KR20040009578A - Cathode material including poly(aminothiophenol) derivatives, non-aqueous secondary battery obtained therefrom and manufacturing methods thereof - Google Patents

Abstract

PURPOSE: A positive electrode composition containing a poly(aminothiophenol) derivative, a nonaqueous secondary battery obtained from the composition and their preparation methods are provided, to allow a positive electrode composition to be produced massively with a low cost and to improve the capacity characteristic of a nonaqueous secondary battery remarkably and the cycle stability in charge/discharge. CONSTITUTION: The positive electrode composition comprises an active material comprising the doped poly(aminothiophenol) derivative having the repeating unit represented by the formula; a conductive agent; and a binder, wherein X is H, Li, Na or K; Y is F, Cl, Br, I, ClO4, PF6, BF4, CF3SO3, HSO4 or C12H25C6H4SO3; k, k' and k'' are 0.01-0.5; m is 0-0.99; and n is 5-50,000. Preferably the conductive agent is an amorphous carbon; and the binder is at least one selected from the group consisting of poly(tetrafluoroethylene), a copolymer of vinylidene fluoride and hexafluoropropylene, poly(vinylidene fluoride), and a copolymer of vinylidene fluoride and tetrafluoroethylene.

Description

Cathode composition including polyaminothiophenol derivative, non-aqueous secondary battery obtained therefrom, and method for producing same {Cathode material including poly (aminothiophenol) derivatives, non-aqueous secondary battery obtained therefrom and manufacturing methods

The present invention relates to a non-aqueous secondary battery and a method for manufacturing the same, and more particularly, to a positive electrode active material composition, a method for producing the same, and a non-aqueous secondary battery and a manufacturing method using the same.

Recently, the demand for small and portable electric and electronic devices such as mobile phones, camcorders, notebook personal computers, and personal digital assistants (PDAs) has increased. Along with this, there is a need for a high performance secondary battery that is compact, lightweight and can be used repeatedly. As a small power supply suitable for various portable information communication devices, lithium ion secondary batteries (LIB) are commercially available. LIB is a cathode using a transition metal oxide capable of intercalation / deintercalation of lithium ions as an active material and a carbon-based material capable of intercalation-deintercalation of lithium ions. A battery prepared by charging an organic electrolyte solution in which lithium ions can move between an anode and a battery, wherein the electrical energy is generated by a redox reaction when lithium ions are intercalated / deintercalated at the cathode and the anode. do.

As a cathode of the lithium secondary battery, a complex oxide of a transition metal and lithium, which exhibits a potential of about 3 to 4.5 V higher than the electrode potential of Li / Li ⁺ and is capable of intercalation / deintercalation of lithium ions, is mainly used. Examples thereof include lithium cobalt oxide (LiCoO ₂ ), lithium nickel oxide (LiNiO ₂ ), lithium manganese oxide (LiMnO ₂ ), and the like.

However, as the development of information and communication devices is accelerated, there is a demand for batteries having improved performance characteristics such as energy density, capacity, and stability. However, current cathode systems based on lithium transition metal oxides, such as Lithium Polymer Battery (LPB), which are about to be commercialized and commercialized LIB, are not satisfied. In particular, the secondary battery for the terminal of the IMT-2000 system, which is the next generation mobile communication system, requires a capacity and a high level of stability corresponding to several times that of a conventional battery. To meet these demands, technological advances in the development of high capacity anode materials must be made first.

In order to improve the capacity of the positive electrode, a realistic method has been first introduced by introducing elemental substituents to LiCoO ₂ , LiNiO ₂ , LiMn ₂ O ₄ , which are conventional lithium-containing metal oxides. This method did not result in significant capacity improvements over existing performance (see JR Dahn et al., Electrochemical and Solid-State Letters, 4, A191, 2000, JY Lee et al., J. Power). Sources, 81-82, 416, 1999).

In addition, grown tight iron based: the (Groutite α-HMnO ₂₎ type, zigzag variety of LiFeO _2, etc. (Zigzag) layered, the layered composite by utilizing the soft chemistry (soft chemistry) method, and early as in the LiCoO ₂ Attempts have been made to achieve reversible 4V discharge using redox of Fe ^{4 + / 3 +} during charging. On the other hand, Fe ^{3 + / 2 +} NASICON type using a redox of _{Fe 2 (SO 4) 3 (} Fe 3 + / 2 +, 3.6V × 100mAh / g) or Olivin type LiFePO ₄ (Fe ^{3 + / 2+} , 3.3V × 150mAh / g) Research is also underway as a 3V-based next-generation cathode active material (J. Yamaki et al., J. Power Sources, 68, 711, 1997, JB Goodenough et al., J Electrochem.Soc., 144, 1609, 1997).

