Flame-retardant solid electrolytes

• US 5,972,539 A
• Filed: 08/18/1997
• Issued: 10/26/1999
• Est. Priority Date: 08/19/1996
• Status: Expired due to Fees

• Current Assignee: Dao-Ichi Kogyo Seiyaku Co., Ltd., DENSO Corporation
• Original Assignee: Dai-Ichi Kogyo Seiyaku Company Limited, DENSO Corporation
• Inventors: Hasegawa, Jun, Saito, Hirohiko, Komori, Hirohito, Muramatsu, Hiromochi, Kono, Michiyuki
• Primary Examiner(s): Nuzzolillo, Maria
• Assistant Examiner(s): Martin, Angela J.
• Application Number:
  US08/912,787
• Time in Patent Office: 799 Days
• Field of Search: 429/306, 429/314, 429/324
• US Class Current: 429/304
• CPC Class Codes: C07F 9/091 with hydroxyalkyl compounds with further substituents on alkyl
• CPC Class Codes: C08G 79/04 Phosphorus linked to oxygen or to oxygen and carbon
• CPC Class Codes: H01B 1/122 Ionic conductors
• CPC Class Codes: H01M 10/052 Li-accumulators
• CPC Class Codes: H01M 10/0565 Polymeric materials, e.g. gel-type or solid-type
• CPC Class Codes: H01M 2300/0082 Organic polymers
• CPC Class Codes: Y02E 60/10 Energy storage using batteries

Abstract

A flame retardant solid electrolyte comprising an ion conductive polymer matrix having moieties capable of imparting flame retardance to the polymer matrix and ether bonds in the molecule and an electrolyte salt dispersed in the polymer matrix. The flame retardant solid electrolyte may be one which comprises a non-ion-conductive polymer matrix and a liquid electrolyte consisting of an electrolyte salt dissolved in a solvent therefor, which is dispersed in the polymer matrix. The flame retardance-imparting moieties are derived from halogen or phosphorus-bearing compounds.

Claims

1. A flame retardant solid electrolyte comprising:

an ion conductive polymer matrix having moieties derived from a halogen or phosphorus-bearing polymer and capable of imparting flame retardance to said polymer matrix; and

an electrolyte salt dispersed in said polymer matrix;

wherein said ion conductive polymer matrix consists of a crosslinked product between a polymer of a first at least one compound selected from the group consisting of alkylene oxides and glycidyl ethers, which polymer is modified with a crosslinkable multiple bond group at part or all of terminal end groups and at functional groups in a polymer chain; and

a second at least one compound selected from the group consisting of a compound represented by formula (1), (2) and (3);

space="preserve" listing-type="equation">(CH.sub.2 ═

CR.sub.2 COO).sub.n R.sub.1 (

     1)

wherein R₁ represents a halogen-containing aliphatic hydrocarbon residue, a halogen-containing aromatic hydrocarbon residue, or R'"'"' OR₁ '"'"', in which R'"'"' represents an aliphatic or aromatic hydrocarbon residue, and R₁ '"'"' represents a halogen-containing aliphatic or aromatic hydrocarbon residue, R₂ represents H or CH₃, and n is an integer of 1 to 3;

space="preserve" listing-type="equation">(CH.sub.2 ═

CR.sub.2 COO).sub.n (R.sub.3 O).sub.m PO(OR.sub.4).sub.3-m(

     2)

wherein R₂ has the same meaning as defined above, R₃ represents an aliphatic or aromatic hydrocarbon residue, R₄ represents hydrogen, an aliphatic or aromatic hydrocarbon residue or a phosphorus-bearing aliphatic or aromatic hydrocarbon group, m is an integer of 1 to 3, and n is an integer of 1 to 3; and

##STR8## wherein R₂ has the same meaning as defined above, R₃ has the same meaning as defined in (2), R₄ '"'"' represents hydrogen, an aliphatic or aromatic hydrocarbon residue, or --(R₃ O)_m'"'"' --R₅, in which R₃ is as defined above, and R₅ represents hydrogen, or an aliphatic or aromatic hydrocarbon residue, and m'"'"' is an integer of from 0 to 20.

2. A flame retardant solid electrolyte according to claim 1, wherein said polymer consists of a homopolymer of at least one compound selected from the group consisting of alkylene oxides and glycidyl ethers.

3. A flame retardant solid electrolyte according to claim 1, wherein said polymer consists of a copolymer of compounds selected from the group consisting of alkylene oxides and glycidyl ethers.

4. A flame retardant solid electrolyte according to claim 1, wherein the second at least one compound includes the compound represented by formula (I);

##STR9##

5. A flame retardant solid electrolyte according to claim 1, wherein the second at least one compound includes the compound represented by formula (II);

6. A flame retardant solid electrolyte according to claim 1, wherein the second at least one compound includes the compound represented by formula (III);

7. A flame retardant solid electrolyte according to claim 1, wherein said multiple bond group is selected from the group consisting of an acrylic acid group, an acryloyl group and a methacryloyl group.

