CN104838534B - Molten salt electrolyte battery and manufacture method thereof - Google Patents
Molten salt electrolyte battery and manufacture method thereof Download PDFInfo
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- CN104838534B CN104838534B CN201380062202.2A CN201380062202A CN104838534B CN 104838534 B CN104838534 B CN 104838534B CN 201380062202 A CN201380062202 A CN 201380062202A CN 104838534 B CN104838534 B CN 104838534B
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- moisture
- barrier film
- negative pole
- salt
- fuse salt
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- 239000011780 sodium chloride Substances 0.000 title claims abstract description 232
- 150000003839 salts Chemical class 0.000 title claims abstract description 225
- 239000003792 electrolyte Substances 0.000 title claims abstract description 119
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 claims description 21
- 229910052783 alkali metal Inorganic materials 0.000 claims description 17
- 150000001340 alkali metals Chemical group 0.000 claims description 17
- 229910052731 fluorine Inorganic materials 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 11
- 229910006080 SO2X Inorganic materials 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 125000001153 fluoro group Chemical group F* 0.000 claims description 7
- 125000003709 fluoroalkyl group Chemical group 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims 1
- 239000010408 film Substances 0.000 description 133
- 239000011734 sodium Substances 0.000 description 71
- 229910052708 sodium Inorganic materials 0.000 description 63
- 229910052751 metal Inorganic materials 0.000 description 61
- 239000002184 metal Substances 0.000 description 57
- KEAYESYHFKHZAL-UHFFFAOYSA-N sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 57
- 238000007792 addition Methods 0.000 description 45
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 33
- 239000010410 layer Substances 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- 230000004087 circulation Effects 0.000 description 23
- 210000001787 Dendrites Anatomy 0.000 description 22
- 239000000463 material Substances 0.000 description 22
- 238000011068 load Methods 0.000 description 20
- 239000007774 positive electrode material Substances 0.000 description 19
- 239000003365 glass fiber Substances 0.000 description 18
- 239000004734 Polyphenylene sulfide Substances 0.000 description 16
- 239000012298 atmosphere Substances 0.000 description 16
- 229920000069 poly(p-phenylene sulfide) Polymers 0.000 description 16
- 239000000377 silicon dioxide Substances 0.000 description 15
- 239000004020 conductor Substances 0.000 description 14
- 229920000098 polyolefin Polymers 0.000 description 14
- 229910052782 aluminium Inorganic materials 0.000 description 13
- 239000006183 anode active material Substances 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 13
- -1 nitrogenous heterocyclic organic cation Chemical class 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 230000001629 suppression Effects 0.000 description 12
- 238000005275 alloying Methods 0.000 description 11
- 239000011737 fluorine Substances 0.000 description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- RWRDLPDLKQPQOW-UHFFFAOYSA-N tetrahydropyrrole Substances C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N al2o3 Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 239000011258 core-shell material Substances 0.000 description 9
- 150000002466 imines Chemical class 0.000 description 9
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminum Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 229910052759 nickel Inorganic materials 0.000 description 8
- 235000012239 silicon dioxide Nutrition 0.000 description 8
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 7
- 239000011149 active material Substances 0.000 description 7
- 239000006258 conductive agent Substances 0.000 description 7
- 239000002608 ionic liquid Substances 0.000 description 7
- 229910001948 sodium oxide Inorganic materials 0.000 description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 7
- 229910052725 zinc Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- 229910000838 Al alloy Inorganic materials 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 210000004027 cells Anatomy 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 6
- 229910052744 lithium Inorganic materials 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000004745 nonwoven fabric Substances 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 210000002356 Skeleton Anatomy 0.000 description 5
- 229910052803 cobalt Inorganic materials 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000005611 electricity Effects 0.000 description 5
- 230000002401 inhibitory effect Effects 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 150000003609 titanium compounds Chemical class 0.000 description 5
- BOSLFXXHUGEHDC-UHFFFAOYSA-N 2-methyl-1-propylpyrrolidine Chemical compound CCCN1CCCC1C BOSLFXXHUGEHDC-UHFFFAOYSA-N 0.000 description 4
- 229920000914 Metallic fiber Polymers 0.000 description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052804 chromium Inorganic materials 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N tin hydride Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 229950000845 Politef Drugs 0.000 description 3
- 229940037179 Potassium Ion Drugs 0.000 description 3
- LPEVOCIDQNXQDM-UHFFFAOYSA-L [Na].[Cr](=O)(O)O Chemical compound [Na].[Cr](=O)(O)O LPEVOCIDQNXQDM-UHFFFAOYSA-L 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910001884 aluminium oxide Inorganic materials 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 150000002892 organic cations Chemical class 0.000 description 3
