Reinforced high polymers, process for preparing same and battery having same

Claim 2

A battery comprising a positive electrode, a negative electrode and an electrolyte, wherein at least one of said positive electrode and said negative electrode is comprised of a reinforced acetylene high polymer shaped article, which comprises (1) an acetylene high polymer or an electroconductive acetylene high polymer doped with a dopant, and (2) 10 to 500 parts by weight, per 100 parts by weight of the acetylene high polymer, of the sheet-form product of a fibrous material, and which is prepared by shaping under pressure a swollen or gel-like acetylene high polymer containing an organic solvent, together with said sheet-form product; said sheet-form product being a woven or knitted fabric, a non-woven fabric or a net or screen, which is composed of an organic high polymer fiber or an inorganic fiber, and said acetylene high polymer being prepared by polymerizing acetylene using a catalyst system comprised of a transitional metal compound and an organic metal compound, said transitional metal compound being used in an amount of 0.0001 to 0.1 mole per liter of a polymerization solvent.

Claim 3

A battery according to claim 1, wherein said net or screen has a 10 to 400 mesh size according to the Tyler standard sieve.

Claim 4

A battery according to claim 1, wherein said net or screen has a porosity of 30 to 90%.

Claim 5

A battery according to claim 1, wherein the acetylene high polymer is in the form of being pressed integrally with the sheet-form product of the fibrous material.

Claim 6

A battery according to claim 1, wherein the acetylene high polymer is of a fibril or lamellar crystalline structure.

Claim 7

A battery according to claim 5, wherein the acetylene high polymer has a crystalline degree of at least 60%.

Claim 8

A battery according to claim 1, wherein the amount of the sheet-form product of the fibrous material is in the range of from 20 to 300 parts by weight per 100 parts by weight of the acetylene high polymer.

Claim 9

A battery according to claim 1, wherein the battery is a primary battery and the acetylene high polymer is doped with said dopant, so that the electrical conductivity of the thus doped electrically conductive acetylene high polymer is at least 10 -4 Ω -1 ·cm -1 .

Claim 10

A battery according to claim 8, wherein the dopant is an anion selected from the group consisting of an anion of a halide of an element of the group VA of the Periodic Table, an anion of a halide of an element of the group IIIA of the Periodic Table, a halogen anion, a perhalo-acid anion and an organic anion.

Claim 11

A battery according to claim 8, wherein the dopant is an anion selected from the group consisting of PF 6 - , SbF 6 - , AsF 6 - , SbCl 6 - , SiF 6 -- , BF 4 - , BCl 4 - , AlCl 4 - , I - or I 3 - , Br - , Cl - , NO 3 - , POF 4 - , CN - , ClO 4 - , IO 4 - , CF 3 SO 3 - , CH 3 CO 2 - , CF 3 CO 2 - , C 6 H 5 SO 3 - , C 6 H 5 CO 2 - and CH 3 C 6 H 4 SO 3 - .

Claim 12

A battery according to claim 8, wherein the dopant is a cation selected from the group consisting of an alkali metal ion and an organic cation which is selected from the group consisting of R 4-x MH x + and R 3 E + , wherein R is alkyl or aryl, M is N, P or AS, E is O or S, and X is an integer ranging from 0 to 4.

Claim 13

A battery according to claim 8, wherein the dopant is HF 2 - .

Claim 14

A battery according to claim 8, wherein the dopant is a cation selected from the group consisting of pyrylium and pyridinium cations represented by the following formula (I): ##STR7## wherein X stands for an oxygen atom or nitrogen atom, R' stands for a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R" stands for a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, n is zero when X is an oxygen atom or n is 1 when X is a nitrogen atom, and m is an integer of from 0 to 5; and carbonium cations represented by the following formulae (II) and (III): ##STR8## wherein R 1 , R 2 and R 3 stand for a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an allyl group, an aryl group having 6 to 20 carbon atoms or a group --OR 5 , in which R 5 stands for an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, with the proviso that the case where all of R 1 , R 2 and R 3 are hydrogen atoms is excluded, and R 4 stands for a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Claim 15

A battery according to claim 1, wherein the battery is a secondary battery and the acetylene high polymer is non-doped and has an electrical conductivity of from 1×10 -5 to 1×10 -9 Ω -1 ·cm -1 .

Claim 16

A battery according to claim 14, wherein both the positive and negative electrodes are made of the reinforced acetylene high polymer shaped article.

Claim 17

A battery according to claim 14, wherein the positive electrode is made of the reinforced acetylene high polymer shaped article and the negative electrode is made of another electrically conductive high polymer.

Claim 18

A battery according to claim 16, wherein the electrically conductive high polymer is polypyrrole, polythiophene or polyparaphenylene.