8. A flame retardant solid electrolyte according to claim 1, wherein said crosslinked product is obtained by irradiation of UV light, an electron beam or a γ

-ray or by application of heat.

9. A flame retardant solid electrolyte according to claim 1, wherein said polymer and the second at least one compound are present at a mixing ratio by weight of 40:

60 to 98;

2.

10. A flame retardant solid electrolyte according to claim 1, wherein said electrolyte salt consists of a combination of a lithium cation and at least one anion selected from the group consisting of BF₄, PF₆, ClO₄, AsF₆, CF₃ SO₃, N(CF₃ SO₂)₂, N(C₂ F₅ SO₂)₂, C(CF₃ SO₂)₃ and derivatives thereof.

11. A flame retardant solid electrolyte according to claim 1, further comprising a solvent dissolving said electrolyte salt therein to provide a liquid electrolyte, and said liquid electrolyte is dispersed in said polymer matrix.

12. A flame retardant solid electrolyte according to claim 11, wherein said solvent consists of a non-aqueous solvent selected from the group consisting of carbonates, lactones, ethers, sulfolanes, dioxolanes and mixtures thereof.

13. A flame retardant solid electrolyte according to claim 11, wherein said liquid electrolyte is present at a ratio by weight, to said polymer matrix, of 90:

10 to 10;

90.

14. A lithium secondary cell comprising the solid electrolyte defined in claim 1.

16. A flame retardant solid electrolyte according to claim 1, wherein said at least one compound includes the compound represented by formula (I);

##STR11##

15. A flame retardant solid electrolyte comprising:

a non-ion-conductive polymer matrix having moieties derived from a halogen or phosphorus-bearing compound and capable of imparting flame retardance to said polymer matrix; and

a liquid electrolyte comprising an electrolyte salt dissolved in a solvent therefor, said liquid electrolyte being dispersed in said polymer matrix;

wherein said non-ion-conductive polymer matrix consists of a copolymer obtained by crosslinking reaction between a copolymerizable monomer and at least one compound selected from the group consisting of a compound represented by formula (1), (2) and (3);

space="preserve" listing-type="equation">(CH.sub.2 ═

CR.sub.2 COO).sub.n R.sub.1 (

     1)

wherein R₁ represents a halogen-containing aliphatic hydrocarbon residue, a halogen-containing aromatic hydrocarbon residue, or R'"'"' OR₁ '"'"', in which R'"'"' represents an aliphatic or aromatic hydrocarbon residue, and R₁ '"'"' represents a halogen-containing aliphatic or aromatic hydrocarbon residue, R₂ represents H or CH₃, and n is an integer of 1 to 3;

space="preserve" listing-type="equation">(CH.sub.2 ═

CR.sub.2 COO).sub.n (R.sub.3 O).sub.m PO(OR.sub.4).sub.3-m(

     2)

wherein R₂ has the same meaning as defined above, R₃ represents an aliphatic or aromatic hydrocarbon residue, R₄ represents hydrogen, an aliphatic or aromatic hydrocarbon residue or a phosphorus-bearing aliphatic or aromatic hydrocarbon group, m is an integer of 1 to 3, and n is an integer of 1 to 3; and

##STR10## wherein R₂ has the same meaning as defined above, R₃ has the same meaning as defined (2), R₄ '"'"' represents hydrogen, an aliphatic or aromatic hydrocarbon residue, or --(R₃ O)_m'"'"' --R₅, in which R₃ is defined above, and R₅ represents hydrogen, or an aliphatic or aromatic hydrocarbon residue, and m'"'"' is an integer of from 0 to 20.

17. A flame retardant solid electrolyte according to claim 15, wherein said at least one compound includes the compound represented by formula (II);

18. A flame retardant solid electrolyte according to claim 15, wherein said at least one compound includes the compound represented by formula (III);

19. A flame retardant solid electrolyte according to claim 15, wherein said copolymerizable monomer consists of at least one member selected from the group consisting of vinylidene chloride, acrylonitrile and methyl methacrylate.

20. A flame retardant solid electrolyte according to claim 15, wherein said at least one compound is present in an amount of 2 to 60 wt % in said non-ion-conductive polymer matrix.

21. A flame retardant solid electrolyte according to claim 15, wherein said electrolyte salt consists of at least one combination of a lithium cation and at least one anion selected from the group consisting of BF₄, PF₆, ClO₄, AsF₆, CF₃ SO₃, N(CF₃ SO₂)₂, N(C₂ F₅ SO₂)₂, C(CF₃ SO₂)₃ and derivatives thereof.

22. A flame retardant solid electrolyte according to claim 15, wherein said solvent is selected from the group consisting of carbonates, lactones, ethers, sulfolanes, dioxolanes and mixtures thereof.

23. A flame retardant solid electrolyte according to claim 15, wherein said liquid electrolyte is present at a ratio by weight, to said polymer matrix, of 90:

10 to 10;

90.

24. A lithium secondary cell comprising the flame retardant electrolyte defined in claim 15.