- 229910001414 potassium ion Inorganic materials 0.000 description 3
- NPYPAHLBTDXSSS-UHFFFAOYSA-N potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 3
- 239000011257 shell material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N Cesium Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 2
- 229910000528 Na alloy Inorganic materials 0.000 description 2
- 235000006508 Nelumbo nucifera Nutrition 0.000 description 2
- 240000002853 Nelumbo nucifera Species 0.000 description 2
- 235000006510 Nelumbo pentapetala Nutrition 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000000996 additive Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 239000005030 aluminium foil Substances 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910052792 caesium Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000005443 coulometric titration Methods 0.000 description 2
- 230000001186 cumulative Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium(0) Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 125000004435 hydrogen atoms Chemical group [H]* 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 239000011229 interlayer Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N n-methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000000630 rising Effects 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 238000003466 welding Methods 0.000 description 2
- OQMIRQSWHKCKNJ-UHFFFAOYSA-N 1,1-difluoroethene;1,1,2,3,3,3-hexafluoroprop-1-ene Chemical compound FC(F)=C.FC(F)=C(F)C(F)(F)F OQMIRQSWHKCKNJ-UHFFFAOYSA-N 0.000 description 1
- AMIGMYIOHANALP-UHFFFAOYSA-N 1,2-diethylpyrrolidine Chemical compound CCC1CCCN1CC AMIGMYIOHANALP-UHFFFAOYSA-N 0.000 description 1
- PXHHIBMOFPCBJQ-UHFFFAOYSA-N 1,2-dimethylpyrrolidine Chemical compound CC1CCCN1C PXHHIBMOFPCBJQ-UHFFFAOYSA-N 0.000 description 1
- WTFJDUDZSYSAGI-UHFFFAOYSA-N 3-ethyl-2-propyl-1H-pyrrole Chemical compound CCCC=1NC=CC=1CC WTFJDUDZSYSAGI-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N Imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium Ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 229910004848 Na2/3Fe1/3Mn2/3O2 Inorganic materials 0.000 description 1
- 229910004591 Na2FePO4F Inorganic materials 0.000 description 1
- 229910020293 Na2Ti3O7 Inorganic materials 0.000 description 1
- 229910020532 Na4Ti5O12 Inorganic materials 0.000 description 1
- 229910021271 NaCrO2 Inorganic materials 0.000 description 1
- 229910019324 NaMnF3 Inorganic materials 0.000 description 1
- 229910019333 NaMnPO4 Inorganic materials 0.000 description 1
- 229910001222 NaVPO4F Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene (PE) Substances 0.000 description 1
- 229920001721 Polyimide Polymers 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910003092 TiS2 Inorganic materials 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J Titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- CFJRPNFOLVDFMJ-UHFFFAOYSA-N Titanium disulfide Chemical compound S=[Ti]=S CFJRPNFOLVDFMJ-UHFFFAOYSA-N 0.000 description 1
- BNBLBRISEAQIHU-UHFFFAOYSA-N [Na+].[Na+].[O-][Mn]([O-])(=O)=O Chemical compound [Na+].[Na+].[O-][Mn]([O-])(=O)=O BNBLBRISEAQIHU-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 229910000573 alkali metal alloy Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- NCMHKCKGHRPLCM-UHFFFAOYSA-N caesium(1+) Chemical compound [Cs+] NCMHKCKGHRPLCM-UHFFFAOYSA-N 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001424 calcium ion Inorganic materials 0.000 description 1
- 239000004917 carbon fiber Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 235000010675 chips/crisps Nutrition 0.000 description 1
- 229920000891 common polymer Polymers 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 230000002349 favourable Effects 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 125000006343 heptafluoro propyl group Chemical group 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-M iodide Chemical compound [I-] XMBWDFGMSWQBCA-UHFFFAOYSA-M 0.000 description 1
- 229940006461 iodide ion Drugs 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000003273 ketjen black Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229910001425 magnesium ion Inorganic materials 0.000 description 1
- JLVVSXFLKOJNIY-UHFFFAOYSA-N magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002891 organic anions Chemical class 0.000 description 1
- 125000006340 pentafluoro ethyl group Chemical group FC(F)(F)C(F)(F)* 0.000 description 1
- NQRYJNQNLNOLGT-UHFFFAOYSA-N piperidine Chemical class C1CCNCC1 NQRYJNQNLNOLGT-UHFFFAOYSA-N 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000011528 polyamide (building material) Substances 0.000 description 1
- 150000004291 polyenes Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 159000000001 potassium salts Chemical class 0.000 description 1
- 230000003334 potential Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 1
- 229910052701 rubidium Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 150000003623 transition metal compounds Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Abstract
A kind of molten salt electrolyte battery, comprise: positive pole, negative pole, the barrier film being placed between described positive pole and described negative pole and electrolyte, wherein said electrolyte comprises fuse salt, and described fuse salt at least contains sodium ion, and moisture We1 in described fuse salt is below 300ppm in mass ratio.
