JPH01172382A - Charge-transfer complex of fulvalene derivative with iodine - Google Patents

Abstract

NEW MATERIAL:A charge-transfer compelx, expressed by formula I (X1-X8 are sulfur, selenium or tellurium; R1-R4 are 3-10C alkyl, 6-20C aryl, etc., having secondary or tertiary carbon atom) and/or formula II (A1-A4 are H, Cl, alkyl, or I; m1 and m2 are integers of 3-10; n is 2-100) and consisting of 2-15mol. iodine based on 1mol. fulvalene derivative having partially or wholly crosslinked carbon atoms. USE:An active material of positive poles in solid electrolytic cells or batteries. PREPARATION:For example, lumps of sodium are added in small portions to ice-cold methanol and bis(carbonyldithio)tetrathiafulvalene is added thereto and reacted. Benzyl bromide is then dripped and reacted therewith to provide tetrathiabenzyltetrathiafulvalene, which is subsequently mixed with iodine and heated to afford the aimed charge-transfer complex of the fulvalene derivative with the iodine.

Description

DETAILED DESCRIPTION OF THE INVENTION L11 31 1 The present invention provides a method of combining fullvalene derivatives and iodine, which are useful as positive electrode active materials of solid electrolyte batteries using light metals such as lithium, sodium, aluminum, and magnesium as negative electrode active materials. Concerning charge transfer complexes.

Solid electrolyte batteries have the advantage of not having to worry about liquid leakage because the positive electrode active material, negative electrode active material, and electrolyte are all solid, and they can be easily made into thin batteries. It is used as a power source for cardiac pacemakers and as a memory backup power source for computers, and its usage technology and applications are also expanding.

Iodine is used as a positive electrode active material, and as a negative electrode active material, for example,
In batteries using lithium, iI generated at the interface between the positive electrode and the negative electrode by the reaction between lithium and iodine serves as a solid electrolyte. However, iodine has low electrical conductivity,
If iodine is used as it is as a positive electrode, the internal resistance of the battery will increase significantly. Therefore, GUTMANN et al. have proposed mixing iodine with an electron donor to generate a charge transfer complex with high electrical conductivity, and using this charge transfer complex as a positive electrode active material for solid electrolyte batteries.
lectrochem, Soc, 114.3
23 (1967) and 115. 359 (1968)
”), charge transfer complexes have been studied as positive electrode active materials.

As the above-mentioned electron donor, tetradeafulvalene (hereinafter abbreviated as TTF) represented by the following formula (III) is well known, forms a charge transfer complex with iodine, and exhibits good electrical conductivity. In order to reduce the internal resistance of a solid electrolyte battery, the use of this charge transfer material of TTF and iodine as a positive electrode active material is disclosed in JP-A-55-161370.

However, although the TTF-iodine charge transfer complex disclosed in JP-A-55-161370 exhibits good conductivity and low iodine vapor pressure, this complex cannot be used as a positive electrode. The fixed electrolyte battery obtained using this as the active material still had insufficient discharge capacity.

The cause of this is, for example, when lithium is used as the negative electrode active material, the electrochemical reaction TTF-1+e-→TTFi +l-2x occurs on the positive electrode side.
2x-1, I- generated on the positive electrode side and the p4 electrode side, respectively.

Reaction 1i”+l−→ in which 1i+ combines to produce LiI
It is possible that ii is not progressing sufficiently.

Steps to Solve the Problems The inventors of the present invention have investigated the usefulness of various electron donor-iodine charge transfer complexes as positive electrode active materials with the aim of solving the above-mentioned problems, and have developed the following. A novel fullvalene derivative represented by the formula <I) or the following formula (
II) A novel fullvalene derivative in which c , c , c , and c are partially or entirely crosslinked easily forms a charge transfer complex with iodine, and the charge transfer 9 complex was obtained as a positive electrode active material. It was discovered that solid electrolyte batteries have good storage stability, high utilization rate of positive electrode active material, and high discharge capacity, and have led to the present invention.

The present invention will be explained in detail below.

In the above formula (I), X −x each independently represents a sulfur atom, a selenium atom or a tellurium atom. R-R is preferably a spatially bulky substituent, each independently having a secondary or tertiary carbon atom @3 to 10 carbon atoms.
, preferably 3 to 6 alkyl groups, secondary or tertiary
Carbon atoms having 3 to 10 carbon atoms, preferably 3
~6 alkenyl groups, or aryl or aralkyl groups having 6 to 20 carbon atoms, preferably 6 to 15 carbon atoms.