In addition to the development of cathode materials based on inorganic materials, the development of cathode materials using conductive polymers such as polyacetylene, polypyrrole, polythiophene, polyaniline, etc. has been steadily studied since the early 80s. However, even in the case of such a conductive polymer, application to the anode did not result in an improvement in capacity compared to conventional inorganic oxides (see MacDiarmid et al., J. Electrochem. Soc., 128, 1651, 1981, Taguchi et al. , J. Power Sources, 20, 243, 1987).

Recently, development of a new positive electrode active material for lithium secondary batteries using organic materials such as disulfide compounds has been attempted. Disulfide compounds are a series of compounds having -SH groups in their molecules, and undergo an energy exchange reaction through a reversible process (2SH ↔ SS), which is very easy to split and recombine. Much higher than that was expected as a new anode material. However, they also showed that the capacity value of the battery was far below the theoretical capacity, and the initial capacity value decreased rapidly as the cycle progressed (see SJ Visco et al., J. Electrochem. Soc., 136, 661, 1989, N. Oyama et al., J. Electrochem. Soc., 142, 354, 1995).

An object of the present invention is to solve the problems in the prior art, to provide a cathode composition for a non-aqueous secondary battery capable of large-scale synthesis at a low cost, and can significantly improve the capacity characteristics of the non-aqueous secondary battery. .

Another object of the present invention is to provide a non-aqueous secondary battery that can provide a stable cycle stability during charging and discharging by forming a positive electrode using a composition of a new structure capable of mass synthesis at low cost as a positive electrode active material It is.

Another object of the present invention is to provide a method for producing a positive electrode composition for a non-aqueous secondary battery having a novel structure capable of mass synthesis at low cost.

Still another object of the present invention is to provide a method of manufacturing a non-aqueous secondary battery, which has improved capacity characteristics and can provide stable cycle stability during charge and discharge.

1 is a flowchart illustrating a method of manufacturing a cathode composition for a non-aqueous secondary battery and a method of manufacturing a non-aqueous secondary battery according to the present invention.

2 is a graph showing UV / VIS (ultraviolet-visable absorbance) spectra of polyaminothiophenol derivatives chemically synthesized by the method according to the present invention.

3 is a SEM (Scanning Electron Microscope) photograph of HCl doped polyaminothiophenol derivative particles chemically synthesized by the method according to the present invention.

4 is a graph showing charge and discharge characteristics of an electrode prepared using a polyaminothiophenol derivative prepared by the method according to the present invention as an active material.

5 is a graph showing a change in discharge capacity value according to the number of cycles of an electrode using a polyaminothiophenol derivative prepared by the method according to the present invention.

In order to achieve the above object, the positive electrode composition for a non-aqueous secondary battery according to the present invention comprises an active material consisting of a doped polyaminothiophenol derivative having a repeating unit represented by the following formula, a conductive agent, and a binder.

Wherein X is H, Li, Na or K and Y is F, Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , CF ₃ SO ₃ , HSO ₄ or C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ K and k 'are 0.01 to 0.5 as mole fractions, m is 0 to 0.99 as mole fractions, and n is 5 to 50,000 as the number of repeating units.

The conductive agent may be made of amorphous carbon such as acetylene black, carbon black, denka black, super-P, ronza, or mixtures thereof.

The binder may be a polytetrafluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, a polyvinylidene fluoride, or a copolymer of vinylidene fluoride and tetrafluoroethylene, or a mixture thereof. Can be done.

In order to achieve the above another object, the non-aqueous secondary battery according to the present invention is a positive electrode comprising a composition according to the present invention as defined above is held in a positive electrode current collector, a negative electrode made of lithium, between the positive electrode and the negative electrode It consists of an organic electrolyte solution interposed. Here, the composition may be maintained in the form of a film on the positive electrode current collector. The organic electrolyte solution is impregnated in a separator interposed between the positive electrode and the negative electrode.