Description
Technical field
The present invention relates to the molten salt electrolyte battery of a kind of precipitation wherein inhibiting sodium dendrite.
Background technology
In recent years, the technology natural energy of sunlight, wind-force etc. being converted to electric energy has caused concern.It addition, conduct
Can store the battery with high-energy-density of a large amount of electric energy, the demand of rechargeable nonaqueous electrolytic battery is the most increasing.
In rechargeable nonaqueous electrolytic battery, it is contemplated that light weight and high electromotive force, lithium rechargeable battery is the most promising.So
And, lithium rechargeable battery each contains inflammable organic bath, it is therefore desirable to for guaranteeing safe high cost and being difficult to
Persistently use in high-temperature region.Additionally, the price of lithium resource raises.
Therefore, the exploitation using anti-flammability fuse salt as the molten salt electrolyte battery of electrolyte has been promoted.Fuse salt has excellent
Different heat stability and the safety that can relatively easily guarantee, be suitable for persistently using in high-temperature region.It addition, molten salt electrolyte battery
The fuse salt of cation containing the cheap alkali metal (particularly sodium) in addition to lithium can be used as electrolyte, thus reduce system
Cause this.
Such as, double (fluorine sulphonyl) imines sodium (NaFSA) and the mixing of double (fluorine sulphonyl) imines potassium (KFSA) are had been developed for
Thing is as the fuse salt (patent documentation 1) with low melting point and superior heat-stability.
It addition, have been proposed for being used as in the positive pole of molten salt electrolyte battery the transition metal oxide containing sodium such as chromous acid sodium
Positive electrode active materials.On the other hand, it has been proposed that by the metal of sodium, sodium alloy and sodium alloying, material with carbon element, pottery material
Material etc. are used as the negative active core-shell material in negative pole.Especially, metal such as zinc, stannum, silicon etc. is relatively inexpensive, and be desired as can
For realizing the negative material (patent documentation 2 and patent documentation 3) of high power capacity.
Prior art literature
Patent documentation
Patent documentation 1: Japanese Patent Laid-Open 2009-67644 publication
Patent documentation 2: Japanese Patent Laid-Open 2011-192474 publication
Patent documentation 3: Japanese Patent Laid-Open 2011-249287 publication
Summary of the invention
Technical problem
But, no matter the type of negative active core-shell material, common molten salt electrolyte battery has easily precipitation on negative pole
The problem of sodium dendrite.Such as, when for a long time molten salt electrolyte battery is repeated discharge and recharge, sodium dendrite is raw towards positive pole from negative pole
Long, penetrate barrier film, then arrive positive pole, thus it may happen that internal short-circuit.It addition, when the dendrite of growth comes off from negative pole
Time, the sodium come off can not act on discharge and recharge reaction, thus reduce the capacity of molten salt electrolyte battery.
In molten salt electrolyte battery, from the viewpoint of the side reaction of suppression fuse salt in addition to discharge and recharge is reacted, incited somebody to action
Moisture in battery is reduced to specific degrees.Generation as the hydrolysis of side reaction may be due to product
Cause the chemical damage to barrier film or be likely to be due to suppress as the product of impedance components stable electrode reaction.Cause
This, before assembling molten salt electrolyte battery, be generally dried positive pole, negative pole, barrier film and fuse salt.By dried just
Pole, negative pole, barrier film and fuse salt each in moisture be reduced in mass ratio be about 400ppm～1000ppm.