Among the above-mentioned alkyl groups, the following are particularly preferred as the alkenyl group, the aryl group as the aralkyl group, and the following as the aralkyl group.

In the formula (I[), X −X each independently represents a sulfur atom, a selenium atom, or a tellurium atom, and A −
A each independently represents a hydrogen atom, a chlorine atom, a bromine atom or an iodine atom, and m.

and m each independently represent an integer of 3 to 10, preferably 3 to 6, and n represents a number of 2 to 100.

In the fulvalene derivative represented by formula (I), some or all of C1 to C are crosslinked with an alkylene chain having 3 to 10 carbon atoms, and the molecular weight is preferably about 1,000 to 50,000. .

The fullvalene derivative of the formula (I) of the present invention or the formula (I)
The charge transfer complex between the fullvalene derivative and iodine in [) is
1 mol of the fullvalene derivative of formula (I), or 1 mol of the fullvalene derivative of formula (I)
After adding 2 to 15 mol, preferably 5 to 10 mol, of iodine to 1 mol of constituent monomer units of the fulvalene derivative in I) and mixing uniformly, it can be added as is or with 40 to 80 mol of iodine.
℃ heating method for 5 to 10 hours, or dichloromethane,
Formula (I) or (I[) in a solvent such as tetrachloroethane
It can be obtained by a method such as dissolving the fulvalene derivative and iodine at the above-mentioned mixing ratio and then evaporating the solvent.

The fullvalene derivatives represented by formulas (I) and (I[) are, for example, G, 5aito et, at, C
hem.

Lett, 44t (j9aa) or G, 5ai
to, J, 5ynth.

Org, Chet Jpn,, Dan502 (1987)
It can be synthesized by the following method.

For (I), for example, add a sodium lump in water-cooled methanol under a stream of argon, then add bis(carbonyldithio)tetrathiafulvalene (IV) at VA;
Leave as it is for 4 hours to form compound (V). This compound (V) is successively added with carbon@alkyl halide having 3 to 10 carbon atoms, alkenyl halide having 3 to 10 carbon atoms, aryl halide having 6 to 20 carbon atoms, and carbon! ! ! 6
to 20 aralkyl halides are added, and "J' fA
The mixture is reacted overnight to obtain the desired compound (Vl).

For (II), for example, compound (IV) is added to water-cooled dimethylformamide (DHF) in which sodium meth-1-oxyto is dissolved at air temperature under an argon stream, and the mixture is stirred for 4 hours to form compound (V). Subsequently, a dihalogenated alkylene having m1 and/or m2 carbon atoms is added and reacted overnight at air temperature to obtain compound (■).

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be explained in more detail in Examples below, but the present invention is not limited by the Examples.

Example 1 Tetrathiabenzyltetrathiafulvalene (
Synthesis of a charge transfer complex of TTC(b) (hereinafter abbreviated as TTF) and iodine in water-cooled methanol 50Id under an argon atmosphere for 1.3 min.
After adding the sodium lumps from
Leave it for a minute. Add 5 bis(carbonyldithio)tetrathiafulvalene (Jy, hereinafter abbreviated as TTCO) to this solution.
g was added thereto, and the mixture was stirred at air temperature for 4 hours.

Next, benzyl bromide 8d was added dropwise and left overnight at air temperature.
Tetrathiabenzyltetrathiafulvalene was obtained. The product was recrystallized from acetonitrile to obtain 2.8 g of purified product.

For the product, F D −M S (ffi/S)
By measurement, 692 (M >, and 'H-NMR (
δ.

CDCII), 5=3.79(s, 8H)
, 7.19~7.25 (m, 20 fl H>
I got the result.

Obtained TTC(b)TTF and TTC(b)TTF
Thoroughly mix 4.8 moles of iodine (<1) per mole in a mortar and heat at 60°C for about 9 hours to obtain TTC (b).
) Charge transfer complex of TTF and iodine (TTC(b)TT
F. Engineering) was obtained.

79.6 Example 2 Charge transfer between tetrathiaisopentyltetrathiafulvalene (hereinafter abbreviated as TTC(i)TTF) and iodine! Instead of your synthetic benzyl bromide 8d, isopentyl bromide 7rr
Tetrathiaisopentyltetrathiafulvalene 2.59 was obtained in the same manner as in Experimental Example 1 except that tl was used.

