KR20160058274A - Binder comprising polymer formed by branching of block copolymer comprising poly(propylene oxide) block and poly(ethylene oxide) block - Google Patents

Abstract

The present invention relates to a binder; an electrode comprising the binder and an electrode active material; and a secondary cell and a supercapacitor, which are provided with the electrode. The binder contains a first polymer formed by branching unit blocks comprising at least one poly(propylene oxide) (PPO) block and at least one poly(ethylene oxide) (PEO) block, wherein the first polymer is formed by binding the unit blocks provided with a functional group having ends capable of being branched, the unit block being a linear block copolymer or being obtained by substituting 1,2-diaminoethane derivatives with two or more linear block copolymers.

Description

[0001] The present invention relates to a binder containing a polymer formed by linking together a block copolymer comprising a polypropylene oxide block and a polyethylene oxide block,

The present invention relates to a binder containing a first polymer formed by bonding together unit blocks each comprising at least one poly (propylene oxide) (PPO) block and a polyethylene oxide (PEO) block, , The first polymer is formed by bonding a unit block having functional groups capable of branching at each end thereof, and the unit block is a linear block copolymer containing at least one of a PPO block and a PEO block, or the linear block copolymer Is substituted for two or more of 1,2-diaminoethane derivatives, an electrode comprising the binder and the electrode active material, and a secondary battery and an ultra-high capacity capacitor having the electrode. .

Electrodes are widely used in non-rechargeable primary batteries, rechargeable secondary batteries, fuel cells, and electrical energy storage devices including capacitors. Important properties as an electrical energy storage device include energy density, power density, maximum charge / discharge rate, internal leakage current, equivalent series resistance and / or durability, i.e., ability to withstand multiple charge / discharge cycles. Dual-layer capacitors, also known as supercapacitors or supercapacitors for many reasons, have been attracting much attention in many energy storage applications due to their utility and long life, which have higher power densities than conventional rechargeable batteries.

A secondary battery, such as a rechargeable lithium ion battery, constitutes a group of batteries in which one or more charge carriers such as lithium, sodium, potassium, calcium, or magnesium ions move from the cathode to the anode while the discharge is occurring, . Rechargeable batteries are widely used in general electronic products because they produce a power output that is superior to the weight, the memory effect is negligible, and the power is slowly consumed when not in use. The secondary battery generally includes an anode, a cathode, and an electrolyte. Typically, the cathode comprises a metal current collector having a graphite-based composite layer, and the anode includes a current collector having a composite layer formed from a material containing the charge carrier species or containing a charge carrier species.

On the other hand, an ultra-high capacity battery uses an electrode immersed in an electrolyte (electrolyte) as an energy storage element. In addition, a pair of electrodes including a separation membrane (electrolyte membrane) containing an electrolyte is provided between the pair of electrodes to prevent contact between the electrodes, thereby blocking direct current flow between the electrodes and enabling ionic current to flow in both directions through the electrolyte .

Thus, in the secondary battery and the ultra-high capacity battery, an interface is formed between the electrodes and the electrolyte membrane. At this time, a binder is used to support the active catalyst on the electrode, to increase the electrochemically active surface area of the electrode, and to ensure interfacial stability between the membrane and the electrode.

One of the widely used electrode materials constituting batteries and batteries is activated carbon having a large specific surface area. However, since the activated carbon is usually present in powder form, it is necessary to form a membrane when used as an electrode material. Therefore, in order to facilitate the molding, it is prepared in the form of a slurry and coated on the substrate. In this case, it is preferable to add a binder in order to improve the bonding force and facilitate film formation.

To this end, PTFE (Teflon) has been used as a conventional binder. However, since PTFE has low electrical conductivity and poor interfacial characteristics with electrolyte, resistance of the PTFE increases, There are disadvantages.

