of Journal of Power Sources 162.For lithium from
The additive agent electrolyte that protective layer is built on the cathode surface of sub- battery pack for example describes：Amine etc., Journal of
Power Sources 129 (2004) 14；(2006) 328- of Abe etc., Journal of Power Sources 153
335；Komaba etc., J. Electrochem. Soc., 152 (2005) A937；Wang etc., CN103280598A
(2013)；Nie etc., J. Electrochem. Soc., 162 (2015) A1186-A1195；Nie etc., J.
Electrochem. Soc., 162 (2015) A1693-A1701；Bian etc., J. Energy Chem., 23 (2014)
383；Zuo etc., J. Electrochem. Soc., 160 (2013) A1199；Zuo etc., J. Power Sources,
219 (2012) 94。
JP 2013/012442 discloses the electrolyte composition for Li-ion batteries piles or lithium-ion capacitor, and it is wrapped
Containing the phosphate compound for being suitable for being formed protective layer on electrode.Described lithium-ion capacitor includes and is used as negative electrode active
Amorphous carbon, graphite, tin and the tin alloy and silicon and silicon alloy of material.The carbon of activation is disclosed as positive electrode active materials.
WO 2013/002186 is related to a kind of composition, and it is suitable for the electricity in Li-ion batteries piles or lithium-ion capacitor
Protective layer is formed on extremely, wherein the composition includes compound and group-M with polymerizable groups-Li+, wherein-M-Tool
There is 100 to 1500 kJ/mol lithium ion coordination energy.Furthermore, it is possible to include specific carbonate oligomer.
It is an object of the present invention to provide electrochemical energy storage system, and it has improved electrode life.The mesh
By it is described below the present invention and realize.
The content of the invention
The present invention relates to a kind of hybrid super capacitor, and it is included
- at least one negative electrode, it includes direct capacitance active material, electrochemical redox active material or its mixture,
- at least one positive electrode, it includes direct capacitance active material, electrochemical redox active material or its mixture,
- at least one the barrier film being arranged between at least one negative electrode and at least one positive electrode, and
- electrolyte composition,
Condition is that at least one electrode includes direct capacitance active material and at least one electrode and lived comprising electrochemical redox
Property material,
Wherein described electrolyte composition is the electrolyte composition of liquid and the aprotic comprising at least one liquid has
Solvent, at least one conducting salt and at least one polymerizable additive agent electrolyte, the additive agent electrolyte is described mixed
Mould assembly ultracapacitor when applying voltage just and/or on negative electrode just and/or on the surface of negative electrode formed oligomer and/
Or polymer architecture and be consequently formed coat, the coat under the service condition of hybrid super capacitor (that is ,-
40 DEG C to 100 DEG C, especially 0 DEG C to 60 DEG C of temperature range and in 0.5 to 5 bar, especially in 0.8 to 2 bar pressure limit)
There is the solubility less than 1 g/L in electrolyte composition.
The hybrid super capacitor of the present invention includes at least one positive electrode and at least one negative electrode.The electrode point
Include the collector of conduction（Also referred to as colelctor electrode）And the active material applied thereon.The collector includes such as copper
Or aluminium is as conductive material.In a preferred embodiment, the collector of the electrode is made of aluminum.
Apply negative active core-shell material on negative electrode.The negative active core-shell material includes direct capacitance active material, electrochemistry
Redox active material or its mixture.
In the sense of the present invention, direct capacitance active material refers to such material, its by traditional two-layer electrode
Know and be suitable for forming static double layer capacity, especially by formation helmholtz layer.Here setting obtains as big as possible
Surface is to form electrochemical double layer.The electrode material for being most frequently used for ultracapacitor be by its it is a variety of it is apparent in the form of
Carbon, such as activated carbon (AC), NACF (ACF), carbon (CDC), carbon-aeroge, graphite (graphite from carbide
Alkene) and CNT (CNT).These electrode materials are suitable as direct capacitance electrode active material within the scope of the invention.
Preferably, using carbon variant, particularly activated carbon.
In the sense of the present invention, electrochemical redox active material is such material, and it is by the secondary electricity of electrochemistry
Pond group, particularly as known to Li-ion batteries piles and it is suitable for being subjected to reversible electrochemistry or the reaction of faraday's Lithium-ion embeding
Or form Lithium-ion embeding compound.
Suitable for the electrochemical redox active material particularly lithium titanate such as Li of negative electrode4Ti5O12, but also phosphoric acid
Vanadium lithium such as Li3V2(PO4)3。
In a preferred embodiment, the negative electrode includes direct capacitance active material and electrochemical redox
The mixture of active material, such as activated carbon and Li4Ti5O12Mixture.Electric capacity active material is lived with electrochemical redox
The ratio of property material is preferably 1:0.25 to 1:In the range of 1.25.
Apply positive electrode active materials on the positive electrode.The positive electrode active materials include direct capacitance active material, electrification
Learn redox active material or its mixture.
On the direct capacitance material of positive electrode, all related embodiments of negative electrode are applicable.It is mentioned that activity
Material is also applied for positive electrode.
Electrochemical redox active material suitable for positive electrode is, for example, the inlaid scheme of lithiumation, and it can be reversible
Ground receives and release lithium ion.The positive electrode active materials can include composite oxides, and the composite oxides contain at least one
Metal of the kind selected from cobalt, magnesium, nickel and lithium.
One embodiment of the invention includes active positive electrode material, and it includes formula LiMO2Compound, wherein M choosing
From Co, Ni, Mn, Cr or its mixture and their mixtures with Al.Specifically mentioned LiCoO2And LiNiO2。
In a preferred embodiment, the active material of cathode is the material for including nickel, i.e. LiNi1-xM‘xO2, its
Middle M ' is selected from Co, Mn, Cr and Al and 0≤x< 1.Example include lithium-nickel-cobalt-aluminium-oxide-negative electrode (such as
LiNi0.8Co0.15Al0.05O2；) and lithium-nickel-manganese-cobalt-oxide-negative electrode (such as LiNi NCA0.8Mn0.1Co0.1O2；NMC
Or LiNi (811)0.33Mn0.33Co0.33O2；NMC (111)).
In addition, it can be mentioned that the stratiform oxygen well known by persons skilled in the art for crossing lithiumation as preferable positive electrode active materials
Compound.Example is Li herein1+xMn2-yMyO4, wherein x≤0.8, y< 2；Li1+xCo1-yMyO2, wherein x≤0.8, y<
1；Li1+xNi1-y-zCoyMzO4, wherein x≤0.8, y<1, z<1 and y+z< 1.In above-mentioned compound, M can be selected
From Al, Mg and/or Mn.
