KR20180040802A - Rechargeable battery and energy storage system using electrochemically active polymer and its manufacturing method - Google Patents

Abstract

The electro-active polymer battery according to the present invention can be applied to dramatically improve the utilization rate of electric power by using the large-capacity storage characteristic and the stable discharge characteristic of the stored power. In the present invention, since the active material must be dissolved in the electrolyte, unlike an existing secondary battery, which requires the use of two electrolytes, one electrolyte is used, so that ion diffusion does not occur and stable characteristics can be maintained even during long-term use.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a secondary battery using an electrochemically active polymer, an energy storage device, and a method of manufacturing the secondary battery, an energy storage device using the electrochemically active polymer,

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electrochemically active polymer battery that improves the performance and safety of a conventional secondary battery such as a lithium ion battery and a redox flow battery, and a method of manufacturing the same.

The present invention relates generally to the storage of electrical energy of a secondary cell using an electrochemically active polymer. The present invention relates to a secondary battery in which a collector plate made of carbon or a nickel-plated stainless steel plate is coated with an electrochemically active polymer to increase the amount of polymer to the maximum, and a separator such as an electrolyte and an anion exchange membrane. The development of lithium ion batteries played a major role in the spread of mobile phone use. The rechargeable secondary battery capable of storing electric energy which is not easy to store and recharging can be widely used in industry today but its development is slow compared to the development of electronic devices typified by semiconductors, It has not changed much in the structure originally proposed in the 1970s.

The rechargeable battery using vanadium has recently attracted attention as a large capacity secondary battery applicable to the grid system. However, due to the high cost of vanadium and the use of sulfuric acid to constitute the electrolyte, it is necessary to use a material that can withstand sulfuric acid . In addition, the pump, which circulates the electrolyte having a high acidity in the structure, is essentially required, which also increases the cost. However, the secondary battery has a low internal resistance, is easy to form a large-capacity battery, and has a long life. Therefore, it is a powerful method for increasing the efficiency of use when combined with renewable energy such as solar power generation and wind power generation. It is considered a viable way to have a coordination function.

This patent focuses on the provision of at least one electrode in a battery as a solid polymer by using a polymer having an electroactive property as an active material.

Electroactive polymers refer to redox polymer, conductive polymer and composite polymer.

references

Patent

U.S. Patent No. 4535039, Aug. 1985, Naarmann et al.

U.S. Pat. No. 4,832,869, May 1989, Cotts

U.S. Patent 5362493, November 1994 Skotheim et al.

U.S. Patent No. 7888229, Feb. 2011, Chepurnaya et al.

U.S. Patent 9325041, April 2016, Kinlen

Other

Guerfi et al., "High cycling stability of zinc-anode / conducting polymer rechargeable batteries with non-aqueous electrolyte ", 2014, Journal of Power Sources, pp. 121-126

Haupler et al., "Aqueous zinc-organic polymer battery with a high rate performance and long lifetime ", 2016, NPG Asia Materials

The present invention utilizes the concept of simultaneous redox reactions in the anode of an existing redox flow cell, in which the electrolyte acting on the charge and discharge of the battery must be separated into a liquid phase and a cathode and two circulation structures must be essential To solve the problem of using two kinds of electrolytes, it is necessary to simplify the structure of the battery by applying solids acting on the structure of the redox flow cell to one pole or both poles, simplifying the circulation structure and using only one electrolyte . As a secondary effect, it is possible to construct a closed secondary battery using only the internal electrolyte as in the case of the conventional secondary battery, so that it can be expected to be applied not only to a large energy storage device but also to a portable device.

In the present invention, as shown in Fig. 2, zinc is disposed on the anode side, polyaniline (PANI) is disposed on the cathode side, a separator is disposed therebetween, and the anode and the cathode are separated. This structure itself is the same as most secondary batteries, but there are differences in constituent materials. The material applied to each pole can be replaced by a material with similar properties. For example, Zn used as an anode active material may be replaced with another element such as iron (Fe) or an electro-active polymer. The material used on the cathode side can be ionized on its own, and it can be applied to an electrically activated polymer material which can be ionized even in the state of bonding with hydrogen. The application of PANI in the present invention is illustrated by way of example, and the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The secondary battery according to the present invention can be applied to a portable device such as a mobile phone because it can realize an enclosed battery that does not require an external tank for electrolyte storage and a circulation pump which are essential elements in existing redox polymer batteries, There is no need to be in a liquid state in order to expand the selection of the active material and there is no need for a solvent to dissolve the active material or the amount of consumption can be reduced so that the size and weight of the whole battery can be greatly reduced.