Claim 19

A battery according to claim 16, wherein the electrically conductive high polymer is polyparaphenylene.

Claim 20

A battery according to claim 16, wherein the electrically conductive high polymer is polypyrrole, polythiophene or polyparaphenylene.

Claim 21

A battery according to claim 16, wherein the electrically conductive high polymer is polyparaphenylene.

Claim 22

A battery according to claim 1, wherein the battery is a secondary battery and the acetylene high polymer is doped with said dopant, so that the electrical conductivity of the thus doped electrically conductive acetylene high polymer is at least 1×10 -9 Ω -1 ·cm -1 .

Claim 23

A battery according to claim 21, wherein the dopant is an anion selected from the group consisting of an anion of a halide of an element of the group VA of the Periodic Table, an anion of a halide of an element of the group IIIA of the Periodic Table, a halogen anion, a perhalo-acid anion and an organic anion.

Claim 24

A battery according to claim 21, wherein the dopant is an anion selected from the group consisting of PF 6 - , SbF 6 - , AsF 6 - , SbCl 6 - , SiF 6 -- , BF 4 - , BCl 4 - , AlCl 4 - , I - or I 3 - , Br - , Cl - , NO 3 - , POF 4 - , CN - , ClO 4 - , IO 4 - , CF 3 SO 3 - , CH 3 CO 2 - , CF 3 CO 2 - , C 6 H 5 SO 3 - , C 6 H 5 CO 2 - and CH 3 C 6 H 4 SO 3 .

Claim 25

A battery according to claim 21, wherein the dopant is a cation selected from the group consisting of an alkali metal ion and an organic cation which is selected from the group consisting of R 4-x MH x + and R 3 E + , wherein R is alkyl or aryl, M is N, P or AS, E is O or S, and X is an integer ranging from 0 to 4.

Claim 26

A battery according to claim 21, wherein the dopant is HF 2 - .

Claim 27

A battery according to claim 21, wherein the dopant is a cation selected from the group consisting of pyrylium and pyridinium cations represented by the following formula (I): ##STR9## wherein X stands for an oxygen atom or nitrogen atom, R' stands for a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R" stands for a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, n is zero when X is an oxygen atom or n is 1 when X is a nitrogen atom, and m is an integer of from 0 to 5; and carbonium cations represented by the following formulae (II) and (III): ##STR10## wherein R 1 , R 2 and R 3 stand for a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an allyl group, an aryl group having 6 to 20 carbon atoms or a group --OR 5 , in which R 5 stands for an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, with the proviso that the case where all of R 1 , R 2 and R 3 are hydrogen atoms is excluded, and R 4 stands for a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Claim 28

A battery according to claim 21, wherein both the positive and negative electrodes are made of the reinforced acetylene high polymer shaped article.

Claim 29

A battery according to claim 21, wherein the positive electrode is made of the reinforced acetylene high polymer shaped article and the negative electrode is made of another electrically conductive high polymer.

Claim 30

A battery according to claim 1 wherein the dopant is an anion selected from the group consisting of an anion of a halide of an element of the group VA of the Periodic Table, an anion of a halide of an element of the group IIIA of the Periodic Table, a halogen anion, a perhalo-acid anion and an organic anion.

Claim 31

A battery according to claim 1 wherein the dopant is an anion selected from the group consisting of PF 6 - , SbF 6 - , AsF 6 - , SbCl 6 - , SiF 6 -- , BF 4 - , BCl 4 - , AlCl 4 - , I - or I 3 - , Br - , Cl - , NO 3 - , POF 4 - , CN - , ClO 4 - , IO 4 - , CF 3 SO 3 - , CH 3 CO 2 - , CF 3 CO 2 - C 6 H 5 SO 3 - , C 6 H 5 CO 2 - , and CH 3 C 6 H 4 SO 3 .

Claim 32

A battery according to claim 1 wherein the dopant is a cation selected from the group consisting of an alkali metal ion and an organic cation which is selected from the group consisting of R 4-x MH x + and R 3 E + , wherein R is alkyl or aryl, M is N, P or AS, E is O or S, and X is an integer ranging from 0 to 4.

Claim 33

A battery according to claim 1, wherein the dopant is HF 2 - .

Claim 34

A battery according to claim 1 wherein the dopant is a cation selected from the group consisting of pyrylium and pyridinium cations represented by the following formula (I): ##STR11## wherein X stands for an oxygen atom or nitrogen atom, R' stands for a hydrogen atom, an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 20 carbon atoms, R" stands for a halogen atom, an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, n is zero when X is an oxygen atom or n is 1 when X is a nitrogen atom, and m is an integer of from 0 to 5; and carbonium cations represented by the following formulae (II) and (III): ##STR12## wherein R 1 , R 2 and R 3 stand for a hydrogen atom, an alkyl group having 1 to 15 carbon atoms, an allyl group, an aryl group having 6 to 20 carbon atoms or a group --OR 5 , in which R 5 stands for an alkyl group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms, with the proviso that the case where all of R 1 , R 2 and R 3 are hydrogen atoms is excluded, and R 4 stands for a hydrogen atom, an alkyl group having 1 to 15 carbon atoms or an aryl group having 6 to 20 carbon atoms.