The inventors of the present invention have found that, since they have a composition similar to that of an electrolyte, they have excellent interfacial characteristics between an electrode and an electrolyte, and have found that a polymer binder having conductivity can be unearthed. As a result, a binder containing a polymer in which linear or branched unit blocks each containing at least one of propylene oxide (PPO) block and polyethylene oxide (PEO) block are bridged through functional groups at the respective terminals, The binder is advantageous for electrode formation because it forms a network structure. The binder has higher conductivity than PTFE used in the prior art, has a chemical structure that shows excellent affinity with an electrolyte, and has excellent interfacial properties with an electrolyte membrane. It is confirmed that the performance of the battery and the capacitor having the electrode can be improved Thus completing the present invention.

In addition, the binder exhibits excellent conductivity as compared with PTFE used as a binder in chemical structure, and exhibits excellent compatibility with organic molecules used as an electrolyte. It is possible to improve the performance of the battery and the capacitor having the same.

The first aspect of the present invention includes a polypropylene oxide (PPO) block represented by the following formula (1) and a polyethylene oxide (PEO) block represented by the following formula (2) Wherein the polymer having the PEO-PPO block copolymer bound thereto is a binder containing a unit block having a functional group capable of branching at each end thereof, Wherein the unit block is a linear block copolymer comprising at least one of a PPO block and a PEO block, or the linear block copolymer is a 1,2-diaminoethane derivative (1, 2-diaminoethane derivatives having two or more substituents.

[Chemical Formula 1]

(2)

(3)

In the above formula, m and n are each independently an integer of 1 or more,

The unit block has a molecular weight of 300 to 100,000 Da.

The polyethylene oxide (PEO) is an ethylene oxide oligomer or a polymer, and is a synthetic polyether having a wide molecular weight, which is also called polyoxyethylene (POE) or poly (ethylene glycol) PEG. A substance having a weight average molecular weight of usually less than 20,000 is referred to as PEG, a substance having a higher molecular weight is referred to as PEO, and a polymer is referred to as POE regardless of molecular weight. The polymer is amphiphilic and can be dissolved in water as well as organic solvents such as methylene chloride, ethanol, toluene, acetone and chloroform. The PEO may be synthesized by reacting an ethylene oxide, which is a triangular cyclic ether containing two carbon atoms and one oxygen atom, with an ethylene glycol monomer or an oligomer, but is not limited thereto. .

The above polypropylene oxide (PPO) is a polymer of propylene oxide and a synthetic polyether having a wide molecular weight, which is also called polypropylene glycol (PPG). Generally, it has similar properties to PEO, but it shows lower hydrophilicity than PEO. The PPO may be synthesized by ring-opening polymerization of propylene oxide, which is a tri-cyclic ether substituted with a methyl group, but is not limited thereto, and commercialized PPO can be purchased and used.

In the present invention, a "block copolymer" is a copolymer in which two or more homopolymer subunits (blocks) are linked by covalent bonds, It may require an intermediate non-repeating subunit as the < RTI ID = 0.0 > The block copolymer comprising two or three distinct blocks is referred to as a diblock copolymer and a triblock copolymer, respectively.

The polymer to which the PEO-PPO block copolymer according to the present invention is bound is formed by combining a unit block having a functional group capable of branching at its terminal, that is, formed in such a manner that two or more unit blocks are bonded to one end of the unit block will be. The unit block may be a linear block copolymer including at least one of a PPO block and a PEO block. Or the above linear block copolymer may be substituted with 2 to 4 substituents on the 1,2-diaminoethane derivative represented by the above formula (3).

Preferably, the linear block copolymer comprising at least one of the PPO block and the PEO block may have the form of PEO-PPO, PEO-PPO-PEO or PPO-PEO-PPO. The linear block copolymer comprising the PEO block and the PPO block may be prepared by polymerizing PEO and PPO or may be purchased from Pluronic under the trade name of Pluronic.

On the other hand, the unit block in which the linear block copolymer is substituted with 2 or more, that is, 2 to 4, in the 1,2-diaminoethane derivatives may be synthesized by a method known in the art , And Tetronic may be purchased and used.