Two or more in the positive electrode active materials can also be especially used in combination with one another.One preferable real
Scheme is applied for example including formula n (Li2MnO3) : n-1(LiNi1-xM‘xO2) compound, wherein M ' be selected from Co, Mn, Cr and
Al, and 0< n <1 and 0< x < 1.
In addition, it can especially emphasize spinel compound (such as LiMn as suitable positive electrode active materials2O4), olivine
Compound (such as LiFePO4), silicate compound (such as Li2FeSiO4), hydroxyl phosphorus lithium iron-stone（Tavorit）Compound
(such as LiVPO4F)、Li2MnO3、Li1.17Ni0.17Co0.1Mn0.56O2And Li3V2(PO4)3。
In a preferred embodiment, the positive electrode includes direct capacitance active material and electrochemical redox
The mixture of active material, such as activated carbon and LiMn2O4Mixture.Electric capacity active material and electrochemical redox activity
The ratio of material is preferably 1:0.25 to 1:In the range of 1.25.
As other compositions, the negative active core-shell material and/or positive electrode active materials can especially include adhesive such as benzene
Ethylene-butylene-copolymer (SBR), Kynoar (PVDF), polytetrafluoroethylene (PTFE) (PTFE), carboxymethyl cellulose
(CMC), polyacrylic acid (PAA), polyvinyl alcohol (PVA) and ethylene/propylene/diene-terpolymer (EPDM), with
Improve the stability of the electrode.Furthermore, it is possible to conductive additive is added, such as conductive black or graphite.
The effect of the barrier film is that guard electrode is not in direct contact with one another and therefore prevented short-circuit.Meanwhile barrier film is necessary
Ensure transfer of the ion from an electrode to another electrode.Suitable material is characterised by that it is by with the exhausted of loose structure
Edge material is formed.Suitable material particularly polymer, such as cellulose, polyolefin, polyester and fluorinated polymer.It is particularly preferred
Polymer is cellulose, polyethylene (PE), polypropylene (PP), polyethylene terephthalate (PET), polytetrafluoroethylene (PTFE)
And Kynoar (PVdF) (PTFE).Ceramic material or be made from it in addition, the barrier film can include, if its
Largely ensure (lithium -) ion-transfer.It can be mentioned that material particularly include MgO or Al2O3Ceramics.The barrier film
Can be made up of the one or more of one layer of above-mentioned material or by be mutually combined respectively wherein above-mentioned material one kind or
A variety of multilayer compositions.
In addition, the hybrid super capacitor includes electrolyte composition, the electrolyte composition includes at least one
Non-proton organic solvent, at least one conducting salt and at least one polymerizable additive agent electrolyte, the organic solvent exist
Leading condition is accounted in electrochemical energy storage system generally when it runs（I.e. -40 DEG C to 100 DEG C, especially 0 DEG C extremely
Within the temperature range of 60 DEG C and in 0.5 to 5 bar, especially in 0.8 to 2 bar pressure limit）Under be in a liquid state.
In this regard, liquid refers to that the solvent has≤100 mPas, especially≤10 mPas viscosities il.It is excellent
Selection of land, viscosities il is in the range of 0.01 to 8 mPas, especially in the range of 0.1 to 5 mPas.
Suitable solvent has enough polarity, so as to dissolve other compositions of the electrolyte composition, especially institute
State one or more conducting salts.Acetonitrile, tetrahydrofuran, diethyl carbonate or gamma-butyrolacton and ring-type are can be mentioned that as example
And non-annularity carbonic ester, especially propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl Asia second
Base carbonic ester (Ethylenmethylcarbonat), methyl ethyl carbonate and its mixture.Particularly preferred acetonitrile, propylene carbonate,
Ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethylenecarbonate, methyl ethyl carbonate and its mixture.
In addition, the electrolyte composition includes at least one conducting salt.Suitable particularly the moon with steric hindrance
The salt of ion and the cation of optional steric hindrance.It is tetra-allkylammonium borate to this example, such as N (CH3)4BF4.So
And specially suitable a kind of conducting salt particularly lithium salts.The conducting salt can for example be selected from lithium chlorate (LiClO4), tetrafluoro
Lithium borate (LiBF4), lithium hexafluoro phosphate (LiPF6), hexafluoroarsenate lithium (LiAsF6), trifluoromethanesulfonic acid lithium (LiSO3CF3)、
Double (trifluoromethyl sulfonyl) imino group lithium (LiN (SO2CF3)2), double (pentafluoroethyl group sulfonyl) imino group lithium (LiN
(SO2C2F5)2), double (oxalate conjunction) lithium borate (LiBOB, LiB (C2O4)2), difluoro (oxalate conjunction) lithium borate (LiBF2
(C2O4)), three (pentafluoroethyl group) three lithium fluophosphate (LiPF3(C2F5)3) and combinations thereof.
It has been found that implementing the rear electrolyte to the hybrid super capacitor of charging and discharging circulation for the first time
Polymerizable additive is added in composition to be caused on the surface of positive electrode and/or negative electrode, especially in electrochemical redox
Restriction, protectiveness oligomer-or polymeric layer on the surface of active material.By so at least one electrode surface
On targetedly form protective layer and reduce or even prevent the composition of the electrode active material and the electrolyte composition
Other unexpected reactions.Thus power of the hybrid super capacitor when it runs is reduced to reduce and improve
The service life of hybrid super capacitor.
It is not only restricted to theory, it is believed that, the carbonic ester picture from electrolyte composition such as propylene carbonate, ethylene carbonate
Corresponding alkyl carbonate is reduced and formed at the electrode surface with diethyl carbonate (referring to Kang Xu, Chem. Rev.
2004, 104, 4303-4417).Equally there occurs the reduction of the additive agent electrolyte.Add for a variety of electrolyte
Add agent to be studied, and especially observe gamma-butyrolacton reduction and form polymer architecture (referring to Kang Xu, Chem.
Rev. 2004,104,4303-4417) and sulfur-bearing additive agent electrolyte such as sultone reduction and its reaction into alkyl
Sulphonic acid ester is (referring to K. Xu, Chem. Rev. 2014,114,11503-11618；B. Li etc.；Electrochimica
Acta 2013, 105, 1-6)。
The coat so formed is characterised by that it is with high resistance and simultaneously with especially for lithium ion
High ionic conductivity.Short-circuit danger caused by electrode contacts with each other is thus reduced, but without decrease electrode
Efficiency.