The organic electrolyte solution is ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, methyl formate, ethyl formate, gamma-butyrolactone, Or organic solvents consisting of mixtures thereof.

In addition, the organic electrolyte is lithium perchlorate (LiClO ₄ ), lithium triplate (LiCF ₃ SO ₃ ), lithium hexafluoro phosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium trifluoromethanesulfonyl Lithium salts consisting of imides (LiN (CF ₃ SO ₂ ) ₂ ), or mixtures thereof.

In order to achieve the above another object, in the method for preparing a positive electrode composition for a non-aqueous secondary battery according to the present invention, an undoped polyaminothiophenol derivative having a repeating unit represented by the following formula is synthesized.

In the formula, k and k 'are each 0.01-0.5 as mole fractions, m is 0-0.99 as mole fractions, and n is 5-50,000 as repeat unit numbers. The undoped polyaminothiophenol derivative is doped to form a doped polyaminothiophenol derivative having a repeating unit represented by the following formula.

Wherein X is H, Li, Na or K and Y is F, Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , CF ₃ SO ₃ , HSO ₄ or C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ K and k 'are 0.01 to 0.5 as mole fractions, m is 0 to 0.99 as mole fractions, and n is 5 to 50,000 as the number of repeating units. The doped polyaminothiophenol derivatives are mixed uniformly with the conducting agent and the binder. In the mixing step, it is possible to quantify the doped polyaminothiophenol derivative, the conductive agent and the binder in a predetermined ratio and mix in a powder state. Alternatively, in the mixing step, the doped polyaminothiophenol derivative, the conductive agent and the binder may be quantified in a predetermined ratio and dissolved in the cosolvent.

In order to achieve the above another object, in the method for manufacturing a non-aqueous secondary battery according to the present invention, the composition prepared by the method according to the present invention as defined above is cast on a current collector to form a positive electrode film. A separator and a lithium negative electrode are sequentially stacked on the positive electrode film. An organic electrolyte is injected into the separator.

According to the present invention, by using a polyaminothiophenol derivative represented by the above formula as an active material, based on the existing conductive polymer and inorganic material by the division and recombination between -SH groups present in the conductive polymer structure constituting the active material It shows the capacity characteristics superior to the active material. Therefore, the lithium secondary battery according to the present invention may provide improved capacity characteristics by excellent capacity retention characteristics according to cycles, and may provide improved cycle stability during charge and discharge.

Next, preferred embodiments of the present invention will be described in detail with reference to the accompanying drawings.

The positive electrode composition for a non-aqueous secondary battery according to the present invention uses a doped polyaminothiophenol derivative having a repeating unit represented by Formula 1 as an active material capable of intercalation-deintercalation of lithium ions.

Wherein X is H, Li, Na or K and Y is F, Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , CF ₃ SO ₃ , HSO ₄ or C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ K and k 'are 0.01 to 0.5 as mole fractions, m is 0 to 0.99 as mole fractions, and n is 5 to 50,000 as the number of repeating units.

In addition, the positive electrode composition for a non-aqueous secondary battery according to the present invention includes a conductive agent and a binder in addition to the active material of Chemical Formula 1. As the conductive agent, amorphous carbon such as acetylene black, carbon black, denka black, Super-P, Lonza, etc. may be used alone or in combination thereof. Examples of the binder include polytetrafluoroethylene, copolymers of vinylidene fluoride and hexafluoropropylene, polyvinylidene fluoride, or copolymers of vinylidene fluoride and tetrafluoroethylene, or mixtures thereof. Can be used. The weight ratio of the active material and the conductive agent is not particularly limited, and may be used in a weight ratio of about 1:99 to 99: 1. In addition, the weight ratio between the active material and the conductive agent mixture and the binder polymer is not particularly limited, and may be used in a weight ratio of about 1:99 to 99: 1.

In the non-aqueous secondary battery according to the present invention, a positive electrode composition prepared by uniformly mixing an active material, a conductive agent, and a binder of Formula 1 is coated on a positive electrode current collector and dried to maintain the positive electrode current collector in a film form. It is provided.

As the negative electrode material of the non-aqueous secondary battery according to the present invention, any material can be used as long as it is generally used for lithium batteries that contain lithium and can be charged and discharged.