But, have appreciated that in molten salt electrolyte battery, not only the side reaction of fuse salt, and the precipitation degree of sodium dendrite
All by the extreme influence of moisture in battery.It addition, it has shown that the generation frequency of the internal short-circuit caused due to dendrite
Rate is very sensitive to the moisture in battery, and it is unsatisfactory that moisture is only reduced to common phase same level.
To this reason unclear, but possible reason is, molten salt electrolyte battery can use at relatively high temperature,
Therefore between sodium and moisture, show high response.Specifically, sodium produces sodium oxide with the reaction of moisture, and sodium dendrite is with wherein
The position producing sodium oxide grows as starting point.
Therefore, in order to suppress the short circuit between positive pole and negative pole, it is important that than generally more reduce at molten salt electrolyte battery
Interior moisture.It addition, particularly importantly control in the migration path of sodium ion, i.e. between positive pole and negative pole every
Moisture in film.
Technical scheme
It is thought that in the moisture contained in positive pole, negative pole and barrier film, moveable moisture moves to melting in battery
In salt.It addition, barrier film is placed between positive pole and negative pole, and fuse salt is impregnated in the hole of barrier film.Therefore, in order to reduce at alkali
Moisture in the migration path of metal ion thus suppress internal short-circuit, it is necessary to strictly control the moisture in fuse salt
Content.
More than in view of, in one aspect of the invention, the present invention relates to comprise positive pole, negative pole, be placed between positive pole and negative pole
Barrier film and the molten salt electrolyte battery of electrolyte, wherein said electrolyte comprises fuse salt, described fuse salt at least contain sodium from
Son, and moisture We1 in fuse salt is below 300ppm in mass ratio.In described molten salt electrolyte battery, can suppress
The precipitation of sodium dendrite, and thus can greatly reduce the frequency that internal short-circuit occurs.
In another aspect of this invention, the present invention relates to the example of a kind of method manufacturing molten salt electrolyte battery.The method bag
Including: prepare the step that moisture Wp is the positive pole of below 300ppm in mass ratio, preparing moisture Wn is in mass ratio
The step of the negative pole of below 400ppm, prepares moisture We2 and is below 50ppm in mass ratio and at least contains the molten of sodium ion
Melt the salt step as electrolyte, prepare the step that moisture Ws is the barrier film of below 350ppm in mass ratio, and by institute
State barrier film be placed between described positive pole and described negative pole and described positive pole and described negative pole stacked thus formed electrode group,
And the step described electrode group impregnated with described fuse salt.I.e., in the process, not only to the moisture in fuse salt
Content and the moisture in positive pole, negative pole and barrier film is strictly controlled.
Moisture We1 in fuse salt in molten salt electrolyte battery is preferably below 300ppm in mass ratio.It addition, work as
When moisture We1 is reduced to below 200ppm, the effect that suppression internal short-circuit occurs becomes notable, and can realize more excellent
Different cycle characteristics.
Fuse salt preferably comprises the free N (SO of choosing2X1)(SO2X2) M (wherein X1And X2The most independent for fluorine atom or tool
Have the fluoroalkyl of 1～8 carbon atom, and M be alkali metal or have nitrogenous heterocyclic organic cation) in the compound that represents
At least one.Fuse salt at least contains following compound, and this compound contains sodium ion as M.Thus, it is possible to the most such as
Molten salt electrolyte battery is used under the high temperature of more than 70 DEG C.Additionally, moisture We1 in the fuse salt in molten salt electrolyte battery is reduced
To below 300ppm and be further reduced to below 200ppm, even if using molten salt electrolyte battery the most for a long time, also
Cause the reaction of sodium ion and moisture hardly.Therefore, hardly from reaction generation as starting point, by sodium with moisture
Sodium oxide growth dendrite.
In a preferred form, fuse salt comprises double (fluorine sulphonyl) imines sodium (NaFSA) and double (fluorine sulphonyl) imines potassium
(KFSA) with the mixture of the mol ratio of NaFSA/KFSA=40/60～70/30.In the most preferably form, fuse salt bag
Containing methyl-propyl pyrrolidineDouble (fluorine sulphonyl) imines (Py13FSA) and double (fluorine sulphonyl) imines sodium (NaFSA) are with Py13FSA/
The mixture of the mol ratio of NaFSA=97/3～80/20.By using this fuse salt, even if can manufacture relatively low
At a temperature of the molten salt electrolyte battery that can also use, the effect causing dendrite inhibition to be formed increases.
