CN107033348A - Colelctor electrode is coated with ultracapacitor of conducting oligomers or polymer and preparation method thereof - Google Patents

Colelctor electrode is coated with ultracapacitor of conducting oligomers or polymer and preparation method thereof Download PDF

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Publication number
CN107033348A
CN107033348A CN201610912860.1A CN201610912860A CN107033348A CN 107033348 A CN107033348 A CN 107033348A CN 201610912860 A CN201610912860 A CN 201610912860A CN 107033348 A CN107033348 A CN 107033348A
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polymer
colelctor electrode
conducting
ultracapacitor
conducting oligomers
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P.弗马
T.瓦格纳
M.维德迈尔
E.比勒
F.戈尔克斯
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Robert Bosch GmbH
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Robert Bosch GmbH
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Abstract

Ultracapacitor of conducting oligomers or polymer and preparation method thereof is scribbled the present invention relates to colelctor electrode.It is related to following formula conducting oligomers or polymer：, wherein R1It is selected from Or its mixture, R2Selected from P (O) (OH)2、AlCl2、SiCl3With its mixture, R3、R4、R5And R6It is independently selected from H and CxH2x+1, x is in the range of 1 to 20, and n is at least 100.Colelctor electrode (10) is further related to, it has metal level (11), it scribbles conducting oligomers or the monolayer (13) of polymer.Prepared in the solution that the colelctor electrode can be by the way that metal level (11) to be immersed to the conducting oligomers or polymer.Multiple colelctor electrodes (10) form ultracapacitor (30) together with multiple electrodes (20).Monolayer (13) of each colelctor electrode (10) through the conducting oligomers or polymer makes electrical contact with least one electrode (20) herein.