The organic electrolyte is interposed between the positive electrode and the negative electrode in the state of being impregnated with the polymer separator. The separator can be used as long as it is generally used for non-aqueous secondary batteries that can be charged and discharged. For example, a microporous polypropylene film, polyethylene film, or the like can be used.

The organic electrolyte may be used by appropriately combining an organic solvent and a solute, and any organic solvent may be used as long as it is widely known in the field of lithium secondary battery manufacturing. Specific examples of the organic solvent include ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, methyl formate, ethyl formate, gamma Butyrolactone, or mixtures thereof. The organic solvent may be used in an amount of about 1 to 2000 wt%, preferably about 1 to 1000 wt%, based on the weight of the polymer separator. As the solute, for example, lithium perchlorate (LiClO ₄ ), lithium triplate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), and lithium trifluoromethane the sulfonyl imide _{(LiN (CF 3 SO 2)} 2), or may be composed of a lithium salt or a mixture thereof. The lithium salt may be used in an amount of about 1 to 100% by weight, preferably about 1 to 50% by weight, based on the weight of the organic solvent.

1 is a flowchart illustrating a method for manufacturing a cathode composition for a non-aqueous secondary battery and a method for manufacturing a lithium secondary battery according to the present invention.

Referring to FIG. 1, first, an undoped polyaminothiophenol derivative having a repeating unit represented by Formula 2 is synthesized (step 10).

In the formula, k and k 'are each 0.01-0.5 as mole fractions, m is 0-0.99 as mole fractions, and n is 5-50,000 as repeat unit numbers.

Thereafter, the doped polyaminothiophenol derivative is doped with an aqueous solution of a dopant at a predetermined concentration to form a doped polyaminothiophenol derivative having a repeating unit represented by Formula 1 (step 20). Thereafter, the doped polyaminothiophenol derivative is used as an active material and uniformly mixed with a conductive agent and a binder at a predetermined ratio to prepare a positive electrode composition (step 30). At this time, the doped polyaminothiophenol derivative, the conductive agent and the binder may be quantified in a predetermined ratio, ground in a mortar, mixed in powder form, or dissolved in a cosolvent to obtain a uniform mixture. As already described, the weight ratio of the active material and the conductive agent is not particularly limited and may be used in a weight ratio of about 1:99 to 99: 1. In addition, the weight ratio between the active material and the conductive agent mixture and the binder polymer is not particularly limited, and may be used in a weight ratio of about 1:99 to 99: 1.

The positive electrode composition obtained in step 30 is cast on the positive electrode current collector to form a positive electrode film (step 40). An aluminum mesh can be used as the positive electrode current collector.

The polymer separator and the lithium negative electrode are sequentially stacked on the positive electrode film (step 50). The laminated film obtained in step 50 is placed in a pouch and the organic electrolyte is injected into the separator after the measurement terminal treatment (step 60).

Next, a specific experimental example will be described in more detail with respect to a method for manufacturing a cathode composition for a non-aqueous secondary battery and a method for manufacturing a non-aqueous secondary battery according to the present invention. However, the following examples are merely examples to aid the understanding of the present invention, and the scope of the present invention should not be construed as being limited thereto.

Synthesis Example

Synthesis of Doped Polyaminothiophenol Derivative Active Material

150 mL of 1M HCl aqueous solution was used as a solvent, 2-aminothiophenol and aniline monomer were added in a weight ratio of 1: 9, and stirred in a nitrogen atmosphere for 30 minutes. After completion of the stirring, ammonium persulfate, an initiator, was injected at 150 wt% based on the weight of the monomer, and reacted at 0 ° C. for 24 hours. After the reaction was completed, the reaction product was washed and filtered repeatedly to obtain a black powdery form. The dark green powder obtained by filtration was dedoped in 1M NH ₄ OH aqueous solution, and then washed and filtered again. After drying for 24 hours in a hood at room temperature, the resultant was dried for at least 48 hours in a vacuum oven to completely remove moisture, thereby obtaining an undoped polyaminothiophenol derivative.

An appropriate amount of undoped polyaminothiophenol derivative was added to 1M aqueous HCl solution and stirred for 12 hours or longer. After repeated washing and filtration, the resultant was dried for 24 hours in a hood at room temperature and again for at least 48 hours in a vacuum oven to obtain a finally doped polyaminothiophenol derivative.