Preferably, the unit block may have the structure of the following formula (4) or (5), but is not limited thereto.

[Chemical Formula 4]

[Chemical Formula 5]

In this formula,

Two or more of X ₁ to X ₄ may contain a functional group capable of binding to each other.

Preferably, the unit block may contain 10 to 90% by weight of PEO. Since the PEO is a crystalline polymer, when the content of PEO exceeds 90 wt%, the ionic conductivity can be reduced due to local crystallization, and the melting point is lowered to less than 60 DEG C, so that it can not be used as a solid electrolyte at 50 DEG C or more Do. On the other hand, the addition of PPO can increase the physical strength due to the increased carbon bonds and weaken the crystallization tendency between the PEO chains, thereby exhibiting an effect of inhibiting crystallization. However, due to the relatively high hydrophobicity of PPO, compatibility with ionic electrolytes such as ionic liquids and organic electrolytes may be lowered.

In the present invention, "branch bonding" means that one molecule binds to two or more neighboring molecules. That is, the unit block according to the present invention may combine with two or more different unit blocks through the terminal thereof to form a polymer having the PEO-PPO block copolymer according to the present invention bound thereto. The polymer to which the PEO-PPO block copolymer formed through branching bonds is bound may exhibit a comical shape, a tree branch shape or a net shape depending on the degree of branching, or may be a combination thereof.

In the present invention, the term "branch bondable functional group" refers to a functional group that includes three or more reactive functional groups and is connected to the unit block through one functional group and to another unit block through two or more other functional groups. The branchable functional group is directly connected to each end of the unit block; Ether, an amide, may be connected via a linker comprising a spacing character (spacer) containing a functional group, and C _{1 -18} alkyl selected from the group consisting of urethane, ester. Further, preferably, the branch-bondable functional group may be triethoxysilane, acrylate or epoxy, but is not limited thereto.

The resin composition for the production of the binder according to the present invention may further comprise a crosslinking agent in addition to the polymer having the PEO-PPO block copolymer bound thereto. By further including the cross-linking agent, the number of branch bonds per unit polymer can be increased. Preferably, the additional cross-linking agent may be a material which causes a chemical reaction of the same kind as the branch-bondable functional group contained in the polymer to which the PEO-PPO block copolymer is bound. For example, when the functional group capable of branching of the polymer having the PEO-PPO block copolymer bound thereto is a triethoxy group, tetraethoxysilane (TEOS) capable of reacting therewith can be added as an additional crosslinking agent. Preferably, the crosslinking agent further included may be an ethoxysilane-based, acrylic-based or epoxy-based compound, but is not limited thereto.

Preferably, the polymer having the PEO-PPO block copolymer included in the binder according to the present invention has a number-average molecular weight (Mw) of 10,000 to 1,000,000 or a weight average molecular weight (Mw) of 10,000 to 10,000,000. weightaverage molecular weight).

In addition, the binder including the polymer having the PEO-PPO block copolymer according to the present invention may further include a fluorine-based polymer as a conventional binder used as a nasal binder. The fluorine-based polymer is preferably added in an amount of not more than 20% by weight based on the total weight of the binder, but is not limited thereto.

Preferably, the fluoropolymer is selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), ethylene chlorotrifluoroethylene (E-CTFE), ethylene tetrafluoroethylene tetrafluoroethylene (E-TFE), polyvinylidine fluoride (PVDF), tetrafluoroethylenehexafluoropropylene (FEP) and chlorotrifluoroethylene (CTFE), hexafluoro But is not limited to, a homopolymer, a copolymer, or a mixture of polymers of a polymer selected from the group consisting of hexafluoropropylene (HFP).

A second aspect of the present invention is a binder comprising: the binder; And an electrode active material.

A third aspect of the present invention provides a secondary battery having an electrode according to the second aspect.