In a preferred form, negative pole comprises the anode collector being made up of the first metal and covers anode collector
Second metal at least some of surface.First metal be not with the metal of sodium alloying, the second metal is and sodium alloying
Metal.Make more specifically, molten salt electrolyte battery contains aluminum or aluminum alloy as the first metal, Yi Jixi, ashbury metal, zinc or kirsite
It it is the second metal.The negative pole with this structure causes sodium to repeat along with discharge and recharge to separate out and dissolve, and thus has high pressing down
The necessity that dendrite processed is formed.By moisture We1 in the fuse salt in molten salt electrolyte battery is reduced to below 300ppm,
Even if in the negative pole that the precipitation and dissolving that use wherein sodium repeat, it is also possible to be significantly improved cycle characteristics.
In the most preferably form, negative pole comprises the anode collector being made up of the first metal and in anode collector
The anode active material layer formed on surface.First metal be not with the metal of sodium alloying, anode active material layer contains choosing
At least one in the titanium compound of self-contained sodium and the graphited carbon of difficulty is as negative active core-shell material.There is the negative pole of this structure
Originally the formation of little dendrite is caused along with discharge and recharge.But, when molten salt electrolyte battery being overcharged or battery is polluted by foreign substance
Time, it is possible that dendrite.On the other hand, even if when above-mentioned situation about not expecting occurs, by by molten salt electrolyte battery
Moisture We1 in fuse salt is reduced to below 300ppm and also significantly decreases the probability that dendrite occurs.Therefore, it can show
Write the reliability improving molten salt electrolyte battery.
In a preferred form, positive pole comprises cathode collector and the positive-active formed on the surface of cathode collector
Material layer.Anode active material layer contains Na1-xM1 xCr1-yM2 yO2(0≤x≤2/3,0≤y≤2/3, and M1And M2The most independent
Be at least one in Ni, Co, Mn, Fe and Al) as positive electrode active materials.Described positive pole be low cost and along with
The reversibility of the structural change of discharge and recharge is excellent, thus can manufacture the molten salt electrolyte battery with excellent cycle characteristics.
In a preferred form, barrier film is made up of glass fibre.Glass fibre easily absorbs moisture and thus melted
The introducing of moisture is generally easily caused in salt battery.On the other hand, when moisture Ws in barrier film is controlled in mass ratio
After below 350ppm, when being introduced in battery by barrier film, eliminate this probability.It addition, by using glass fibre to be formed
Barrier film makes the thermostability of barrier film be obviously enhanced, and thus can manufacture and be more suitable for the at high temperature long-time fuse salt electricity used
Pond.
The barrier film being made up of glass fibre preferably has 20 μm～the thickness of 500 μm.This can more effectively suppress internal
Short circuit and make the barrier film volume occupying in battery be in beneficially to manufacture in the range of high-capacity battery.Therefore, it can manufacture tool
There is the battery of high reliability and high power capacity.It addition, in molten salt electrolyte battery, be applied to the thickness of the barrier film being made up of glass fibre
Compressive load on direction is preferably 0.1MPa～1MPa.This can more effectively suppress internal short-circuit.
In the most preferably form, barrier film is made up of the polyolefin containing silicon dioxide.Silicon dioxide is prone to absorb water
Divide and thus generally easily cause in molten salt electrolyte battery the introducing of moisture.On the other hand, when by the moisture in barrier film
After Ws controls in mass ratio as below 350ppm, when being introduced in battery by barrier film, eliminate this probability.It addition, by making
Forming barrier film with the polyolefin containing silicon dioxide makes the thermostability of barrier film be obviously enhanced.
The barrier film being made up of the polyolefin containing silicon dioxide preferably has 10 μm～the thickness of 500 μm.This can more have
Effect ground suppression internal short-circuit and make the barrier film volume occupying in battery be in beneficially to manufacture in the range of high-capacity battery.Separately
Outward, in molten salt electrolyte battery, the compression being applied on the thickness direction of barrier film be made up of the polyolefin containing silicon dioxide carries
Lotus is preferably 0.1MPa～14MPa.This can more effectively suppress internal short-circuit and can reduce internal resistance.