The resistance of the coat is more than 0 Ω cm2And preferably there is >=1 Ω cm2, preferably >=2 Ω cm2, especially
≥ 3 Ω cm2Value.Particularly preferred scope includes 10 to 1000 Ω cm2Resistance.
The lithium ion conductivity σ of the coatLi More than 0 S/cm.Preferably, the lithium ion conductivity of the coat
σLiFor σLi ≥ 10-15 S/cm, particularly preferred σLi ≥ 10-12 S/cm and particularly σLi ≥ 10-10 S/cm。
Suitable polymerizable additive agent electrolyte is hereafter expanded on further.Each in these additives can be independent
Ground uses in combination with one or more other additives.Suitable additive agent electrolyte is：
(1) carbonic ester of formula (Ia) or (Ib) acyclic and cyclic：
(Ia) (Ib)
Wherein R1And R2Can with it is identical or different and represent saturation or undersaturated, straight chain or it is branched, there is 1 to 12 carbon original
The hydrocarbon chain of son.Preferably, R1And R2It is straight chain, there is the hydrocarbon chain of 1 to 6 carbon atom.Preferably, group R1Or R2Extremely
One of few is undersaturated.Especially, R1Or R2Represent methyl-, ethyl-, propyl group-, butyl-, amyl group-or hexyl and another respectively
One represent vinyl-, pi-allyl-or propargyl.R3Represent saturation or alkyl undersaturated, that there is 1 to 4 carbon atom.
R1、R2And R3Can optionally by halogen atom, saturation or undersaturated, straight chain or it is branched, there is 1 to 6 carbon atom and can
With the alkyl that is substituted with halogen atoms or ring-type, saturation or it is undersaturated, there are 3 to 7 carbon atoms and can be former by halogen
The alkyl substitution of son substitution, wherein adjacent alkyl can be connected with each other, so as to form ring.R3Preferably saturation or unsaturation
, alkyl that there is 2 carbon atoms, it is substituted by least one undersaturated alkyl.Preferable halogen atom be F, Cl, Br,
I, especially F and Cl.
The instantiation of the compound of formula (Ia) is vinyl methyl carbonic ester (VMC), vinyl ethylenecarbonate
(VEC), vinyl propyl carbonate, Allyl methyl carbonate (AMC), pi-allyl ethyl carbonate ester (AEC), pi-allyl third
Base carbonic ester, propargylmethyl carbonic ester (PMC), propargyl ethyl carbonate ester, propargyl propyl carbonate and asymmetric
Dialkyl carbonate such as methyl-n-propyl carbonic ester, methyl-butylperoxyisopropyl carbonate, ethyl-n-propyl carbonic ester and ethyl-different
Propyl carbonate.
The instantiation of the compound of formula (Ib) is ethylene carbonate, methyl ethylenecarbonate, dimethylethylene
Carbonic ester, phenyl-ethylene carbonic ester (PhEC), ethenylidene carbonic ester (VC), phenyl vinylene carbonic ester (PhVC),
Vinyl ethylenecarbonate, pi-allyl ethylenecarbonate, propargyl ethylenecarbonate and pyrocatechol carbonic ester.
The instantiation of the halo derivatives of the carbonic ester of the ring-type and non-annularity be chlorethylidene carbonic ester (CEC),
Fluorine ethylenecarbonate (FEC), trifluoropropylidenyl carbonic ester (TFPC), trifluoromethyl propylene carbonate.
(2) there is the polycyclic aromatic hydrocarbon of 9 to 30 carbon atoms, such as biphenyl (BP), ortho-terphenyl (OTP), meta-terphenyl, right
Terphenyl, bibenzyl (DBZ), indenes, fluorenes, naphthalene, anthracene, BaP, acenaphthene, acenaphthene, phenanthrene, fluoranthene, pyrene, benzanthracene, coronene, simultaneously
Four benzene, pentacene and.Particularly preferably there is the polycyclic aromatic hydrocarbon of 12 to 24 carbon atoms, especially biphenyl (BP), ortho-terphenyl
And bibenzyl (DBZ) (OTP).The group of the polycyclic aromatic hydrocarbon is also separated from each other including wherein aromatic ring by hetero atom such as oxygen or nitrogen
Compound, such as diphenyl ether (DPE).
Biphenyl (BP), ortho-terphenyl (OTP), bibenzyl (DBZ) and diphenyl ether are preferably referred to from this group
(DPE).Very particularly preferably biphenyl (BP).
(3) heterocyclic aromatic compounds of formula (II)：
(II)
Wherein E represents to be selected from O, S and NR8Element, R4To R7Hydrogen atom, halogen atom, cyano group, saturation or insatiable hunger are represented respectively
Sum, with 1 to 6 carbon atom and the alkyl that can be substituted with halogen atoms or saturation or it is undersaturated, with 1 to 6 carbon
Atom and the alkoxy that can be substituted with halogen atoms, wherein adjacent group R4And R5、R5And R6、R6And R7Can phase each other
Even, so as to form ring.R8Represent hydrogen atom or saturation or undersaturated, straight chain or branched there is 1 to 6 carbon atom and can be with
The alkyl being substituted with halogen atoms.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.Preferably, group R4To R7Choosing
From hydrogen atom, cyano group, chlorine atom, fluorine atom, saturation, alkyl with 1 to 3 carbon atom or saturation, with 1 to 3
The alkoxy of carbon atom.
The example of the compound of formula (II) is furans, 2- cyanofurans, thiophene, especially N- alkyl pyrroles, N- methyl
Pyrroles and N- N-ethyl pyrrole Ns.Preferable formula (II) dicyclic compound includes 3,4- ethene-dioxythiophenes (EDT).
(4) pyridine and pyridine derivate and its boron trihalide adducts of formula (III)：
(III)
Wherein R9To R13Hydrogen atom, halogen atom, nitrile, saturation or undersaturated, straight chain or branched can be independently from each other
, alkyl with 1 to 6 carbon atom and ring-type, saturation or alkyl undersaturated, with 3 to 12 carbon atoms, wherein
Adjacent alkyl can be connected with each other, so as to form ring.Preferably, group R9To R13It is undersaturated, branched selected from hydrogen atom
, alkyl with 2 to 4 carbon atoms or ring-type, undersaturated, with 6 to 9 carbon atoms alkyl.Preferable halogen
Atom is F, Cl, Br, I, especially F and Cl.Additionally it contained the boron trihalide adducts of the compound, wherein X expression F,
Cl, Br and particularly F.