A fourth aspect of the present invention provides an ultra-high capacity capacitor having an electrode according to the second aspect.

A secondary battery or secondary cell is a form of an electrical battery, also referred to as a rechargeable battery, a storage battery, and includes at least one electrochemical cell, and includes energy for electrochemical energy storage It is a form of an energy accumulator. Since the electrochemical reaction occurring in the battery is electrically reversible, it is referred to as a secondary battery. The secondary cells have a wide variety of sizes and shapes ranging from coin cells to megawatt systems connected to stabilize the power distribution network. Different combinations of compounds are widely used, including lead-acid, NiCd, NiMH, Li-ion, and Li-ion polymer have. An example of a secondary battery is a redox flow battery. Non-limiting examples of the redox flow cell include a V (IV) / V (V) redox couple as a positive electrode electrolyte and a V (II) / V (III) redox couple as a negative electrode electrolyte. Dog cell; A vanadium-based redox battery using a halogen redox couple as a cathode electrolyte and a V (II) / V (III) redox couple as a cathode electrolyte; A polysulfide bromine redox cell using a halogen redox couple as a positive electrode electrolyte and a sulfide redox couple as a negative electrode electrolyte; Or a zinc-bromine (Zn-Br) redox battery using a zinc redox couple as a cathode electrolyte and a zinc redox couple as a cathode electrolyte.

An ultra-high capacity capacitor (supercapacitor or ultracapacitor), also referred to as an electric double-layer capacitor, may be a generic term for an electrochemical capacitor. Unlike nanoscale dielectric capacitors with high capacitance values, they do not contain conventional solid dielectrics. The electrostatic capacitance value of an electrochemical capacitor is determined by the two storage principles of double layer capacitance and pseudocapacitance, which inevitably contribute to the total capacitance. The ultra-high capacity capacitor is composed of two electrodes separated by an ion permeable membrane (separator) and an electrolyte electrically connecting the two electrodes. When the electrode is polarized by applying a voltage, the ions in the electrolyte form an electric double layer of polarity opposite to the polarity of the electrode. For example, a positively polarized electrode has a layer of anions with a charge-balance layer of cations adsorbed on the negative charge layer at the electrode / electrolyte interface. When the electrode is polarized negatively, the opposite phenomenon occurs.

The electrode of the battery or capacitor may be in the form of a thin film coating comprising an electrode active material applied to the conductive metal current collector and electrically connected thereto. At this time, it is preferable that the electrode has excellent conductivity, high temperature stability, long-term chemical stability, high corrosion resistance, and surface area per unit volume and mass. Additional requirements include environmental friendliness and low cost. Above all, it is important to be able to provide a wide electrode surface area to achieve good performance. Thus, activated carbon, especially porous, spongy materials with a high specific surface area can be used. For example, by using a powder having a small particle size as an electrode active material and coating it on a collector to form a porous electrode, the electrode surface area can be dramatically increased. At this time, in the case of an active material having a low electron conductivity including a contact resistance, a resistance increases and a potential distribution occurs at the time of charging and discharging, so that the utilization ratio of the powder active material may be lowered. Therefore, a carbon material or the like may be added as a conductive material. Further, the polymer can be used as a binder (binder) for stably applying the powder.

As used herein, the term "binder" may refer to bindings, that is, materials capable of providing a bonding force, such as polymers, copolymers, and similar ultra-high molecular weight materials. These materials can be used to improve the cohesion of loosely aggregated particulate materials, that is, active fillers that perform some useful function in a particular application. For example, it can be added to the electrode active material to provide a bonding force between the electrode active material particles, thereby facilitating the formation of the electrode. Generally, the binder used for the electrode serves to fix the powdery electrode active material and / or conductive material to the current collector, for example, a metal substrate. The binder usually used is an insulator, so that the conductivity of the electrode can be reduced when the content thereof is increased.