In the most preferably form, barrier film is made up of fluororesin or polyphenylene sulfide (PPS).Fluororesin and PPS have height
Thermostability and be difficult to absorb moisture, from there through be at high temperature dried the short time can by barrier film moisture Ws reduce
To below 350ppm.Therefore, this advantageously reduces the moisture in molten salt electrolyte battery.
The barrier film being made up of fluororesin or PPS preferably has 10 μm～the thickness of 500 μm.In this can more effectively suppress
Portion's short circuit and make the barrier film volume occupying in battery be in beneficially to manufacture in the range of high-capacity battery.
It addition, in molten salt electrolyte battery, the compression being applied on the thickness direction of barrier film be made up of fluororesin or PPS carries
Lotus is preferably 0.1MPa～14MPa.This can more effectively suppress internal short-circuit and can reduce internal resistance.
Barrier film has many can keep the hole of moisture, and is placed between positive pole and negative pole, it is thus regarded that reduce water
The importance dividing content is the biggest.Therefore, in above-mentioned manufacture method, in the step preparing barrier film, preferably more than 90 DEG C
Under baking temperature, in the reduced pressure atmosphere of below 10Pa, barrier film is dried.As a result, it is possible to will be every within the relatively short time
Moisture Ws in film is reduced to below 350ppm in mass ratio.Although the upper limit of baking temperature changes along with the material of barrier film
Becoming, but temperature is the highest, the time that being dried needs can be the shortest.It addition, also, it is preferred that under baking temperature more than 90 DEG C and
Positive pole and negative pole are dried by the reduced pressure atmosphere of below 10Pa.
On the other hand, prepare fuse salt step in, preferably below-50 DEG C in the atmosphere of dew point temperature by solid base
Metal immerses in the fuse salt of molten condition and is carrying out less than fuse salt to molten condition at a temperature of alkali-metal fusing point
Stirring.As a result, it is possible to change places at relatively short time content, moisture We2 in fuse salt is reduced in mass ratio
Below 50ppm and be further reduced to below 20ppm.
Beneficial effect
According to the present invention, the moisture in each parts in battery is suitably controlled, thus suppression is due to sodium
The formation of the sodium oxide that the reaction with moisture causes and dendrite are from the precipitation of the sodium oxide as starting point.It addition, be just placed on
Moisture We1 in fuse salt between pole and negative pole controls at below 300ppm, thus can dendrite inhibition edge effectively
The growth of pore (i.e. the migration path of sodium ion) in barrier film.Therefore, it can suppression short circuit between positive pole and negative pole, and can
To realize excellent cycle characteristics.
Accompanying drawing explanation
[Fig. 1] Fig. 1 is the front elevation of the positive pole according to one embodiment of the present invention.
[Fig. 2] Fig. 2 is the cross-sectional view that the line II-II along Fig. 1 takes.
[Fig. 3] Fig. 3 is the front elevation of the negative pole according to one embodiment of the present invention.
[Fig. 4] Fig. 4 is the cross-sectional view that the line IV-IV along Fig. 3 takes.
[Fig. 5] Fig. 5 is the perspective of a part of incised notch of battery case of the molten salt electrolyte battery according to one embodiment of the present invention
Figure.
[Fig. 6] Fig. 6 is the longitudinal cross-section schematic diagram that the line VI-VI along Fig. 5 takes.
[Fig. 7] Fig. 7 is the figure of the charging and discharging curve of the molten salt electrolyte battery of display embodiment 1.
[Fig. 8] Fig. 8 is the figure of the charging and discharging curve of the molten salt electrolyte battery of display comparative example 1.
Detailed description of the invention
The present invention relates to molten salt electrolyte battery, described molten salt electrolyte battery comprises positive pole, negative pole, is placed between positive pole and negative pole
Barrier film and the electrolyte comprising fuse salt, described fuse salt at least contains sodium ion.But, by the moisture in fuse salt
We1 is reduced to below 300ppm in mass ratio.In addition to fuse salt, electrolyte contains various additive, but from guaranteeing ionic conduction
From the viewpoint of property and heat stability, electrolyte the most only comprises fuse salt.Even if when electrolyte contains additive, electrolyte
It is also preferred that comprise the fuse salt of more than more than 90 mass % and more preferably 95 mass %.
