JPS6065477A - Battery - Google Patents

Abstract

PURPOSE:To form a battery having the high cell voltage and energy density by doping conductive polymer compounds with an electron receiving dopant and an electron giving dopant respectively for making them into the positive pole and negative pole active materials. CONSTITUTION:A conductive polymer compound such as polythiophene or the like obtainable from a monomer feasible for electrochemical polymerization is doped with an electron receiving dopant for making it into a positive pole active material. Further, an electron said conductive polymer compound is doped with giving dopant for making it into a negative pole active material. Said both active materials are used to assemble a secondary battery or the like. Said battery has the excellent discharge properties as well as the enormous density of the maximum output.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a battery in which both the positive electrode and negative electrode active materials are made of conductive polymer materials, and more specifically, bo1j thiophene, polypyrrole, polyphenylene sulfide,
The positive electrode active material is a conductive polymer compound obtained from an electrochemically polymerizable monomer such as polybilinopyridine, poly7rane, or polyselenophene, and is doped with an electron-accepting dopant. 7oid, polybilinoviridine,
The present invention relates to a battery characterized in that the negative electrode active material is a conductive polymer compound obtained from an electrochemically polymerizable monomer such as polyfuran or polyselenophene, doped with an electron-donating dopant.

Recently, a variety of batteries have been proposed in which a conductive polymer material such as polyacetylene doped with an electron-accepting dopant is used as the positive electrode active material and a metal such as lithium is used as the negative electrode active material. A battery has also been proposed in which a donor doped matrix is used and both the positive and negative active materials are made of conductive polymer materials (Japanese Patent Laid-Open No. 56-52868.56).
-71277°58-54553.58-54554.
58-54567, 56-]361169 ■).

The present inventors have also conducted intensive research into secondary batteries with excellent properties in which both the positive and negative electrode surface active materials are conductive materials. Phenylene sulfoid, polypyrinobiridine, No.? Conductive polymer compounds obtained from monomers that can be electrochemically polymerized such as polyselenophene and polyselenophene have good properties as electrode materials for batteries, and these polymer compounds can be used as electron-accepting dopants and electron-donating We found that when a battery is constructed using dopants doped as the positive electrode active material Jfi and the negative electrode active material, the cell voltage and energy density are high, and the maximum output density is extremely large ↑ + q cell q4t,
The present invention will be explained in detail below, which constitutes the present invention.

As described above, one cell according to the present invention uses a cathode active material obtained by doping a conductive polymer compound obtained from monomers that can be electrochemically polymerized with an electron-accepting dopant, and is electrochemically polymerizable. The negative electrode active material is a conductive polymer compound obtained from Monomo, which is doped with electron-donating bepan-14.As a result, it has a high cell voltage and an extremely high energy density. It is possible to obtain a plastic secondary battery with a large output U (power).

Here, as a conductive polymer compound obtained from an electrochemically polymerizable monomer, polythiophene (poly-2,
5-chenylene), polypyrrole (poly-2,5-pyrrole), poly p-phenylene sulfoid% poly-m
Examples include -phenylene sulfide, polybilinobilinone, polyfuran, polyselenophene, etc. Among these, polythiophene is particularly preferably used.

It is preferable to use these polymer compounds produced by electrochemical hybridization, but they are not necessarily limited to -(-), 1, for example, polyphenylene sulfide or polypyrinobinol. For lysine etc., it is possible to use one polymerized by other methods.1.When using a conductive polymer compound in the present invention, 10-
50-5S' or above, special K 1 (J-"8crn-'
It is preferable to exhibit the above conductivity.

Further, the electron-accepting dopant to be doped into the polymer compound is any one that can extract electrons from the conductive polymer material at the positive electrode and impart initiative to the metal conductor. For example, F2,
C12, Br2, I2. ICl, 1c13゜lB
r,' HaC7 species such as lF5, PF"s + A"
F5 + SbF+ + BF3 +BC4+ BBr
3+ FeCIJs r 'A11(-11s r Z
r C14+ Lewis acids such as SOs, HF, HCl
, HBr, HBF4. HCl0. , R2804
1FSO1H, C1803H,'CF3803)i
, 1 (protonic acids such as NOs, etc. 02 , X
eOF4, XeF2 r AgC1 (J4+kBF
< etc. or these anions can be mentioned.

Furthermore, the electron-donating dopant may be any substance that imparts η to the conductive polymer substance at the negative electrode, imparts electrical conductivity, and carves metallic conductivity.
For example, alkali metals such as Li, Na, K, Rb, and Cs, tetraalkyl ammonia A (R4
N+), tetraphenylphosphonium.