Preferably, 2.5 to 8.8 parts by weight of the binder may be added based on 100 parts by weight of the electrode active material. When the content of the binder is less than 2.5 parts by weight, the bonding force during the production of the electrode may be low and it may be difficult to produce the sheet or film. On the other hand, if it exceeds 8.8 parts by weight, the electrical conductivity value of the electrode itself may be decreased and the performance of the battery produced therefrom may be significantly lowered.

"Active electrode material" means a material that provides or enhances the function of an electrode. For example, in a double layer capacitor electrode, the electrode active material includes particles having a high porosity.

Examples of the electrode active material include, but not limited to, activated carbon, carbon nanotube (CNT), vapor grown carbon fiber (VGCF), carbon aerogel, hydrocarbon or fluorinated hydrocarbon Carbon nanofiber (CNF), graphene, graphite, metal, metal oxide, alloy, or a mixture thereof, which is prepared by carbonizing a polymer.

The electrode of the present invention may further include a conductive material.

Non-limiting examples of the conductive material include carbon black, carbon powder, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotube, carbon nanowire, carbon nano-horn, carbon nano ring), and they may be used in combination.

Preferably, the electrode active material or the conductive material may be in a powder state.

Preferably, the electrode of the present invention is produced by cross-linking a binder precursor by treating an electrode composition containing an uncrosslinked binder precursor and an electrode active material, which are uniformly mixed, with an acidic solution, or crosslinking prepared by treating a binder precursor with an acidic solution A binder, and an electrode active material.

Preferably, the acidic solution may be a mixed solution of water, ethanol and hydrochloric acid. More preferably, the acidic solution may be a solution prepared by mixing water, ethanol and hydrochloric acid in a volume ratio of 1: 3 to 3.5: 0.1 to 0.15, but if it is a solution capable of inducing binding through a functional group capable of branch bonding, It does not.

The binder used in the electrode according to the present invention is a binder having a functional group capable of branching at each end and having a linear or branching unit block containing at least one polypropylene oxide block and a polyethylene oxide block, Since the polymer has a composition similar to that of the electrolyte, the polymer has an excellent interfacial property between the electrode and the electrolyte, and has conductivity. Accordingly, the performance of the electrode including the polymer is minimized by the addition of the binder, The resistance that can be generated at the interface can be effectively used for a secondary battery and an ultra-high capacity capacitor because it can provide a reduced excellent performance.

Preferably, the electrode may be used in the form of a membrane-electrode assembly by bonding it to a membrane containing an ion conductive polymer, or in the form of an electrode-electrolyte combination impregnated with an electrolyte solution directly on the electrode.

Since the binder according to the present invention has a network structure and is advantageous in terms of the electrode active material and chemical structure and compatibility with the electrolyte, the deterioration of the electrode performance due to the addition of the binder is minimized and the composition is the same as that of the electrolyte It is possible to reduce the resistance that may occur at the interface due to the excellent interfacial property with the electrolyte and thus it can be usefully used as a material capable of improving the disadvantages of the PTFE used as the conventional binder.

1 is a schematic view illustrating a method of synthesizing a first polymer from a bound PEO-PPO block copolymer according to the present invention.
FIG. 2 is a SEM image of a graphene electrode manufactured using a binder according to the present invention. As a control group, an electrode prepared by using Teflon (PTFE) as a binder was used.
FIG. 3 is a graph showing electrochemical characteristics of an ultra-high capacity capacitor having an electrode manufactured using the binder according to the present invention, as measured by cyclic voltammetry (CV) using an impedance.
4 is a graph showing a capacitance of a coin cell including an electrode manufactured using the binder according to the present invention.
FIG. 5 is a graph showing the results of electrochemical cell performance measurement of an electrode manufactured using the same amount of PTFE and the binder according to the present invention.
FIG. 6 is a graph showing the results of cyclic voltammetry (CV) analysis using an impedance of an ultra-high-capacity capacitor having an electrode manufactured using a binder containing a PTFE as a co-binder and a branched PEO-PPO block copolymer. , Which shows electrochemical characteristics. As a comparative example, an ultra-high capacity capacitor having an electrode prepared by using only PTFE as a binder was used.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are for further illustrating the present invention, and the scope of the present invention is not limited to these examples.