The instantiation of the compound of formula (III) is pyridine, 3- fluorine pyridine, 2- fluorine pyridine, 3- pyridine carbonitriles, 3,4- bis-
Picoline, 2- vinylpyridines, 4-vinylpridine, 4- trifluoromethyl pyridines and 2,2 '-bipyridyl, pyridine-BF3- adduction
Thing (C5H5N·BF3), 3- fluorine pyridines-BF3- adduct (C5H4FN·BF3), 2- fluorine pyridines-BF3- adduct (C5H4FN·
BF3), 3- pyridine carbonitriles-BF3- adduct, 3,4- lutidines-BF3- adduct, 2- vinylpyridines-BF3- adduct,
4-vinylpridine-BF3- adduct, 4- trifluoromethyl pyridines-BF3- adduct, particularly preferred 2- vinylpyridines, 4- ethene
Yl pyridines, 2- vinylpyridines-BF3- adduct and 4-vinylpridine-BF3- adduct.
(5) sulfite of formula (IVa) and (IVb) acyclic and cyclic：
(IVa) (IVb)
Wherein R14And R15Can be with identical or different, and represent saturation or undersaturated, straight chain or branched there is 1 to 6 carbon
The hydrocarbon chain of atom.Preferably, R14And R15It is the hydrocarbon chain of straight chain.Preferably, group R14And R15At least one of be undersaturated.
Especially, R14Or R15Represent methyl-, ethyl-, propyl group-, butyl-, amyl group-or hexyl and respectively another represent vinyl-,
Pi-allyl-or propargyl.R16Represent saturation or the undersaturated alkyl with 1 to 4 carbon atom.R14、R15And R16Can be optional
Ground by halogen atom, saturation or undersaturated, straight chain or it is branched, have and 1 to 6 carbon atom and can be substituted with halogen atoms
Alkyl or ring-type, saturation or it is undersaturated, have 3 to 7 carbon atoms and can be substituted with halogen atoms alkyl substitution,
Wherein adjacent alkyl can be connected with each other, so as to form ring.R16Preferably saturation or it is undersaturated, there are 2 or 3 carbon atoms
Alkyl.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.
The instantiation of the compound of formula (IIIa) be dimethyl sulfite, sulfurous acid diethyl ester, dipropyl sulfite,
Dibutyl sulfite, diamyl sulfite and sulfurous acid dihexyl.Particularly preferred dimethyl sulfite and sulfurous acid diethyl ester.
The instantiation of the compound of formula (IIIb) be glycol sulfite, sulfurous acid Asia propyl ester, sulfurous acid butylene,
Sulfurous acid vinyl ethyl, sulfurous acid phenyl ethyl, sulfurous acid phenylene vinylene ester.Particularly preferred glycol sulfite and
Sulfurous acid Asia propyl ester.
(6) formula (Va) and (Vb) sulphonic acid ester and disulfonate：
(Va) (Vb)
Wherein R17And R18It is straight chain or branched, saturation or hydrocarbon undersaturated, that there is 1 to 6 carbon atom independently of one another
Chain, the halogenated alkane that it can be optionally by halogen atom or with 1 to 5 carbon atom substitutes, and m and n are 1 independently of one another
To the integer of 5, particularly 1 to 3.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.Preferable halogenated alkane is-
CF3With-CCl3.In a preferred embodiment, R17And R18It is connected with each other and therefore forms ring.In particular it is preferred to formula (V)
Compound, wherein group R17And R18It is connected and is formed and is made up of three carbon atoms and O- and S- atoms bonded thereto
Ring.The particularly preferred embodiment of the compound of formula (Va) is sultone, especially PS, in 1,3- propylene sulphurs
Ester, Isosorbide-5-Nitrae-butane sultone, Isosorbide-5-Nitrae-butene sultone and its halo derivatives, especially fluoro-propane sultone.The chemical combination of formula (Vb)
The particularly preferred embodiment of thing is methane-disulfonic acid methylene ester (MMDS).
(7) sulfuric ester of formula (VI) is led to：
(VI)
Wherein R19And R20It is straight chain or branched, saturation or hydrocarbon undersaturated, that there is 1 to 6 carbon atom independently of one another
Chain, it can optionally be substituted with halogen atoms.In a preferred embodiment, R19And R20It is connected with each other, so as to be formed
Ring.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.
Particularly preferred formula (VI) compound is allyl methyl sulphonic acid ester (AMS), pi-allyl ethylsulfonic acid ester, alkynes third
Ylmethyl sulphonic acid ester (PMS), propargyl ethylsulfonic acid ester and 1,3,2- dioxy tiacyclopentane -2,2- dioxide (DTD).
(8) carboxylic acid derivates of the ring-type of formula (VII)：
(VII)
Wherein E1Represent O or NR24, R21Represent alkyl or formula-R with 1 to 5 carbon atom22-C(O)-E2-R23- group,
Wherein R22And R23Represent the alkyl with 1 to 2 carbon atom, E independently of one another respectively2Represent O or NR24And R24Respectively each other
Hydrogen atom, straight chain or branched, saturation or alkyl undersaturated, that there is 1 to 6 carbon atom are independently represented, it is optionally
By halogen atom, can have the alkyl or formula-C (O) R of 1 to 6 carbon atom25Group substitution, wherein R25Represent straight chain or
Branched, saturation or alkyl undersaturated, that there is 1 to 6 carbon atom.Preferable halogen atom is F, Cl, Br, I, especially
F and Br.
Formula (VII)（Wherein E1= O）The instantiation of compound be lactone, as α-, β-, γ-, δ-and ε-lactone and
Its halo derivatives.Wherein preferred gamma lactone, especially gamma-butyrolacton and its derivative, especially halo derivatives such as α-fluoro- γ-
Butyrolactone, α-bromo- gamma-butyrolacton, β-bromo- gamma-butyrolacton, β-fluoro- gamma-butyrolacton, γ-bromo- gamma-butyrolacton, γ-fluoro- γ-
Butyrolactone.
Formula (VII)（Wherein E1 = NR24）The example of compound be lactams, as α-, β-, γ-, δ-and ε-lactams
And its halo derivatives, N- alkyl-lactams, N- acetyl group-lactams.One particularly preferred embodiment is N- acetyl group
Caprolactam.
Formula (VII)（Wherein E1=O and R21 = –R22-C(O)-E2-R23-）Compound instantiation include second hand over
Ester and its derivative substituted by the alkyl with 1 to 6 carbon atom, especially glycolide (dimer of hydroxyacetic acid), diformazan
Base glycolide and tetramethyl glycolide.