In the present invention, the method for doping the donocent may be either a chemical method or an electrochemical method.

In the battery of the present invention, a supporting force, fIl', may be used, and the dissolving agent in the supporting cylinder 1 may be a liquid electrolyte or a solid electrolyte, and examples thereof include water or an organic compound such as biphenyl, tetrahydrofuran, propion carbonate,
Examples include acetonitrile, benzonitrile, L)MF, birinone, and nitrobenzene.

The electrochemical component of the battery according to the present invention is, for example, polythiophene (Cs H2S)
The positive electrode dopant was BF4- using an acetolyl solution containing tetra-n-butylammonium fluorate (TEA'BF'4-) as an electrolyte.
1. Taking as an example the case where TBA+ is used as the negative electrode dopant, the principle is as follows.

Positive electrode (C4112S)X -xye-xy BIi'4
- Burden [2 (C, h,,S)X + xye -→-XyTBA
-' Here, an example of the structure of the battery of the present invention is shown in FIG. That is, in FIG. 1, l is a glass tube, 2 is a collector electrode, 3 is a conductive polymer compound, 4 is a separator, 5 and 6 are lead wires, and the glass tube l
The open end (A, glass seal 7) is made, and the inside of the glass tube 1 is filled with electricity 1'l'fi'?'l. 4. Of course, the configuration of the uninvented battery is limited to that shown in the drawings. In the present invention, as the active material of the positive electrode, a polymer compound such as ``double borinaophene'' doped with a deuteron-accepting dopant is not used, but in this case, a thin film of the positive electrode active material is A conductive material plate, such as a platinum plate or a Ni-Nkel plate, is formed or a thin film is peeled off to make it conductive.

It is preferable to use the positive electrode as a collector electrode material, either by placing it on a plate or by applying a conductive material or coating it with stripes or by vapor deposition.The negative electrode may also be a conductive material plate formed with a thin film of negative electrode active material, or the same as the positive electrode. It is preferable that the configuration is as follows.

In this case, the depth of the thin film of the positive and negative electrode active materials is not necessarily limited, but from the viewpoint of increasing the capacity for output cans,
It is preferable that the thickness is from μm to 2000 μm. In addition, it is preferable that the thin films of the positive and negative electrode active materials are arranged to face each other, and in this case, the distance between them can be changed in various ways, but from the viewpoint of reducing internal resistance, it is 10 μm to 1000 μm.
force) is preferred. It is clear that the present invention is not limited to glass cells, cells, bilaters, etc.

Note that the N film of the polymer compound can be obtained by electrochemical polymerization. For example, to obtain a polythiophene thin film, a conductive material such as conductive glass, platinum, or nickel is used for the positive electrode, and the same material as the positive electrode is used for the negative electrode. By doing so, a polythiophene # film can be formed on the positive electrode.

In this case, this polythiophene thin film can be easily peeled off by forming it on a conductive plate or the like.
It is doped with an anion such as 4-, or it can be electrochemically undoped, or an andso thin film can be obtained by immersing it in ammonia gas or aqueous ammonia for several hours.

Hereinafter, the present invention will be specifically explained by showing examples.
The present invention is not limited to the first embodiment.

[Example of actual distribution]

Using platinum as a negative electrode, using 1×2 cIl ln-811 oxide conductive glass plate (IT(J) as a positive electrode, 0.4 mol/l thiophene and 0.5 mol
A current of IU ~ 20 V, 101 ηA ~ was applied to a benzonitrile solution containing /lL i BF4 in an argon gas atmosphere to electrochemically polymerize thiophene and deposit a polythiophene film of about 0.75 μm on the positive electrode. .

This film exhibits a conductivity of 106106s' (290°K) when 30 to 50 mo1% of BF,- is added.

The film was then immediately AND-70'd by shorting it in the same electrolyte for a few minutes.

In this way, the and-
Two shiborithiophine films were placed in a glass cell with a gap of about 1 cIrLN [about 0.2rnol/l tetra-n-butylammonium fluoropolymer] (
The sample was immersed in 15 cc of a solution of TEABF4) containing attenutonite 1norca). Next, when a pressure of 2.1 cm or more was applied, the charging current rt % Mll
ML It' (The color of one missing file changes from red to blue, each direction is 1 row 1') -f-, t7xn7i/
It was confirmed that the l/me was reduced by TBA+ and Bk"%-k.

The electrochemical reaction during the charging stage of the battery is as follows.