As it has been described above, by the moisture in battery being controlled the reaction suppressing sodium ion with moisture, described
Sodium ion is the carrier worked in the ionic conduction of molten salt electrolyte battery.Result, it is suppressed that the formation of sodium oxide and sodium gold
The dendrite belonged to is from the precipitation of the sodium oxide as starting point, and reduces the generation of internal short-circuit and the reduction of cycle characteristics.Separately
Outward, the moisture during the precipitation degree of dendrite depends greatly on particularly sodium ion migration path between positive pole and negative pole contains
Amount.Barrier film is placed between positive pole and negative pole, and fuse salt is impregnated in the hole of barrier film.Positive pole, negative pole and barrier film contain
Moisture (moisture that can be detected by karl Fischer (Karl Fischer) method) in great majority movably moisture recognized
For moving in the fuse salt in battery.It is therefore important that moisture We1 in the fuse salt in molten salt electrolyte battery is entered
Row strictly controls, specifically, it is necessary to moisture We1 is reduced to below 300ppm in mass ratio.Work as molten salt electrolyte battery
When interior moisture We1 in fuse salt is more than 300ppm, then it is difficult to suppress generation and the fall of cycle characteristics of internal short-circuit
Low.
Preferably moisture We1 in the fuse salt in molten salt electrolyte battery is reduced to below 200ppm in mass ratio.No
The type of opinion negative material how, and this all increases the effect that dendrite inhibition separates out, and prevents the generation of internal short-circuit further.Separately
Outward, the effect of improvement cycle characteristics is increased.
Fuse salt preferably comprises the free N (SO of choosing2X1)(SO2X2) M (wherein X1And X2It is each independently fluorine atom or tool
Have the fluoroalkyl of 1～8 carbon atom, and M be alkali metal or have nitrogenous heterocyclic organic cation) in the compound that represents
At least one.In this case, fuse salt at least contains N (SO2X1)(SO2X2)·Na.Described fuse salt has relatively low
Fusing point and excellent heat stability, and be advantageous in that and can easily moisture be controlled by aftermentioned method.
From the viewpoint of making the molten salt electrolyte battery with more high power capacity, it is preferably used and comprises for active material layer
The negative pole of metal material.For example, it is possible to alkali metal such as sodium is used for active material layer, maybe can be by the gold with alkali metal alloy
Belong to for active material layer.
The preferred form of negative pole includes the anode collector being such as made up of the first metal and covers anode collector extremely
Second metal on a few part (preferably more than the 80% of the surface of anode collector) surface.Described first metal is not close with sodium
The metal of aurification.Second metal is the metal with sodium alloying and is used as anode active material layer.By not with the of sodium alloying
The anode collector that one metal is constituted can keep intensity within a very long time.It addition, by by the with sodium alloying
Two metals are used for anode active material layer, even if when the cell reaction of precipitated sodium occurs on negative pole, also can easily suppress branch
Brilliant precipitation.
The example of the material of barrier film include but be not especially limited glass fibre, silica containing polyolefin, fluororesin,
Polyphenylene sulfide (PPS), ceramic material (such as aluminium oxide particles) etc..Such as being heated by relatively simple method can be to these
Moisture in any one in material is controlled.
The barrier film being made up of glass fibre preferably has 20 μm～the thickness of 500 μm.This is because under this thickness, can
Maintain the capacity of molten salt electrolyte battery with relative highland, and internal short-circuit seldom occurs.It addition, in molten salt electrolyte battery, be applied to
Compressive load on the thickness direction of the barrier film being made up of glass fibre is preferably 0.1MPa～1MPa.This is considered as because working as
When applying described compressive load, the impedance between positive pole and negative pole is properly controlled, and does not has internal short-circuit to occur.
From the viewpoint of identical, the barrier film being made up of the polyolefin containing silicon dioxide preferably has 10 μm～500 μm
Thickness, and in molten salt electrolyte battery, be applied on the thickness direction of barrier film be made up of the polyolefin containing silicon dioxide
Compressive load is preferably 0.1MPa～14MPa.Additionally, the barrier film being made up of fluororesin or PPS preferably has 10 μm～500 μm
Thickness, and in molten salt electrolyte battery, the compressive load being applied on the thickness direction of barrier film be made up of fluororesin or PPS is preferred
For 0.1MPa～14MPa.