Example 1

According to the method described in the synthesis example, 2-aminothiophenol and aniline monomers were put in a reactor in a weight ratio of 1: 9, and synthesized to prepare a doped polyaminothiophenol derivative active material. The powder was mixed with the conductive material so that the weight ratio was 7: 3, and then polytetrafluoroethylene was added thereto as a binder to 12% by weight of the powder mixture, and mixed for 30 minutes or more in a mortar. . The mixture was coated on an aluminum current collector to prepare a positive electrode film. The polymer separator and the lithium negative electrode film were sequentially laminated on the prepared positive electrode film. Put the laminated films in the pouch and the final terminal treatment, and then injected into the mixed solvent of ethylene carbonate and propylene carbonate mixed in a 1: 1 molar ratio by injecting an organic electrolyte solution of 1 molar concentration of lithium hexafluorophosphate to finally unit cell Prepared.

Example 2

An electrode and a unit cell were manufactured in the same manner as in Example 1, except that 2-aminothiophenol and aniline monomer were added to a reactor in a weight ratio of 3: 7 according to the method described in the synthesis example, and the synthesized active material was used.

Example 3

An electrode and a unit cell were manufactured in the same manner as in Example 1, except that 2-aminothiophenol and aniline monomer were added to a reactor in a weight ratio of 5: 5 according to the method described in the synthesis example, and the synthesized active material was used.

Example 4

An electrode and a unit cell were manufactured in the same manner as in Example 1, except that 2-aminothiophenol and aniline monomer were added to a reactor in a weight ratio of 7: 3 according to the method described in the synthesis example, and the synthesized active material was used.

Example 5

An electrode and a unit cell were manufactured in the same manner as in Example 1, except that 2-aminothiophenol and aniline monomer were added to a reactor in a weight ratio of 10: 0 according to the method described in the synthesis example, and the synthesized active material was used.

Comparative example

An electrode and a unit cell were manufactured in the same manner as in Example 1, except that polyaniline was used as the active material.

Table 1 shows the results of measuring the discharge capacity of the unit cells obtained in Examples 1 to 5 and the unit cells obtained in Comparative Examples.

From Table 1, the polymer electrode manufactured by the method according to the present invention has a capacity per active material of up to 200 mAh / g, which is significantly larger than that of a conventional polyaniline-based polymer electrode, and has a capacity according to a cycle. It is understood that the retention properties are excellent and the performance is excellent as a new organic electrode material.

2 is a UV of a conductive polymer in which 2-aminothiophenol and aniline monomers are chemically synthesized according to the method according to the present invention in a weight ratio of 7: 3, and synthesized into a reactor by doping with HCl. / VIS (ultraviolet-visible absorbance) spectrum. In Figure 2, it can be confirmed that the synthesis of the polymer well by controlling the molecular exciton peak in the vicinity of 500nm.

FIG. 3 is a SEM (Scanning Electron Microscope) photograph of a conductive polymer active material doped with HCl by adding 2-aminothiophenol and aniline monomer in a weight ratio of 7: 3 among chemically synthesized polyaminothiophenol derivatives in a reactor (20,000 ×), showing that the elliptical particles average 25 μm.

Figure 4 is a graph showing the charge and discharge characteristics of Example 4 of the electrode prepared using the synthesized polyaminothiophenol derivative as an active material. When compared with the comparative example, it can be seen that by showing a high discharge capacity value exhibits excellent capacity characteristics compared to the anode based on a conventional conductive polymer.

5 shows a change in the discharge capacity value according to the cycle of Example 4. In Figure 5, it can be seen that the capacity retention characteristics according to the cycle is excellent.

The lithium secondary battery according to the present invention includes an electrode prepared by using a new polyaminothiophenol derivative having -SH group introduced into a polyaniline, which is a conductive polymer, as an active material, as represented by Chemical Formula 1. The polyaminothiophenol derivatives can be synthesized in large quantities at low cost by a chemical oxidation-reduction method. The polymer active material constituting the positive electrode composition for a lithium secondary battery according to the present invention exhibits excellent capacity characteristics compared to an active material based on a conventional conductive polymer and an inorganic material by division and recombination between -SH groups present in the conductive polymer structure. In addition, energy is stored by repeating the connection and disconnection of interchain disulfide bonds. Therefore, due to the reversibility peculiar to the disulfide reaction, the capacity retention characteristic of the charge / discharge cycle can be remarkably improved. Therefore, the lithium secondary battery according to the present invention may provide improved capacity characteristics by excellent capacity retention characteristics according to cycles, and may provide improved cycle stability during charge and discharge.