1 shows a general structure of an existing redox flow cell.
FIG. 2 is a view showing the state of the sealed zinc polymer battery according to the present invention when charging starts.
FIG. 3 is a view showing a state where the sealed zinc polymer battery according to the present invention is almost fully charged.
FIG. 4 is a view showing a state of the sealed zinc polymer battery according to the present invention when the discharge is started.
FIG. 5 illustrates a state in which the sealed zinc polymer battery according to the present invention is substantially discharged.

Hereinafter, a closed zinc polymer battery according to the present invention will be described. It is to be understood that the invention is not limited thereto and that the present invention is only defined by the scope of the appended claims.

There is provided a structure in which zinc is arranged on one side and polyaniline (PANI) is arranged on the other side, and a separator is present therebetween and an electrolyte is present therebetween.

At the start of charging, as shown in FIG. 2, Zn ²⁺ ions are mainly present in the electrolyte and H ⁺ ions are present in a trace amount. When electrons are supplied to the cathode side electrode by an external power source, Zn ²⁺ ions contained in the electrolyte bind to electrons and are reduced to metallic Zn and attached to the cathode side electrode. In order to balance the equilibrium state in the electrolyte, the hydrogen bound in the PANI is dissociated and the electrons are sent to the anode electrode and released to the electrolyte in the state of H ⁺ ions. 3, the concentration of Zn ²⁺ ions in the electrolyte is lowered and the concentration of H ⁺ ions is increased and Zn is attached to the cathode side so that Zn is attached to the cathode side electrode more than at the start of charging. When the discharge start, the Zn ²⁺ ion and Zn as shown in Fig. 4 as a separate electron and Zn ²⁺ ions are released into the electrolyte electrons move through the cathode-side electrode. The transferred electrons, like H ⁺ ions in the electrolyte, combine with PANI to form a PANI hydride.

This process is represented by the chemical reaction formula as follows.

When charging

Anode side reaction cathode side reaction

^{_{PANIH 3 → PANIH 2 + + H}} + + 2e - (C.1) Zn 2+ + 2e - → Zn (C.4)

PANIH ₂ ^{+ -} & gt ^; PANIH ²⁺ + H ⁺ + 2e ^- (C.2)

PANIH ² + ^- & gt ^; PANI ³⁺ + H ⁺ + 2e ^- (C.3)

The anode side reaction can be summarized as follows.

PANIH _{3 -} > PANI ³⁺ + 3H ⁺ + 6e ^- (C.5)

The reaction during charging is summarized as follows.

PANIH ₃ + 3Zn ²⁺ ? PANI ³⁺ + 3H ⁺ + 3Zn (C.6)

Upon discharge

Anode side cathode side

^{PANI 3+ + H + + 2e -} → PANIH 2+ (D.1) Zn → Zn 2+ + 2e _ (D.4)

PANIH ² + + H ⁺ + 2e ^- ? PANIH ₂ ⁺ (D.2)

PANIH ₃ ⁺ + H ⁺ + 2e ^- ? PANIH ₃ (D.3)

The anode side reaction can be summarized as follows.

PANI ³⁺ + 3H ⁺ + 6e ^- ? PANIH ₃ (D.5)

The overall response of the discharge is as follows.

PANI ³⁺ + 3H ⁺ + 3Zn ^- > PANIH ₃ + 3Zn ²⁺ (D.6)

In addition to the examples given above, the following schemes can be combined to form a battery.

Redox pair applicable to cathode

Cr (III) EDTA + e ^- ? Cr (II) EDTA 0.9 V

Fe ²⁺ + 2e ^- ? Fe 0.44 V

V ³⁺ + e ^- > V ²⁺ -0.26 V

S + 2e ^{- -} > S ^2- -0.48 V

^{_{PbSO 4 (s) + 2e -}} → Pb (s) + SO 4 2- -0.36 V

MV2 + (methyl viologen dication) + e ^- → MV + (methyl violen cation radical) -0.45 V

Methyl viologen polymer ²⁺ + e ^- → methyl violen polymer ⁺ -0.45 V

Redox pair applicable to anode

Polymers

PANI ³⁺ + e ^- + H ^{+ -} & gt ^; PANI ²⁺ + 1.15 V (E1 / 2)

PANI ²⁺ + e ^- + H ^{+ -} & gt ^; PANI ⁺ + 0.9 V (E1 / 2)

PANI + + e + H + - > PANI + 0.75 V (E1 / 2) PANI: Poly Aniline

Poly (TEMPO ⁺ ) + e ^- > TEMPO + 0.93 V TEMPO: 2,2,6,6-tetramethyl piperidinyl-N-oxyl