Description

Colelctor electrode is coated with ultracapacitor and its preparation of conducting oligomers or polymer Method
Technical field
The present invention relates to conducting oligomers or polymer and its its preparation method.It is conductive oligomeric the invention further relates to be coated with Colelctor electrode of thing or polymer and preparation method thereof.It is last that the present invention relates to the ultracapacitor for including the colelctor electrode.
Background technology
Ultracapacitor can provide the high power density more than 10 kW/kg, but only have limited less than 10 Wh/kg Energy density.Hybrid super capacitor (HSC), as such as lithium-ion capacitor is ultracapacitor of new generation, it has Gao Gong Rate density and with the energy density higher than conventional Super capacitor.
The power of hybrid super capacitor depends primarily on its equivalent series resistance (Equivalent Series Resistance - ESR).Equivalent series resistance is the complex combination of multiple single resistance, as the intrinsic electricity of such as electrode material Contact resistance between resistance, the ion resistance of electrolyte and electrode and colelctor electrode（Also referred to as collector）.The contact resistance It can be modified to reduce by targetedly colelctor electrode surface.
The content of the invention
The conducting polymer has following formula：,
In this group R1It is selected from Or Their mixture.This is the construction unit that the conducting polymer is assigned when being doped.Here, conducting polymer is interpreted as Such a polymer, it especially has at least 10 in the undoped state-6 S/m intrinsic conductivity and doping shape Have at least 10 under state3 S/m electrical conductivity.The doping of conducting polymer can be by the chemistry or electrochemistry oxygen of the conducting polymer Change or also original progress.
Group R2Selected from P (O) (OH)2、AlC12、SiCl3With their mixture, wherein R3、R4、R5And R6Independently of each other Selected from H and CxH2x+lAnd x is in the range of 1 to 20.The group can make the conduction together with its terminal hydroxy group and/or chlorine atom Polymer is attached on the metal surface of the oxidation with hydroxyl.
N is at least 100.The compound can be manufactured as oligomer or polymer by this.
It can be covalently bound to by the conducting oligomers or polymer on the metal surface of oxidation, it is adapted to provide in collection The company having than smaller contact resistance in conventional surface processing method (ü bergangswiderstand) between electrode and electrode Connect.
Conducting oligomers or preparing for polymer can be carried out by the oxidisability oligomerization or polymerisation of material.It is described Material is selected from Or they Mixture, wherein X=H.After the predeterminable time terminates, X=R is added to reactant mixture2Same substance.It is described Second material is used as oligomerization or chain terminating agent in polymerisation at this and drawn at this into the oligomer or polymer Enter group R2, it can be used as the anchoring group on contacting metal surface.
The colelctor electrode has metal level, and it is coated with the conducting oligomers or the monolayer of polymer.The unimolecule Layer is preferably configured to self assembled monolayer (Self Assembled Monolayer-SAM), so that colelctor electrode can pass through letter Singly make metal level with conducting oligomers or polymer contact to obtain, and consistently form the electricity for ultracapacitor herein Optimal monolayer for the contact of pole.The formation of the layer of multilayer will cause the contact electrode between colelctor electrode and electrode to become Difference.In addition, the weight and volume and traditional current collection with thick carbon coating of colelctor electrode can be made by forming only monomolecular layer Pole is compared to reduction.
Preferably, metal level has metal oxide layer in its surface, and it causes the conducting oligomers or polymer Can be by anchoring group and oxide skin(coating) covalent bond.Therefore, the anchoring group preferably has at least one hydroxyl.The hydroxyl Covalent bond or and AlC1 can be formed in the case of elimination of water with the hydroxyl of metal oxide layer2- or SiCl3- group is being eliminated Covalent bond is formed in the case of HCl.
It is particularly preferred that the metal level is especially made up of aluminium with the aluminium of aluminum foam or aluminium foil form.This is super capacitor Conventional collector material in device, especially hybrid super capacitor.Aluminium has advantages below as the material of metal level, i.e., its The metal oxide layer being made up of aluminum oxide, the metal oxide layer facile hydrolysis, so that itself and the conduction are just formed in air The anchoring group sound response of oligomer or polymer.
Even when substantially various conducting oligomers or polymer can be used in the coating for colelctor electrode, but especially examine Consider the coating by conducting oligomers of the present invention or polymer.
In order to prepare the colelctor electrode, in the solution that metal level can be immersed to the conducting oligomers or conjunction polymers.Here, According to the reactivity of anchoring group and metal oxide layer the conducting oligomers or polymer can be made to be covalently bound to colelctor electrode On surface, other reactions steps are not needed to this.
Especially suitable solvent for these solution is chloroform, acetonitrile, toluene, dimethyl sulfoxide and hexamethylene.
Ultracapacitor, it is particularly hybrid super capacitor, with multiple electrodes and multiple colelctor electrodes.Each colelctor electrode Monolayer through the conducting oligomers or polymer contacts at least one electrode.When conducting oligomers or polymer are this hair When bright conducting oligomers or polymer, then at least one of the monolayer preferably through the conducting oligomers or polymer is made electrical contact with Individual group R1 is realized.Here, electronics can pass through conducting polymer owner from covalent bond of the metal through anchoring group of colelctor electrode Chain is spilt out, and is delivered to therefrom in electrode material.Thus it can make between colelctor electrode and the electrode for contacting the colelctor electrode Contact resistance is significantly reduced.
If ultracapacitor is fabricated to hybrid super capacitor, it includes electrolyte.The electrolyte is that at least one is led Solution of the electric salt at least one solvent.The conducting salt is especially selected from LiClO4、LiBF4、LiPF6、LiAsF6、LiSO3CF3、 LiN(SO2CF3)2、LiN(SO2C2F5)2、LiB(C2O4)2、LiBF2(C2O4)、LiPF3(CF3CF2)3、N(CH4)4BF4With they Mixture.
The solvent not reacted as the enough solubility for ensuring the conducting salt and with the material of negative electrode and anode, especially It is suitable selected from following solvent：Acetonitrile, propylene carbonate, ethylene carbonate, dimethyl carbonate, diethyl carbonate, carbonic acid first Base ethyl ester and their mixture.
The hybrid super capacitor can be prepared in the following manner, wherein providing has multiple electrodes and multiple present invention The hybrid super capacitor of colelctor electrode, so that each colelctor electrode makes electrical contact with least through conducting oligomers or the monolayer of polymer One electrode.Here, by the way that ultracapacitor is charged, conducting oligomers or polymer to the colelctor electrode are doped.
Brief description of the drawings
Embodiments of the invention are shown in the drawings and are expanded on further in the following description.
Fig. 1 shows the synthesis of conducting polymer according to embodiments of the present invention in reaction icon.
Fig. 2 schematically shows colelctor electrode and electrode in ultracapacitor according to embodiments of the present invention.
Embodiments of the invention
1,4 g iron chloride (lIl) are dissolved in the M hydrochloric acid of 50 ml 1 in a nitrogen atmosphere.Add 1.2 thereto after 30 minutes Ml pyrroles.According to Fig. 1, pyrroles's molecule forms polymer chain I in oxidative polymerization reaction.Added after other 15 minutes 0.1 ml it is same figure 1 illustrates compound II.The reaction of two kinds of compounds I and II cause the chain termination of polymerisation Reaction, it is produced with the group R as anchoring group2Conducting polymer III.During whole synthesis, temperature maintains 0 ℃.Hereafter the solid of generation is filtered out and with methanol and then being washed several times with acetone.Final product then exists in a vacuum Dried 12 hours at 40 DEG C.The final product is obtained with 20% yield, and its number-average molecular weight is 32537 g/mol, this correspondence 500 n values.
In order to prepare colelctor electrode 10 according to an embodiment of the invention, 1 g conducting polymers are dissolved in 1 ml chlorine In imitative.Aluminium foil is immersed as metal level 11 in the solution of the conducting polymer.The aluminium foil is set to retain 20 in the solution at room temperature Minute simultaneously then takes out from solution, with chloroform, finally dries.The aluminium foil has what is be made up of aluminum oxide in its surface Metal oxide layer 12.The hydroxyl of the hydroxyl of the metal oxide layer 12 in the solution in the case of hydrolysis with anchoring group A Reaction, so that conducting polymer III is covalently bound on metal oxide layer 12 and is formed on monolayer 13.This Schematically shown in Fig. 2, wherein being merely displayed in the coating on the side of metal level 11.But in fact, all sides of metal level 11 Face is all coated.The electrode 20 that graphite for example lithium ion doped in this situation can now constituted is contacted with colelctor electrode 10, So that the surface contact conducting polymer III of electrode 20 main polymer chain, so that through monolayer 13 in colelctor electrode 10 Simple charge-exchange can be carried out between electrode 20.It is described in this embodiment to be made up of colelctor electrode 10 and electrode 20 It is for a pair the part of ultracapacitor 30, the ultracapacitor is fabricated to lithium-ion capacitor and to be consequently belonging to mixing super Level capacitor.It includes LiClO4The 1 M solution in the mixture of ethylene carbonate and dimethyl carbonate is used as electrolyte.With Hitherto known lithium-ion capacitor is compared, and it is provided due to the smaller sheet resistance between colelctor electrode 10 and electrode 20 Higher power.
In the case of the initial charge of lithium-ion capacitor, conducting polymer is not only carried out also on negative electrode on anode III electrochemical doping.Thus the initial low intrinsic conductivity of the polymer is made to improve to about 104S/m.Here, in anode The upper following oxidation for occurring conducting polymer III：
In addition, conducting polymer III following reduction occurs on negative electrode：
This two reactions are reversible, so as to which the hybrid super capacitor can be used as rechargeable electrochemical cell.