At the negative electrode (C, H2S)
H2s)-yTBA+y] At the positive electrode (C4H2S)X-xye-+xyBFt-→[(C,
H2S) + 3' (BF4-)y)
A-Rework Also, the above-mentioned reverse reaction occurs during the discharge stage.

In addition, it was confirmed by absorption measurement and elemental analysis that the polythiophene was doped with p-type and n-type.

Next, using the above-mentioned battery, after charging at a constant voltage, the cell potential was immediately measured (after 2 to 3 seconds), and the relationship between the cell potential and the concentration of each dome was investigated. The result is 1-0 as shown in Figure 2. Note that the dopant concentration is 1-0 when the load resistance is 1-0.
Evaluation was made from the total nayaso when discharged at 0Ω.

From the curve shown in Figure 2, the energy density is 1kg of electrode active material (both films and TBABF424rno1%)
75Wh for each film, 7 to 11 for 1 kg of both films
It was calculated to be 0wh.

Further, the discharge characteristics, ie, the relationship between discharge voltage and time at various resistance values, were investigated, and the results shown in FIG. 3 were obtained. In this case, the cell used was an i51i24mo1% film charged at 3.2cm for 2 minutes using an i5107 film with a total area of about 0.13 m9 for both the positive and negative electrodes.

From the curve in Figure 3, the total discharge charge bar 1 is the dopant concentration 2
A constant of approximately 36 mC was calculated, corresponding to 4 ma1%.

Also, when the voltage due to the internal resistance] is ignored compared to the cell voltage? From the discharge curve at a load resistance of Ω or more, the energy density is approximately 9 for 1 kg of both films.
It was introduced that it is 3Wh. In this case, the electrode active materials (both films and 24 mai 1% TBABF4)
The energy density for 1 k3i is 63 Wb, which is the average radiation i! 24 A at tolerance pressure 2.7v
Corresponds to 9 to h/.

Further, from the emission 1T curve at a small resistance value of 100Ω shown in FIG. 3, it was observed that the maximum power density was 89 KW/9 and 61 KW/9 for the film and electrode active material, respectively. In this case, when a battery was used in which each thickness of both films was about 0.2 μm, a maximum output density of 300 KW/kli1 or more was obtained for the electrode active material. The maximum power density of (CH)x/Li battery is 35 K
W/kg, (CH)x/ (C)l)x Maximum output sound 19 of current is l 7 KW/kl? Therefore, the maximum power density of the battery of the present invention is more than 20 times the lightning power density of the (CH) x/ (CH) x battery, and the maximum power density of the lead battery is 1.2 KW/kg. It was found that the maximum power density of the battery of the present invention was significantly higher.

The reason why the maximum output density of the battery of the present invention is so large is that the polythiophene film is porous and has a very large surface area, and that the diffusion coefficient of the donor into the film is large.

In addition, the battery of the present invention had a sufficiently long life as long as the charging voltage was 3.2 V or less.

From the above, it can be seen that polythiophene has a cell voltage of 3.0 at a dopant concentration of 24 mo/%. IV, an energy density of 110 Wh/9 and a maximum output density of 300 KW/9 or more.

[Brief explanation of drawings]

FIG. 1 is a cross-sectional view showing an example of the structure of the battery of the present invention, and FIG. 2 is a cross-sectional view of a cell included in the polythiophene/TBABB''4/a7tonitri/I//polythiophene battery of the present invention.
, Graph showing the relationship between EE and dopant concentration, 3rd
The figure shows the same battery (dopant concentration 1!,!'24 mo7%)
) is a graph showing the discharge characteristics of the battery. DESCRIPTION OF SYMBOLS 1...Crow tube, 2...Collecting electrode, 3-way exclusive polymer compound, 5.6...Lead wire, 8...IQγ
agent. Applicant Kei Kinfuji - Katsumi Yoshino Agent Patent attorney ratio Takashi Shima Dopant concentration (mo1%) Figure 3 11+j interval (seconds)

Claims (1)

[Claims] 1. A conductive polymer compound obtained from a monomer that can be electrochemically polymerized and doped with an electron-accepting dopant is used as a positive electrode active material, and a conductive polymer compound obtained from a monomer that can be semipolymerized by lightning or vaporization is used as a positive electrode active material. 1. A battery characterized in that a negative electrode active material is a polymer compound doped with a lightning or child dopant. 2. The battery according to claim 1, wherein the conductive polymer compound is selected from polythiophene, polypyrrole, polyphenylene sulfide, polybilinoviridine, poly7rane, and polyselenophene.