(9) the undersaturated carboxylic acid derivates of the non-annularity of formula (VIII) are led to
(VIII)
Wherein R26Represent hydrogen, halogen atom or saturation or undersaturated, aliphatic, straight chain or it is branched, there is 1 to 12 carbon
Atom and the alkyl that can be substituted with halogen atoms or aromatics, there are 6 to 12 carbon atoms and can be substituted with halogen atoms
Alkyl, and R27Represent saturation or undersaturated, straight chain or alkyl branched, that there is 1 to 12 carbon atom, and E3Represent O
Or NR28, and R28And R27There are identical meanings independently of one another.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.
If R26Aromatic group, then R27It is preferred that saturation, straight chain or alkyl branched, that there is 1 to 6 carbon atom.If R26
Aliphatic hydrocarbyl, then R27It is preferred that represent vinyl-, pi-allyl-or propargyl.Particularly preferred formula (VII) compound is carboxylic
Acid esters, especially vinyl acetate (VA), methylchloroformate, methyl benzoate and methyl cinnamate, and carboxylic acid amide, especially N,
N- dimethyl trifluoroacetamide (DTA), DMAC N,N' dimethyl acetamide and N, N- diethyl trifluoroacetamide.
(10) formula (IXa) and (IXb) carboxylic acid anhydrides and carboxylic acid imide：
(IXa) (IXb)
Wherein E4Represent O or NR31, R29And R30Can be selected from independently of one another hydrogen atom, halogen atom and straight chain or it is branched,
Saturation or alkyl undersaturated, that there is 1 to 6 carbon atom and can optionally be substituted with halogen atoms.It is preferable at one
In embodiment, R29And R30It is connected with each other, so as to form ring.R31Represent hydrogen atom or straight chain or branched, saturation or unsaturation
, alkyl that there is 1 to 6 carbon atom.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.
The instantiation of the compound of formula (IXa) is succinic anhydride, maleic anhydride, succinimide and maleimide
Amine.The instantiation of the compound of formula (IXb) is phthalic anhydride and phthalimide.
(11) compound of formula (X)
(X)
Wherein n represents 1 to 10 integer, R32And R33Straight chain or branched, saturation or undersaturated, tool are represented independently of one another
There are the alkyl and R of 1 to 6 carbon atom34Represent methyl, ethyl, n-propyl or isopropyl.Particularly preferred four (ethylene glycol) dimethyl
Ether (TEGME).
(12) organic nitrile of formula (XI)：
R35-CN (XI)
Wherein R35Represent straight chain, saturation or it is undersaturated, there is 1 to 6 carbon atom and optionally can be by least one cyanogen
The alkyl of base substitution.Preferred embodiment is acetonitrile (AN) and adiponitrile (ADN).
(13) organophosphorus ester of formula (XII)：
(O)P(OR36)(OR37)(OR38) (XII)
Wherein R36To R38Aliphatic hydrocarbyl with 1 to 6 carbon atom is represented independently of one another or with 6 to 12 carbon atoms
Aromatic hydrocarbyl, it can optionally be substituted by one or more halogen atoms.Preferably aliphatic hydrocarbyl.These can be saturation
Or it is undersaturated.Preferable halogen atom is F, Cl, Br, I, especially F and Cl.Preferred embodiment is triallyl phosphorus
Acid esters and three (2,2,2- trifluoroethyls) phosphates (TTFP).
(14) organic boric acid ester of formula (XIII)：
Mt[B(OR39)(OR40)(OR41)(OR42)] (XIII)
Wherein Mt represents the metal cation of monovalence, preferably lithium, and R39To R42Represent that there is 1 to 6 carbon atom independently of one another
Aliphatic hydrocarbyl or aromatic hydrocarbyl with 6 to 12 carbon atoms, it can optionally be substituted by one or more halogen atoms,
Or the carbonyl with 1 to 6 carbon atom is represented, it can optionally be substituted by one or more halogen atoms.Preferable halogen
Atom is F, Cl, Br, I, especially F and Cl.Preferably, group R39To R42Each two be connected with each other, so as to form ring.It is excellent
The embodiment of choosing is double (oxalate conjunction) borates (LiBOB) of lithium and the fluoro of lithium two (oxalate conjunction) borate
(LiDFOB)。
(15) organic dialkyl dicarbonate of formula (XIV)：
(XVI)
Wherein R43And R44Straight chain or ring-type, saturation can be independently from each other or undersaturated there is 1 to 6 carbon original
The alkyl of son.Preferably saturation, there is the alkyl of 1 to 6 carbon atom.
(16) organic phosphite of formula (XVII)：
R45、R46And R47It can be selected from independently of one another：
Straight chain is branched, preferably straight chain, the alkyl of saturation or undersaturated, preferably saturation, and it has 1 to 18, and preferably 1
To 12, especially 1 to 6 carbon atom and optionally can be by halogen atom, especially fluorine atom substitutes,
Saturation or undersaturated cycloalkyl, its have 1 to 9, especially 1 to 6 carbon atom and optionally can by halogen atom,
Especially fluorine atom substitutes,
With 6 to 12, the aryl of especially 6 to 9 carbon atoms, it optionally can be by halogen atom ,-CF3- group or-
CF2CF3- group substitutes, and
Formula-SiR48 R49 R50Alkyl tin groups, alkyl silane groups, wherein R48、R49、R50Straight chain or branched can be selected from independently of one another,
It is preferred that straight chain, the alkyl of saturation or undersaturated, preferably saturation, it has 1 to 18, preferably 1 to 12, especially 1 to 6
Carbon atom.Preferred embodiment is trimethyl phosphite, triethyl phosphorite, three-n-propyl phosphite ester, three isopropyls
Base phosphite ester, three-normal-butyl phosphite ester, triisobutyl phosphite ester, three-tri, three amyl group phosphorous acid
Ester, three hexyl phosphite esters and (trimethyl silyl) phosphite ester of three (trialkylsilkl) phosphite ester such as three and three
(triethylsilyl) phosphite ester.Particularly preferred three (trimethyl silyl) phosphite esters and three (triethyl-silicanes
Base) phosphite ester.
All above-mentioned additive agent electrolytes can use individually or in combination with each other.
In above-mentioned additive agent electrolyte, particularly preferred sultone, lactone and polycyclic aromatic hydrocarbon.Here, sultone
The coat of the present invention is especially formed on the negative electrode, and lactone and polycyclic aromatic hydrocarbon form this on the positive electrode
The layer of sample.
It is to most 10 weight %, preferably 0.1 to 9 weight %, especially 0.5 to 5 weight that the electrolyte composition, which includes amount,
Measure %, such as 2 weight % at least one polymerizable additive agent electrolyte, the gross weight based on the electrolyte composition.