Example  1: With triethoxysilane Capped  Quad functionality tetrafunctional ) Preparation of block copolymer (unit block)

A three-necked round bottom flask was equipped with a stirrer and an oil bath was prepared and then 1 mole of a quadruplicated functional PEO-PPO block copolymer (Tetronic 90R4 and 701, Sigma-Aldrich) and (3-isocyanatopropyl) triethoxysilane (2-ethyl-hexanoate, Sigma-Aldrich) was added under nitrogen atmosphere and the reaction was carried out at 70 ° C for 1 hour . After completion of the reaction, unreacted monomers were removed by washing with chloroform, precipitated with petroleum ether (SAMCHUN P0222), and filtered. The resultant was sufficiently dried in a vacuum oven to obtain a quadrifunctional PEO-PPO block copolymer (TPL-TPEs) whose terminals were capped with triethoxysilane.

Example  2: Quadruple functionality  Block copolymers Bridged  Formed Bridged Quadruple function Block copolymer ( cTPL - TPEs )

(TPL-TPEs) prepared in Example 1 and capped with triethoxysilane were placed in a 30 ml vial, and anhydrous tetrahydrofuran (Sigma-Aldrich 401757) 4 Ml was added to dissolve and then filtered, and an acidic solution was added for a sol-gel reaction. A solution prepared by mixing water, ethanol and hydrochloric acid in a volume ratio of 1: 3.2: 0.13 was used as the acid solution for the sol-gel reaction. Through this sol-gel reaction, cross-linked quadruplicated functional PEO-PPO block copolymers (cTPL-TPEs) were obtained.

Example  3: as a binder Bridged Quadruple functionality  Block copolymer ( cTPL - TPEs ) ≪ / RTI >

According to the slurry preparation method, an electrode containing a quadrivalent functional PEO-PPO block copolymer (cTPL-TPEs) bound in a binder was prepared. Specifically, 800 mg of graphene as an electrode active material, 150 mg of carbon black as a conductive material, and 50 mg of the combined quadrupole functionalized PEO-PPO block copolymer (cTPL-TPEs) obtained from Example 2 Was cast into a slurry and coated on a current collector. After drying, the prepared electrode was cut to an appropriate size and used as an electrode of a pouch or a coin cell type secondary battery or an ultra-high capacity capacitor.

Example  4: as a binder Bridged Quadruple functionality  Block copolymer ( cTPL - TPEs ) ≪ / RTI > < RTI ID = 0.0 >

An ultra-high capacity capacitor having electrodes prepared according to Example 3 was prepared according to the coin cell manufacturing method. Specifically, the graphene electrode was cut into 14 pies using a punching tool. The polymer membrane was placed on the electrode prepared in Example 3 or 4 using the above-mentioned graphene as an active material, and the electrode prepared in Example 3 or 4 was further placed thereon and sufficiently dried in a vacuum oven to prepare a coin cell.

Example  5: Bridged Quadruple functionality  Block copolymer ( cTPL - TPEs ) And As a nose binder  Manufacture of an electrode containing PTFE and an ultra-high capacity capacitor having the electrode

(CTPL-TPEs) binder according to the present invention prepared in accordance with the above-described Example 2, except that an electrode and an electrode were prepared according to the methods described in Examples 3 and 4 above, And PTFE, which is a binder conventionally used as a nose binder, in an amount of 17.8 wt% and 2.5 wt%, respectively. At this time, the conductive material was used in an amount of 8.9 wt%.