PMPy ⁺ + e ^{- -} PMPy + 0.8 V PMPy: Poly Methyl Pyrrole

Metal

Fe ³⁺ + e ^- > Fe ²⁺ 0.77 V

Fe (III) EDTA + e ^- > Fe (II) EDTA 0.12 V

Fe (III) Bipy + e ^- > Fe (II) Bipy 1.0 V

^{Fe (III) Phen + e _} → Fe (II) Phen 1.0 V

Mn ³⁺ + e ^- > Mn 2+ 1.51 V

_{^{MnO 4 - + e - → MnO}} 4 2- 0.56 V

Co ³⁺ + e ^- ? Co ²⁺ 1.92 V

Br ₂ + 2e ^{- -} > 2Br ^- 1.09 V

I2 + 2e ^- > 2I ^- 0.53 V

Ag + + e ^- > Ag 0.80 V

1. Electrolyte (V ⁴⁺ / V ⁵⁺ )
2. Electrolyte (V ²⁺ / V ³⁺ )
3. Pump
4. Membrane
5. + electrode
6. Electrodes
7. Load / Source
8. + side reaction zone
9.-side reaction zone
10. Reaction vessel
21. Positive electrode
22. Anode side active material (Poly Aniline in the embodiment)
23. Anode side electrolyte
24. Membrane
25. Cathode electrolyte
26. An anode active material (zinc metal (Zn) in the embodiment)
27. Cathode electrode
28. Reaction vessel
29. Voltage Source
30. Load

Claims (7)