In addition, the electrolyte composition can contain other additive, these additives are suitable for improving its property,
As long as these additives sufficiently can be dissolved in non-polar solven, and the presence of additive can not adversely influence mentioned component
Function.Suitable additive is well known by persons skilled in the art.For example, it can be added to the electrolyte composition fire-retardant
Agent or wetting agent.
These additives concentration contained in the electrolyte composition is preferably 0 to 3 mol/L, especially 0.1 to 2
mol/L。
The present invention also aims to a kind of electrolyte composition of the liquid for hybrid super capacitor, it is included
The non-proton organic solvent of at least one liquid, at least one conducting salt and at least one polymerizable electrolyte addition
Agent, the additive agent electrolyte is when the hybrid super capacitor applies voltage just and/or on negative electrode just and/or negative
Oligomer and/or polymer architecture are formed on the surface of electrode and is consequently formed coat, the coat is in hybrid super
There is the solubility for being less than 1 g/L under the service condition of capacitor in electrolyte composition.
In a preferred embodiment, the electrolyte composition first by by each composition it is admixed together and
Prepare.Then the electrolyte composition is contacted with the electrode of hybrid super capacitor and by the hybrid super capacitor
It is charged and discharged one or many.Therefore ensure that, formed at least a portion of at least one of the electrode surface by institute
State enough layers that the oligomer of polymerizable additive agent electrolyte and/or polymer are formed.The protective layer prevents the electrode
The composition of active material and electrolyte composition or the impurity wherein contained（Such as water or acid）Later uncontrollable reaction.
Advantageously, hybrid super capacitor of the invention be applied to electric car (EV), hybrid electric vehicle (HEV) or
Plug-in hybrid electric vehicle (PHEV).Especially in recovery system（Rekuperationssystemen）In can advantageously use
The hybrid super capacitor.Other application examples are instrument and consumer electronics product.Instrument particularly relates to herein
Household appliance and garden instrument.Consumer electronics product particularly relates to mobile phone, tablet personal computer or notebook computer.
Advantages of the present invention
The hybrid super capacitor of the present invention is characterised by, by adding at least one polymerizable additive agent electrolyte,
Formed after the charging and discharging of hybrid super capacitor at least a portion of at least one of the electrode surface
The oligomer layer and/or polymeric layer being made up of polymerizable additive agent electrolyte.The protective layer prevents the electrode activity material
Expect and the composition of electrolyte composition or the impurity wherein contained（Such as water or acid）Later uncontrollable reaction.In addition, pass through
The protective layer prevents the composition of the electrode active material, and particularly transition metal ions discharges therefrom, so may
The change of active material composition and the stability problem of electrode active material layers can be caused.In addition, by the layer reduce due to
Short-circuit danger caused by being in direct contact with one another of positive electrode and negative electrode.
Brief description
Embodiment of the present invention is expanded on further by accompanying drawing and following description.
Fig. 1 schematically illustrates hybrid super capacitor.
Embodiment
Hybrid super capacitor 2 is schematically illustrated in Fig. 1.The hybrid super capacitor 2 includes capacitor case
3, the shell is configured to prismatic, is herein cuboid.The capacitor case 3 is configured to conductive herein, and for example by
Aluminium is made.The capacitor case 3 but it can also be made up of electrically insulating material, such as plastics.
The hybrid super capacitor 2 includes cathode terminal 11 and anode terminal 12.Pass through terminal 11,12
The voltage provided by hybrid super capacitor 2 can be provided.In addition, the hybrid super capacitor 2 can also lead to
Cross the charging of terminal 11,12.The terminal 11,12 is arranged in the coverage rate of prismatic capacitor case 3 at each interval
On.
Arrangement has two electrodes, i.e. negative electrode inside the capacitor case 3 of the hybrid super capacitor 2
21 and the electrode winding of positive electrode 22.The negative electrode 21 and positive electrode 22 be respectively structured as film-form and insertion every
Electrode winding is wound into the case of film 18.It is also contemplated that multiple electrodes winding is set in capacitor case 3.Instead of
Electrode winding, electrode stack (Elektrodenstapel) can also be for example set.
The negative electrode 21 includes the negative active core-shell material 41 for being configured to film-form.The negative active core-shell material 41 has
As the activated carbon (direct capacitance active material) of base-material, apply Li thereon4Ti5O12(electrochemical redox activity material
Material).The negative electrode 21 includes negative active core-shell material 41 existing for particle form.Negative active core-shell material 41 particle it
Between arrange additive, particularly conductive black and adhesive.The negative active core-shell material 41 and described additive are distinguished herein
Form the compound for being configured to film-form.
Negative electrode 21 is in addition comprising the collector 31 equally constituted as film-form.By the He of negative active core-shell material 41
The compound that the additive is formed is placed and is connected with each other with the collector 31 with facing each other.The negative electrode 21
Collector 31 be configured to conductive and be made of such as copper by metal, example.The collector 31 of the negative electrode 21 is with mixing
The cathode terminal 11 of type ultracapacitor 2 electrically connects.
The positive electrode 22 is included by activated carbon (direct capacitance active material) and LiMn herein2O4 (electrochemical oxidation
Reducing activity material) mixture form positive electrode active materials.The positive electrode 22 includes positive pole existing for particle form
Active material 42.Additive, particularly conductive black and adhesive are arranged between the particle of positive electrode active materials 42.Institute
State positive electrode active materials 42 and described additive and form the compound for being configured to film-form respectively herein.
The positive electrode 22 is in addition comprising the collector 32 equally constituted as film-form.By the positive electrode active materials
42 and the additive form compound place and be connected with each other with facing each other with the collector 32.The positive electrode
22 collector 32 is configured to conductive and is made up of metal, such as aluminium.The collector 32 of the positive electrode 22 is with mixing
The anode terminal 12 of mould assembly ultracapacitor 2 electrically connects.
The negative electrode 21 and the positive electrode 22 are separated from each other by barrier film 18.The barrier film 18 equally constitutes
For film-form.The barrier film 18 is configured to what is be electrically insulated, but ionic conductivity, that is, allow ion, particularly lithium ion
Pass through.