Comparative Example  1: as a binder PTFE And an electrode containing the electrode Second employment Manufacture of Capacitor Capacitors

(CTPL-TPEs) according to the present invention as a binder, and a binder, which is generally used in place of the crosslinked quadrupole functional block copolymer (cTPL-TPEs) according to the present invention, Gt; PTFE < / RTI >

Experimental Example  1: Used as a binder in the electrode Bridged Quadruple functionality  Block copolymer ( cTPL - TPEs ) Confirm dispersion of

Sectional SEM image of the electrode prepared according to Example 2 or Comparative Example 1 was obtained, and the degree of dispersion of the crosslinked quadrupole functional block copolymer (cTPL-TPE) or PTFE used as the binder in the electrode was confirmed Respectively. As shown in FIG. 2, it was confirmed that both the electrode prepared using PTFE as a binder and the electrode prepared using cTPL-TPE as a binder were uniformly dispersed in the graphene electrode.

Experimental Example  2: as a binder Bridged Quadruple functionality PEO - PPO  An electrode comprising a block copolymer and Organic  Electrochemical Characterization of an Electrolyte Membrane and a Super Capacitor with the Electrode

In order to confirm the electrochemical characteristics of the super high capacitance capacitor of the electrode and coin cell type fabricated according to Example 4 or 5, cyclic voltammetry (CV), galvanostat and battery resistance were measured using an impedance Respectively. The cyclic current method was performed from 0V to 3.2V, and the constant current method was performed by charging to 3.2V according to the current density and discharging to 0V. The cells were fabricated using PTFE, a binder that was commercialized as a control. The results are shown in Figs. 3 to 5, respectively.

As shown in FIG. 3, it was confirmed that the electric current intensity of a capacitor including an electrode manufactured using cTPL-TPE was significantly increased as compared with an electrode manufactured by using PTFE as a binder in a cyclic voltage-current curve. That is, when charging / discharging was performed, the value of the non-discharging capacity of the battery was remarkably improved in the electrode manufactured using the binder according to the present invention. This indicates that cTPL-TPE effectively reduced the internal resistance of the electrode based on its excellent compatibility with the organic electrolyte. In addition, it was confirmed that the capacitor having the electrode manufactured using the cTPL-TEP as a binder exhibited a non-discharge capacity value about twice as high as that of the charge / discharge curve shown in FIG.

FIG. 5 shows the results of confirming the resistance in the electrode prepared by including PTFE and cTPL-TEP as a binder in the preparation of the electrode. The electrochemical capacity (electrochemical) of the electrode prepared using the same amount of PTFE and cTPL- capacitor, it was confirmed that the electrode containing cTPL-TPE shows better diffusion resistivity and ESR. This means that the cTPL-TEP, which is a binder in the electrode, is excellent in compatibility with the organic electrolyte, thereby lowering the resistance inside the electrode.

Experimental Example  3: Bridged Quadruple functionality  Block copolymer ( cTPL - TPEs ) And As a nose binder  Electrodes containing PTFE and / Organic  Electrochemical Characterization of an Electrolyte Membrane and a Super Capacitor with the Electrode

The cyclic voltammetry of an electrode manufactured using a binder containing both cTPL-TPE and PTFE as a co-binder prepared according to Example 5 and Comparative Example 1 and an electrode manufactured using only PTFE as a binder was measured And the results are shown in Fig. As shown in FIG. 6, the electric current intensity of the capacitor including the electrode further comprising PTFE as the nasal binder, that is, including both the cTPL-TPE and the PTFE, compared to the capacitor having the electrode manufactured using only PTFE (CTPL-TPE + PTFE) which further contains PTFE as a novolak binder in the binder according to the present invention is 36.5 F / g, and the ratio of the non-reactive capacity to the ratio It was confirmed that even though the content of cTPL-TPE, which is a fluoropolymer, was 18% by weight, it was increased by about 40%, indicating a significantly higher value.