The present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications can be made by those skilled in the art within the scope of the technical idea of the present invention. Do.

Claims (13)

(a) an active material comprising a doped polyaminothiophenol derivative having a repeating unit represented by the following formula: Wherein X is H, Li, Na or K and Y is F, Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , CF ₃ SO ₃ , HSO ₄ or C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ K and k 'are 0.01 to 0.5 as mole fractions, m is 0 to 0.99 as mole fractions, and n is 5 to 50,000 as repeating unit numbers. (b) a conductive agent, (c) A positive electrode composition for a non-aqueous secondary battery comprising a binder. The method of claim 1, The conductive agent is a positive electrode composition for a non-aqueous secondary battery, characterized in that consisting of amorphous carbon. The method of claim 2, The conductive agent is a positive electrode composition for a non-aqueous secondary battery, characterized in that made of acetylene black, carbon black, denka black, Super-P, Lonza, or a mixture thereof. The method of claim 1, The binder may be a polytetrafluoroethylene, a copolymer of vinylidene fluoride and hexafluoropropylene, a polyvinylidene fluoride, or a copolymer of vinylidene fluoride and tetrafluoroethylene, or a mixture thereof. A cathode composition for a non-aqueous secondary battery, characterized in that made. A positive electrode in which the composition according to claim 1 is held in a positive electrode current collector; A negative electrode made of lithium, A non-aqueous secondary battery comprising an organic electrolyte interposed between the positive electrode and the negative electrode. The method of claim 5, The non-aqueous secondary battery according to claim 1, wherein the composition according to claim 1 is maintained in a film form on the positive electrode current collector. The method of claim 5, The organic electrolyte is a non-aqueous secondary battery, characterized in that the separator is impregnated between the positive electrode and the negative electrode. The method according to claim 5 or 7, The organic electrolyte solution is ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane, methyl formate, ethyl formate, gamma-butyrolactone, Or an organic solvent comprising a mixture thereof. The method according to claim 5 or 7, The organic electrolyte is lithium perchlorate (LiClO ₄ ), lithium triplate (LiCF ₃ SO ₃ ), lithium hexafluorophosphate (LiPF ₆ ), lithium tetrafluoroborate (LiBF ₄ ), lithium trifluoromethanesulfonylimide A non-aqueous secondary battery comprising a lithium salt consisting of (LiN (CF ₃ SO ₂ ) ₂ ), or a mixture thereof. (a) synthesizing an undoped polyaminothiophenol derivative having a repeating unit represented by the formula: In the formula, k and k 'are each 0.01-0.5 as mole fractions, m is 0-0.99 as mole fractions, and n is 5-50,000 as a repeating unit number. (b) doping the undoped polyaminothiophenol derivative to form a doped polyaminothiophenol derivative having a repeating unit represented by the following formula: Wherein X is H, Li, Na or K and Y is F, Cl, Br, I, ClO ₄ , PF ₆ , BF ₄ , CF ₃ SO ₃ , HSO ₄ or C ₁₂ H ₂₅ C ₆ H ₄ SO ₃ K and k 'are 0.01 to 0.5 as mole fractions, m is 0 to 0.99 as mole fractions, and n is 5 to 50,000 as the number of repeating units. (C) a method for producing a positive electrode composition for a non-aqueous secondary battery comprising the step of uniformly mixing the doped polyaminothiophenol derivative with a conductive agent and a binder. The method of claim 10, In the mixing step, the doped polyaminothiophenol derivative, conductive agent and binder are quantified in a predetermined ratio and mixed in a powder form, characterized in that the method for producing a positive electrode composition for a non-aqueous secondary battery. The method of claim 10, In the mixing step, the doped polyaminothiophenol derivative, conductive agent and binder are quantified in a predetermined ratio and dissolved in a co-solvent, a method for producing a positive electrode composition for a non-aqueous secondary battery. (a) casting a composition prepared by the method according to any one of claims 10 to 12 on a current collector to form a positive electrode film, (b) sequentially depositing a separator and a lithium negative electrode on the positive electrode film; (c) a method of manufacturing a non-aqueous secondary battery, comprising the step of injecting an organic electrolyte into the separator.