The capacitor case 3 of the hybrid super capacitor 2 is filled by the electrolyte composition 15 of liquid.Institute
State electrolyte composition 15 and surround negative electrode 21, positive electrode 22 and barrier film 18 herein.The electrolyte composition 15
And ionic conductivity, and the solvent comprising liquid, for example, at least a kind of cyclic carbonate (such as carbonic acid Asia second herein
Ester (EC), propylene carbonate (PC), butylene carbonate (BC)) and at least one linear carbonate (such as dimethyl carbonate
(DMC), diethyl carbonate (DEC), methyl ethyl carbonate (MEC)) mixture, and lithium salts (such as LiPF6、LiBF4)
With the 4-vinylpridine as polymerizable additive agent electrolyte.The amount of 4-vinylpridine is, for example, to be based on whole electrolyte
2 weight % of composition 15.In another embodiment, the electrolyte composition 15 is for example comprising selected from following
Additive：Double (oxalate conjunction) lithium borate (LiBOB "), biphenyl, ortho-terphenyl, bibenzyl, diphenyl ether, N- methylpyrroles, furans
Mutter, thiophene, 3,4- ethene-dioxythiophenes, vinyl acetate, pyridine-BF3- adduct, 3- fluorinated pyridines-BF3- adduct,
2- fluorinated pyridines-BF3- adduct, 3- pyridine carbonitriles-BF3- adduct, 3,4- lutidines-BF3- adduct, 4- vinyl
Pyridine-BF3- adduct, 4- trifluoromethyl pyridines-BF3- adduct, propyl- 1- alkene sultone (PES), methane-disulfonic acid methylene ester
(MMDS), three (trimethyl silyl) phosphite esters (TTSPi), triallyl phosphate (TAP) or 1,3,2- sulphur dioxides
Heterocycle pentane -2,2- dioxide (DTD).
The invention is not restricted to specific embodiments described herein and wherein prominent aspect.On the contrary, passing through right
In the range of claim provides, many changes in those skilled in the art's process range are feasible.
Claims (10)
1. hybrid super capacitor (2), it is included
- at least one negative electrode (21), it includes direct capacitance active material, electrochemical redox active material or it is mixed
Compound,
- at least one positive electrode (22), it includes direct capacitance active material, electrochemical redox active material or it is mixed
Compound,
- it is at least one be arranged between at least one negative electrode (21) and at least one positive electrode (22) every
Film (18), and
- electrolyte composition (15),
Condition is, at least one electrode (21), (22) include direct capacitance active material and at least one electrode (21),
(22) electrochemical redox active material is included,
Wherein described electrolyte composition (15) is the electrolyte composition of liquid and the non-matter comprising at least one liquid
Sub- property organic solvent, at least one conducting salt and at least one polymerizable additive agent electrolyte, the additive agent electrolyte exist
The hybrid super capacitor when applying voltage just and/or on negative electrode (22), (21) just and/or negative electrode
(22) oligomer and/or polymer architecture, are formed on the surface of (21) and is consequently formed coat, the coat is mixing
There is the solubility for being less than 1 g/L under the service condition of type ultracapacitor in electrolyte composition (15).
2. hybrid super capacitor (2) according to claim 1, wherein at least one polymerizable electrolyte
Additive is selected from following compounds (1) to (16)：
(1) carbonic ester of formula (Ia) or (Ib) acyclic and cyclic：
(Ia) (Ib)
Wherein R1And R2Can with it is identical or different and represent saturation or undersaturated, straight chain or it is branched, there is 1 to 12 carbon original
The hydrocarbon chain of son, R3Represent saturation or alkyl and R undersaturated, that there is 1 to 4 carbon atom1、R2And R3Optionally can be by halogen
Plain atom, saturation or undersaturated, straight chain or alkyl branched, that there is 1 to 6 carbon atom and can be substituted with halogen atoms
Or ring-type, saturation or alkyl substitution undersaturated, that there are 3 to 7 carbon atoms and can be substituted with halogen atoms, wherein phase
Adjacent alkyl can be connected with each other, so as to form ring；
(2) aromatic hydrocarbon polycyclic, that there is 9 to 30 carbon atoms, wherein each aromatic ring can be by selected from the miscellaneous of O, S and N
Atom is connected；
(3) aromatic compounds of the heterocycle of formula (II)：
(II)
Wherein E represents to be selected from O, S and NR8Element, R4To R7Hydrogen atom, halogen atom, cyano group, saturation or insatiable hunger are represented respectively
Sum, with 1 to 6 carbon atom and the alkyl that can be substituted with halogen atoms or saturation or it is undersaturated, with 1 to 6 carbon
Atom and the alkoxy that can be substituted with halogen atoms, wherein adjacent group R4And R5、R5And R6、R6And R7Can phase each other
Even, so as to form ring, and R8Represent hydrogen atom or saturation or undersaturated, straight chain or it is branched, have 1 to 6 carbon atom and
The alkyl that can be substituted with halogen atoms；
(4) pyridine and pyridine derivate and its boron trihalide adducts of formula (III)：
(III)
Wherein R9To R13Can be independently from each other hydrogen atom, halogen atom, saturation or undersaturated, straight chain or it is branched,
Alkyl and ring-type, saturation or alkyl undersaturated, with 3 to 12 carbon atoms with 1 to 6 carbon atom, wherein phase
Adjacent alkyl can be connected with each other, and so as to form ring, wherein X represents F, Cl or Br；
(5) sulfite of formula (IVa) and (IVb) acyclic and cyclic：
(IVa) (IVb)
Wherein R14And R15Can with it is identical or different and represent saturation or undersaturated, straight chain or it is branched, there is 1 to 6 carbon original
The hydrocarbon chain of son, and R16Represent saturation or alkyl undersaturated, that there is 1 to 4 carbon atom, wherein R14、R15And R16Optionally
Can by halogen atom, saturation or undersaturated, straight chain or it is branched, have and 1 to 6 carbon atom and can be taken by halogen atom
The alkyl in generation or ring-type, saturation or alkyl that is undersaturated, having 3 to 7 carbon atoms and can be substituted with halogen atoms take
Generation, wherein adjacent alkyl can be connected with each other, so as to form ring；
(6) formula (Va) and (Vb) sulphonic acid ester and disulfonate：
(Va) (Vb)
Wherein R17And R18Represent independently of one another straight chain or branched, saturation or it is undersaturated, there is 1 to 6 carbon atom and appoint
Selection of land can be represented independently of one another by halogen atom or the hydrocarbon chain that there is the halogenated alkane of 1 to 5 carbon atom to substitute, and m and n
1 to 5 integer；
(7) sulfuric ester of formula (VI) is led to：
(VI)
Wherein R19And R20Straight chain or branched, saturation are represented independently of one another or undersaturated there is 1 to 6 carbon atom and optionally