Claims (19)

(PPO) block represented by the following formula (1) and a polyethylene oxide (PEO) block represented by the following formula (2) Wherein the PEO-PPO block copolymer formed is a binder containing a branched polymer,
The polymer in which the PEO-PPO block copolymer is bound is formed by bonding a unit block having functional groups capable of branching at each end thereof,
The unit block may be a linear block copolymer containing at least one of a PPO block and a PEO block, or the linear block copolymer may be a 1,2-diaminoethane derivative represented by the following general formula (3) Wherein the binder is two or more substituted:
[Chemical Formula 1]

(2)

(3)

In the above formula, m and n are each independently an integer of 1 or more,
The unit block has a molecular weight of 300 to 100,000 Da.
The method according to claim 1,
Wherein the linear block copolymer is in the form of PEO-PPO, PEO-PPO-PEO or PPO-PEO-PPO.
The method according to claim 1,
Wherein the unit block has a structure of Formula 4 or 5:
[Chemical Formula 4]

[Chemical Formula 5]

In this formula,
Two or more of X ₁ to X ₄ include a functional group capable of binding to each other.
The method according to claim 1,
Wherein the unit block comprises 10 to 90% by weight of PEO.
The method according to claim 1,
The bridgeable functional group is directly connected to the end of the unit block; The binder ether, an amide, that are linked through a linker comprising a polyurethane, character spacing (spacer) containing a functional group, and C _{1 -18} alkyl selected from the group consisting of ester.
The method according to claim 1,
Wherein the branch-linkable functional groups are selected from the group consisting of triethoxysilane, acrylate, and epoxy.
The method according to claim 1,
Wherein the first polymer has a number average molecular weight (Mn) of 10,000 to 1,000,000 or a weight average molecular weight (Mw) of 10,000 to 10,000,000.
The method according to claim 1,
Wherein the binder further comprises a fluoropolymer in an amount of not more than 20% by weight based on the total binder weight.
9. The method of claim 8,
The fluorinated polymer may be at least one selected from the group consisting of polytetrafluoroethylene (PTFE), perfluoroalkoxy (PFA), ethylene chlorotrifluoroethylene (E-CTFE), ethylene tetrafluoroethylene (TFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene hexafluoropropylene (FEP), chlorotrifluoroethylene (CTFE), hexafluoropropylene ; HFP). ≪ / RTI > The binder is a homopolymer, copolymer or polymer blend of polymers.
10. A binder according to any one of claims 1 to 9, And an electrode active material.
11. The method of claim 10,
Wherein the binder contains 2.5 to 8.8 parts by weight of a binder based on 100 parts by weight of the electrode active material.
11. The method of claim 10,
The electrode active material is prepared by carbonizing activated carbon, carbon nanotube (CNT), vapor grown carbon fiber (VGCF), carbon aerogels, hydrocarbons or fluorinated hydrocarbons Wherein the electrode is selected from the group consisting of carbon nanofibers (CNF), graphene, graphite, metals, metal oxides, alloys, and mixtures thereof.
11. The method of claim 10,
And further comprising a conductive material.
14. The method of claim 13,
The conductive material may be carbon black, carbon powder, acetylene black, activated carbon, carbon fiber, fullerene, carbon nanotube, carbon nanowire, carbon nano-horn, carbon nano ring, ≪ / RTI > and mixtures thereof.
11. The method of claim 10,
The electrode may be prepared by crosslinking a binder precursor by treating an electrode composition containing an uncrosslinked binder precursor and an electrode active material with an acidic solution uniformly mixed or a crosslinked binder prepared by treating the binder precursor with an acidic solution and an electrode Wherein the electrode composition is prepared from an electrode composition comprising an active material.
16. The method of claim 15,
Wherein the acid solution is a mixed solution of water, ethanol and hydrochloric acid.
17. The method according to claim 10 or 16,
Wherein the electrode active material or the conductive material is in a powder state.
A secondary battery comprising the electrode according to claim 10.
An ultra-high capacity capacitor having the electrode according to claim 10.

Images