Claims (12)

1. the conducting oligomers or polymer of following formula：
Wherein RlIt is selected from Or Their mixture, wherein R2Selected from P (O) (OH)2、AlC12、SiC13With their mixture, wherein R3、R4、R5And R6Mutually Independently selected from H and CxH2x+lAnd wherein x is in the range of 1 to 20, and n is at least 100.
2. conducting oligomers according to claim 1 or the method for polymer are prepared, wherein the oxidisability for carrying out material is oligomeric anti- Answer or polymerisation, the material is selected from Or Their mixture, wherein X=H, and wherein after the predeterminable time terminates, X=R is added to reactant mixture2It is same One material.
3. colelctor electrode (10), it has metal level (11), and the metal level is coated with the unimolecule of conducting oligomers or polymer Layer (13).
4. colelctor electrode (10) according to claim 3, it is characterised in that the metal level (11) has metal oxygen in its surface Compound layer (12), and the conducting oligomers or polymer are by anchoring group (R2) and the oxide skin(coating) covalent bond.
5. colelctor electrode (10) according to claim 4, it is characterised in that the metal level (11) is made up of and the metal aluminium Oxide skin(coating) (12) includes aluminum oxide.
6. according to the colelctor electrode (10) of any one of claim 3 to 5, it is characterised in that the conducting oligomers or polymer For the conducting oligomers or polymer according to claim 1.
7. the method for the colelctor electrode (10) according to any one of claim 3 to 6 is prepared, wherein the metal level (11) is immersed In the solution of the conducting oligomers or polymer.
8. ultracapacitor (30), it has multiple electrodes (20) and multiple colelctor electrodes according to any one of claim 3 to 6 (10), wherein monolayer (13) of each colelctor electrode (10) through the conducting oligomers or polymer makes electrical contact with least one electricity Pole (20).
9. ultracapacitor (30), it has multiple electrodes (20) and multiple colelctor electrodes according to claim 6 (10), wherein often At least one group R of monolayer (13) of the individual colelctor electrode (10) through the conducting oligomers or polymer1Electrical contact is at least One electrode (20).
10. ultracapacitor (30) according to claim 9, it is characterised in that it is hybrid super capacitor.
11. ultracapacitor (30) according to claim 10, it is characterised in that it includes the electrolyte with conducting salt, institute State conducting salt and be selected from LiClO4、LiBF4、LiPF6、LiAsF6、LiSO3CF3、LiN(SO2CF3)2、LiN(SO2C2F5)2、LiB (C2O4)2、LiBF2(C2O4)、LiPF3(CF3CF2)3、N(CH4)4BF4With their mixture.
12. prepare the method for the ultracapacitor (30) according to claim 10 or 11, it is characterised in that providing has multiple electricity Pole (20) and the hybrid super capacitor of multiple colelctor electrodes (10) according to any one of claim 3 to 6, so that each current collection Monolayer (13) of the pole (10) through the conducting oligomers or polymer makes electrical contact with least one electrode (20), wherein by inciting somebody to action Ultracapacitor (30) is charged, and conducting oligomers or polymer to colelctor electrode (10) are doped.
CN201610912860.1A 2015-10-21 2016-10-20 Colelctor electrode is coated with ultracapacitor of conducting oligomers or polymer and preparation method thereof Pending CN107033348A (en)

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