The hydrocarbon chain that ground can be substituted with halogen atoms；
(8) carboxylic acid derivates of the ring-type of formula (VII)：
(VII)
Wherein E1Represent O or NR24, R21Represent alkyl or formula-R with 1 to 5 carbon atom22-C(O)-E2-R23- group,
Wherein R22And R23Represent the alkyl with 1 to 2 carbon atom, E independently of one another respectively2Represent O or NR24And R24Respectively each other
Independently represent hydrogen atom, straight chain or branched, saturation or it is undersaturated, there is 1 to 6 carbon atom and optionally can be by halogen
Plain atom, the alkyl or formula-C (O) R with 1 to 6 carbon atom25Group substitution alkyl, wherein R25Represent straight chain or branch
Change, saturation or alkyl undersaturated, that there is 1 to 6 carbon atom；
(9) non-annularity, the undersaturated carboxylic acid derivates of formula (VIII) are led to
(VIII)
Wherein R26Represent hydrogen, halogen atom or saturation or undersaturated, aliphatic, straight chain or it is branched, there is 1 to 12 carbon original
Son and the alkyl that can be substituted with halogen atoms, or aromatics, there are 6 to 12 carbon atoms and can be substituted with halogen atoms
Alkyl, and R27Represent saturation or undersaturated, straight chain or alkyl branched, that there is 1 to 12 carbon atom, and E3Represent O or
NR28, and R28And R27There are identical meanings independently of one another；
(10) formula (IXa) and (IXb) carboxylic acid anhydrides and carboxylic acid imide：
(IXa) (IXb)
Wherein E4Represent O or NR31, R29And R30Hydrogen atom, halogen atom and straight chain or branched, full can be selected from independently of one another
And/or alkyl undersaturated, that there is 1 to 6 carbon atom and can optionally be substituted with halogen atoms, and R31Represent hydrogen atom
Or straight chain or branched, saturation or alkyl undersaturated, that there is 1 to 6 carbon atom；
(11) compound of formula (X)
(X)
Wherein n represents 1 to 10 integer, R32And R33Represent independently of one another straight chain or branched, saturation or it is undersaturated, have
The alkyl of 1 to 6 carbon atom, and R34Represent methyl, ethyl, n-propyl or isopropyl；
(12) organic nitrile of formula (XI)：
R35-CN (XI)
Wherein R35Represent straight chain, saturation or undersaturated there is 1 to 6 carbon atom and optionally can be by least one cyano group
Substituted alkyl；
(13) organophosphorus ester of formula (XII)：
(O)P(OR36)(OR37)(OR38) (XII)
Wherein R36To R38The aliphatic hydrocarbyl with 1 to 6 carbon atom or the virtue with 6 to 12 carbon atoms are represented independently of one another
Race's alkyl, they optionally can be substituted by one or more halogen atoms；
(14) organic boric acid ester of formula (XIII)：
Mt[B(OR39)(OR40)(OR41)(OR42)] (XIII)
Wherein Mt represents the metal cation of monovalence, preferably lithium, and R39To R42Represent that there is 1 to 6 carbon atom independently of one another
Aliphatic hydrocarbyl or aromatic hydrocarbyl with 6 to 12 carbon atoms, they optionally can be taken by one or more halogen atoms
Generation, or the carbonyl with 1 to 6 carbon atom is represented, they optionally can be substituted by one or more halogen atoms；
(15) organic dialkyl dicarbonate of formula (XIV)：
(XVI)
Wherein R43And R44Can be independently from each other straight chain or ring-type, saturation or it is undersaturated, there is 1 to 6 carbon original
The alkyl of son；
With
(16) organic phosphite of formula (XVII)：
R45、R46And R47It can be selected from independently of one another：
Straight chain or branched, saturation or it is undersaturated, there is 1 to 18 carbon atom and optionally can be by halogen atom, especially
It is the alkyl of fluorine atom substitution,
Saturation or cycloalkyl undersaturated, that there is 1 to 9 carbon atom and can optionally be substituted with halogen atoms,
And optionally can be by halogen atom ,-CF with 6 to 12 carbon atoms3- group or-CF2CF3The aryl of-group substitution,
With
Formula-SiR48 R49 R50Alkyl tin groups, alkyl silane groups, wherein R48、R49、R50Can be independently from each other straight chain or it is branched,
Saturation or alkyl undersaturated, that there is 1 to 18 carbon atom；
The compound (1) to (16) can be wherein used individually or in combination with each other.
3. hybrid super capacitor (2) according to claim 1 or 2, wherein at least one polymerizable electrolysis
Matter additive is selected from the pyridine and pyridine derivate and its boron trihalide adducts of formula (III).
4. hybrid super capacitor (2) according to claim 1 or 2, wherein at least one polymerizable electrolysis
Matter additive is selected from formula (Va) and the sulphonic acid ester and disulfonate of (Vb).
5. hybrid super capacitor (2) according to claim 1 or 2, wherein at least one polymerizable electrolysis
Matter additive is selected from the polycyclic aromatic hydrocarbon with 9 to 30 carbon atoms, wherein each aromatic ring can be by selected from O, S and N
Hetero atom be connected with each other.
6. the hybrid super capacitor (2) according to any one of claim 1 to 5, wherein at least one is polymerizable
Additive agent electrolyte to the total amount at most accounting for the electrolyte composition (15) 10 weight %.
7. the hybrid super capacitor (2) according to any one of claim 1 to 6, wherein at least one liquid
Non-proton organic solvent is selected from acetonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl Asia second
Base carbonic ester, methyl ethyl carbonate and its mixture.
8. for the electrolyte composition (15) of hybrid super capacitor (2), it includes the non-proton of at least one liquid
Property organic solvent, at least one conducting salt and at least one polymerizable additive agent electrolyte, the additive agent electrolyte is in institute
State hybrid super capacitor when applying voltage just and/or on negative electrode (22), (21) just and/or negative electrode (22),
(21) oligomer and/or polymer architecture are formed on surface and is consequently formed coat, the coat is in hybrid super
There is the solubility for being less than 1 g/L under the service condition of capacitor in electrolyte composition (15).
9. electrolyte composition (15) according to claim 8 is as the electricity in hybrid super capacitor (2)
Solve the purposes of matter composition (15).
10. purposes according to claim 9, wherein making electrolyte composition according to claim 8 (15) with mixing
Then the electrode contact of type ultracapacitor, and is charged and discharged hybrid super capacitor, so as to so that it is described extremely
A kind of few polymerizable additive agent electrolyte formed at least a portion of at least one electrode surface oligomer and/or
Polymer.
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| DE102016209609.5A DE102016209609A1 (en) | 2016-06-01 | 2016-06-01 | Hybrid supercapacitor with increased lifespan |
| DE102016209609.5 | 2016-06-01 |
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