Obtained TTC(i)TTF and TTC(i)TTF
A charge transfer complex of TTC(i)TTF and iodine (TTC(i)TTF-I) 5 was prepared in the same manner as in Example 1 using 4.8 mol of iodine per 1 mol.
9.6 was obtained.

Example 3 Synthesis of charge transfer complex of polytetrathiapentyltetrathiafulvalene (hereinafter abbreviated as PTTCTTF) and iodine 1.949 g of sodium methoxide was dissolved in ice-cooled dimethylformamide 407, and 5 g of TTCo was added.

After stirring at air temperature for 4 hours, 5.98 g of dibromopentane
was added dropwise and left overnight at air temperature to obtain polytetrathiapentyltetrathiafulvalene. After thoroughly washing the obtained product with methanol, 6.4 g of a black-brown purified product was obtained.

When the product was analyzed by IR, it was found to be 2920CIA-
In No. 1, a peak due to C-H stretching of the pentyl group was confirmed, and the disappearance of a peak due to the carbonyl group of the raw material TTCO was confirmed.

The result of elemental analysis is C:H:S:Br-34,79:2
．． It was 59:52.10:10.52.

A charge transfer complex of PTTC5TTF and iodine (PTTC5TTF) was obtained in the same manner as in Example 1 using 4.8 mol of iodine per 1 mol of the constituent monomer units of the obtained PTTCTTF and PTTCTTF.

9.6 Test Examples Each of the charge transfer complexes obtained in Examples 1 to 3 was pressurized (400
1 (5F/eJ) to produce disk-shaped pellets each having a diameter of 1 cI. Furthermore, for comparison, a charge transfer complex of tetrathiafulvalene and iodine was pressure molded to create a disk-shaped pellet with a diameter of 1c11. Using each disk-shaped pellet as a positive electrode active material, the solid electrolyte batteries shown in FIG. 1 were produced in a dry box in an argon gas atmosphere. In order to examine the discharge characteristics of each solid electrolyte battery, the time change in discharge voltage was measured when a resistance of 100Ω was loaded. The results are shown in Figure 2. Also, the first
The table shows the open circuit voltage and initial internal resistance of each solid electrolyte battery.

Effects of the Invention The charge transfer complex of the fullvalene derivative and iodine of the present invention is
It can increase the discharge capacity of solid electrolyte batteries, and is useful as a positive electrode active material for solid electrolyte batteries.

[Brief explanation of the drawing]

FIG. 1 shows a solid electrolyte battery used to evaluate the usefulness of the charge transfer complex of the fulvalene derivative and iodine of the present invention as a positive electrode active material. In the figure, A to A3 are Teflon containers, B1 and B2 are gaskets, C is a stainless steel plate (current collector), D is a positive electrode pellet, and E is a negative lithium plate. Figure 2 shows a solid electrolyte battery obtained using a charge transfer complex of a fulvalene derivative and iodine of the present invention as a positive electrode active material, and a solid electrolyte battery obtained using a charge transfer complex of tetrathiafulvalene and iodine as a positive electrode active material. FIG. 3 is a diagram showing a change in discharge voltage over time.

Claims (1)

[Claims] (1) The following formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1 to X_8 each independently represent a sulfur atom, a selenium atom, or a tellurium atom, and R_1 to R_4
is an alkyl group having 3 to 10 carbon atoms each independently having a secondary or tertiary carbon atom, an alkenyl group having 3 to 10 carbon atoms having a secondary or tertiary carbon atom,
Alternatively, it represents an aryl group or an aralkyl group having 6 to 20 carbon atoms. ) and/or the following formula (I
I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, X_1-X_8 are each independently a sulfur atom,
Represents a selenium atom or a tellurium atom, A_1 to A_4
each independently represents a hydrogen atom, a chlorine atom, a bromine atom, or an iodine atom, m_1 and m_2 each independently represent an integer of 3 to 10, and n represents 2 to 100. ), and a part or all of C_1, C_2, C_3, and C_4 are crosslinked, and the composition of the fullvalene derivative of the formula (I) per mol of the fullvalene derivative of the formula (I) or the fullvalene derivative of the formula (II) 2 to 1 per mole of monomer unit
Charge transfer complex consisting of 5 moles of iodine (I_2).