Claim 35

A battery according to claim 1, wherein the amount of the dopant is in the range of 2 to 40 moles per mole of the recurring unit --CH-- in the acetylene high polymer.

Claim 36

A battery according to claim 1, wherein the reinforced acetylene high polymer shaped article further comprises 1 to 5 parts by weight of an electrically conductive material.

Claim 37

A battery according to claim 35, wherein at least one of the positive and negative electrodes is made of the reinforced acetylene high polymer shaped article.

Claim 38

A battery according to claim 36, which is a primary battery.

Claim 39

A battery according to claim 36, which is a secondary battery.

Claim 40

A battery according to claim 38, wherein both the positive and negative electrodes are made of the reinforced acetylene high polymer shaped article.

Claim 41

A battery according to claim 38, wherein the positive electrode is made of the reinforced acetylene high polymer shaped article and the negative electrode is made of another electrically conductive high polymer.

Claim 42

A battery according to claim 35, wherein the sheet-form product of a fibrous material is a net or screen having a 10 to 400 mesh size according to the Tyler standard sieve.

Claim 43

A battery according to claim 35, wherein the sheet-form product of a fibrous material is a net or screen having a porosity of 30 to 90%.

Claim 44

A battery according to claim 35, wherein the electrically conductive material is carbon black, acetylene black or carbon fiber.

Claim 45

A battery according to claim 35, wherein said reinforced acetylene high polymer shaped article is prepared by blending the acetylene high polymer with the electrically conductive material in the presence of an organic solvent.

Claim 46

A battery according to claim 35, wherein said reinforced acetylene high polymer shaped article is prepared by blending the acetylene high polymer with the electrically conductive material in the absence of an organic solvent.

Claim 47

A battery according to claim 1 wherein the amount of said organic solvent comprises up to 500 parts by weight per 100 parts by weight of said acetylene high polymer.

Claim 48

A battery according to claim 1, wherein said pressing or calendering is effected at a pressure of at least 10 kg/cm 2 and at a temperature not in excess of 200° C.

Claim 49

A battery according to claim 1, wherein the sheet-form product has an electrical conductivity of at least 1×10 -3 Ω -1 ·cm -1 .

Claim 50

A battery according to claim 1, wherein the sheet-form product has an electrical conductivity of not more than 1×10 -3 Ω -1 ·cm -1 .

Claim 51

A battery according to claim 1 wherein the amount of said organic solvent is up to 500 parts by weight per 100 parts by weight of said acetylene high polymer.

Claim 52

A battery according to claim 1 wherein said shaping of the swollen or gel-like acetylene high polymer is effected at a pressure of at least 10 kg/cm 2 and at a temperature not in excess of 200° C.

Claim 53

A battery according to claim 1 wherein said acetylene high polymer is a short fiber having a length smaller than 5 cm.

Claim 54

A battery according to claim 1 wherein said acetylene high polymer shaped article is prepared by polymerizing acetylene in the presence of the sheet-form product of a fibrous material which has been coated or impregnated with a catalyst solution or dispersion whereby the resulting acetylene high polymer is deposited on the sheet-form product of the fibrous material at the polymerization step, and then, pressing or calendarizing the combination of the acetylene high polymer with the sheet-form product of the fibrous material.

Claim 55

A battery according to claim 53 wherein acetylene is polymerized in the presence of the sheet-form product of the fibrous material impregnated with a catalyst solution in an organic solvent to obtain an acetylene high polymer deposited on the sheet-form product, and then, the resulting combination of the acetylene high polymer with the sheet-form product is pressed or calendered in the state where the organic solvent is still contained in the sheet-form product.

Claim 56

A battery according to claim 1 wherein said swollen or gel-like acetylene high polymer containing an organic solvent is superposed upon the sheet-form product of the fibrous material, and then, the superposed assembly is pressed and calendered.

Claim 57

A battery according to claim 1 wherein a powdery or short fibrous swollen or gel-like acetylene high polymer containing an organic solvent is superposed upon the sheet-form product of the fibrous material, and then, the superposed assembly is pressed or calendered.

Claim 58

A battery according to claim 56 wherein the organic solvent-containing powdery or short fibrous acetylene high polymer is prepared by pulverizing an acetylene high polymer which has been swollen or gel-like with the organic solvent.