The material constituting one pole of the cell can be molecularly ionized, and it can be composed of a material that can act as a molecular ion even when it absorbs cations such as hydrogen ions. When the battery discharges, it absorbs the cations in the electrolyte. Wherein the cathode and the cathode are made of materials that emit into the electrolyte and emit and absorb cations on the opposite electrode, respectively, so that oxidation and reduction reactions occur simultaneously at both electrodes without exchanging substances with the outside during charging and discharging. In the battery having the structure of claim 1, the positive electrode and the negative electrode include a cation exchange membrane, an anion exchange membrane, or a microporous membrane such as a polymer, a chisel, or a ceramic as a separation membrane, and apply an electrolyte of the same composition to the anode, And a secondary battery. The liquid electrolyte or solid electrolyte is used in claim 2, and examples of the electrolyte solution include the use of a concentration condition using a solution of 0.1 M to 30 M zinc salt, 0.1 to 1 M ammonium salt, 0.1 to 1 M boric acid, The method of using the pH of the yarn and the pH of the positive electrode chamber differently. The method according to claim 2, wherein the pH of the electrolytic solution on the anode side is lowered to the cathode side so as to smoothly control the movement of the cation. A method of using a supporting electrolyte to maintain the conductivity of the solution of claim 1 at a high level and constituting the electrolyte with a buffer solution to keep the pH constant. In claim 2, the active material on the anode side is an electrochemically active polymer having an oxidation-reduction potential and all of the following polymers such as polyaniline, polypyrrole, and imine polymer are used.
- Below -
The redox polymer in which the redox group is bonded to the chain
Poly (Tetracyanoquinodimethane) (PTCNQ)
Poly (Viologens); Poly (N, N'-alkylated bipyridines
Redox Polymers with Pendant Redox Groups (Redox Polymers with Pendant Redox Groups)
Poly (tetrathiafulvalene) (PTTF)
Quinone Polymers; Poly (vinyl-p-benzoquinone), poly (acryloyldopamine), poly
Poly (naphthoquinone), poly (anthraquinone)
Poly (vinylferrocene) (PVF or PVFc) (Organometallic Redox Polymer)
[Ru or Os (2,20 -Bipyridyl) 2 (4-Vinylpyridine) n Cl] Cl
Ion Exchange Polymers Containing Electrostatically Bound Redox Centers (Ion Exchange Polymers Containing Electrostatically Bound Redox Centers)
Perfluorinated Sulfonic Acids (Nafion ^® )
Poly (Styrene Sulfonate) (PSS)
Poly (4-vinylpyridine) (PVP, QPVP)
The electrically conductive polymer (inner conductive polymer)
Polymers from Aromatic Amines;
Polyaniline (PANI) and PANI Derivatives,
Poly (Diphenylamine) (PDPA),
Poly (2-Aminodiphenylamine) (P2ADPA),
Poly (o-Phenylenediamine) (PPD),
Poly (o-Aminophenol) (POAP),
Polyluminol (PL)
Polymers from Aromatic Heterocyclic Compounds
Polypyrrole (PP) and PP Derivatives,
Polyindole and Derivatives [618, 635-658], Polymelatonin (PM) [659], and Polyindoline,
Polycarbazoles (PCz)
Polythiophene (PT) and PT Derivatives
Polyazines; (PPh), Poly (1-Hydroxyphenazine) (PPhOH), Poly (Acridine Red) (PAR), Poly (Neutral Red) (PNR), Poly (phenosafranin) Polythiazines; Polyflavin (PFI), Poly (New Fuchsin) (PnF)
Polymers from Nonheterocyclic Aromatic Compounds < RTI ID = 0.0 >
Polyfluorene (PF), Poly (9-Fluorenone) (PFO), and Poly (9,10-Dihydrophenanthrene)
Poly (p-Phenylene) (PPP) and Poly (Phenylenevinylene) (PPPV)
Polytriphenylamine (PTPA) and Poly (4-Vinyl-Triphenylamine) (PVTPA)
Other Polymers
Polyrhodanine (PRh)
Poly (Eriochrome Black T)
Electrically Conducting Polymers with Built-In or Pendant Redox Functionalities
Poly (5-Amino-1,4-Naphthoquinone) (PANQ),
Poly (5-Amino-1-Naphthol),
Poly (4-Ferrocenylmethylidene-4H-Cyclopenta- [2,1-b; 3,4-b '] - Dithiophene),
Fullerene-Functionalized Poly (Terthiophenes) (PTTh-BB),
Poly [Iron (4- (2-Pyrrol-1-Ylethyl) -4'-Methyl-2,2'-Bipyridine) ₃ ²⁺ ]
Polypyrrole Functionalized by Ru (bpy) (CO) ₂ ,
Poly (Tetra-Substituted Porphyrins) and Poly (Tetra-Substituted Phthalocyanines)
3- {7-Oxa-8- (4-Tetrathiafulvalenyl) Octyl] -2,5-bis (3,4-ethylenedioxy) thien-2-yl] Tetrathiafulvalene (PEDOT- -2,2'-Bithiophene} (PT-TTF)
Copolymers
Poly [bis (3,4-ethylenedioxythiophene) - (4,4'-dinonyl-2,2'-bithiazole)],
Poly (Aniline-co-Diaminodiphenyl Sulfone),
Poly (Aniline-Co-2/3-Amino or 2,5-Diamino Benzenesulfonic Acid),
Poly (Aniline-co-o-Aminophenol),
Poly (m-Toluidine-co-o-Phenylenediamine),
Poly (Luminol-Aniline)
Composite Materials
Composites of polymers with carbon nanotubes and other carbon systems
Composites of polymers with metal hexacyanoferrates
Conducting polymer composites with metals
Conducting polymer and metal oxides composites
Conducting polymer-inorganic compounds composites
Polymer-polymer composites The method according to claim 6, wherein a pair of the active material of the negative electrode chamber and the positive electrode chamber is configured as follows
- Below -
Reaction Reduction Pair at Minus Poles
Zn ²⁺ + 2e = Zn -0.76 V
Cr (III) EDTA + e = Cr (II) EDTA -0.9 V
Fe ²⁺ + 2e = Fe -0.44 V
V ³⁺ + e = V ²⁺ -0.26 V
S + 2e = S ^2- = 0.48 V
_{PbS0 4 (s) + 2e =} Pb (s) + S0 4 2 - -0.36 V
MV ²⁺ (methyl viologen dication) + e = MV ^+. (methyl violen cation radical) -0.45 V
Methylviologen polymer ²⁺ + e = methylviolgen polymer ⁺ -0.45 V
Anaerobic microbe + 2e = reduced anaerobic microbe -0.30 V
Reaction Reduction Pair at the Plus Pole
Conductive polymer
PAn ³⁺ + e + H ⁺ = PAn ²⁺ to 1.15 V (E _1/2 )
PAn ²⁺ + e + H ⁺ = PAn ⁺ ~ 0.9 V (E _1/2 )
PAn ⁺ + e + H ⁺ = PAn - 0.75 V (E _1/2 )
PAn is polyaniline.
Poly (TEMPO ⁺ ) + e = TEMPO ~ 0.93 V
TEMPO is 2,2,6,6-tetramethyl piperidinyl-N-oxyl.
PMPy ⁺ + e = PMPy ~ 0.8 V
PMPy is polymethylpyrrole.
PPy + + e = PPY
Metal or metal complex redox pair
Fe ³⁺ + e = Fe ²⁺ 0.77 V
Fe (III) EDTA + e = Fe (II) EDTA 0.12 V
Fe (III) Bipy + e = Fe (II) Bipy 1.0 V
Fe (III) Phen + e = Fe (II) Phen 1.0 V
Mn ³⁺ + e = Mn ²⁺ 1.51 V
_{^{MnO 4 - + e = MnO 4}} 2- 0.56 V
Co ³⁺ + e = Co ²⁺ 1.92 V
Br ₂ + 2e = 2Br ^- 1.09 V
I ₂ + 2e = 2I ^- 0.53V
Ag ⁺ + e = Ag 0.80 V
Organic matter
Naphthalene diimmide

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