The molten salt electrolyte battery of the present invention can be manufactured by the manufacture method comprised the following steps: prepares moisture
Wp is the step of the positive pole of below 300ppm in mass ratio, prepares the negative pole that moisture Wn is below 400ppm in mass ratio
Step, preparing moisture We2 is below 50ppm and the fuse salt step as electrolyte at least containing sodium ion in mass ratio
Suddenly, prepare the step that moisture Ws is the barrier film of below 350ppm in mass ratio, and described barrier film is placed in described positive pole
And stack between described negative pole and to described positive pole and described negative pole thus form the step of electrode group.By electrode group with molten
Melt salt to be disposed along in battery case, thus complete molten salt electrolyte battery.
As it has been described above, to positive pole, negative pole, fuse salt and barrier film each in moisture be controlled individually, thus
Promote the overall moisture in molten salt electrolyte battery is contained the management of quantitative limitation.But, such as by formation comprise positive pole, negative pole and
The electrode group of barrier film, then carries out reducing the process of the moisture of electrode group, can the moisture in each parts be controlled
In above-mentioned scope.
The step preparing to have the barrier film of moisture within the above range includes, such as more than 90 DEG C (more preferably
90 DEG C～300 DEG C) baking temperature under, below 10Pa, preferred below 1Pa, more preferably below 0.4Pa reduced pressure atmosphere in right
Barrier film is dried.This method is simple and because not increasing manufacturing cost but favourable.Setting up as processing atmosphere
Reduced pressure atmosphere before, beforehand through noble gas (such as nitrogen, helium or argon) or have the dry of less than-50 DEG C dew point temperatures
Dry air replacement processes the air in atmosphere, therefore can effectively remove moisture removal from barrier film.
More specifically, when barrier film is made up of glass fibre, preferably by little for barrier film drying under reduced pressure 2 at 100 DEG C～300 DEG C
Time～24 hours.Preferably by the Stress control of dry atmosphere at below 10Pa and more preferably below 1Pa.
It addition, when barrier film comprises the barrier film containing silicon dioxide, preferably by barrier film drying under reduced pressure at 90 DEG C～120 DEG C
2 hours～24 hours.In this case, also, it is preferred that by the Stress control of dry atmosphere at below 10Pa and more preferably 1Pa
Below.
It addition, when barrier film is by fluororesin such as politef (PTFE) or time PPS makes, preferably by barrier film at 100 DEG C～
Drying under reduced pressure 2 hours～24 hours at 260 DEG C.In this case, also, it is preferred that by the Stress control of dry atmosphere at 10Pa
Below and more preferably below 1Pa.
Furthermore it is possible to carry out under the same terms as above for reduce positive pole and negative pole each in moisture
Drying steps.More specifically, it is preferable to by drying under reduced pressure 2 hours～24 hours at each to positive pole and negative pole comfortable 90 DEG C～200 DEG C.
Preferably by the Stress control of dry atmosphere at below 10Pa and more preferably below 1Pa.
The step preparing to have the fuse salt of moisture We2 in the range of as mentioned above includes, such as-50 DEG C with
In the atmosphere of lower dew point temperature (such as, the inert gas atmosphere of nitrogen, helium or argon or in atmosphere), by solid alkali metal
It is immersed in the fuse salt of molten condition, and is stirring less than fuse salt to molten condition at a temperature of alkali-metal fusing point
Mix.This method removes moisture removal by the chemical reaction of solid alkali metal with the moisture in fuse salt.Because alkali metal is with melted
The reaction of the moisture in salt is quickly carried out, and moisture is in this way reduced to extremely low level by institute.Such as, easily will
Moisture We2 is reduced to below 20ppm in mass ratio.Furthermore it is possible to easily reclaim solid base from the mixture of stirring
Metal, therefore the method be advantageous in that manufacturing cost does not increases.
According to alkali-metal type, solid alkali metal is preferably such as 60 DEG C with the whipping temp of the fuse salt of molten condition
～90 DEG C.Can be by lithium, sodium, caesium etc. as alkali metal, and sodium is cheap, is suitable for removing the moisture in motlten metal.
In this case, positive pole contains the material being electrochemically reacted with sodium ion as positive electrode active materials, and
Negative pole contains the material being electrochemically reacted with sodium ion as negative active core-shell material.Described electrochemical reaction can be to dissolve
Or the reaction of precipitated sodium, release from predetermined material sodium ion or by the reaction sodium ion occlusion to predetermined material, make sodium
Ion departs from from predetermined material or sodium ion is adsorbed the reaction on predetermined material or other kinds of reaction.
Barrier film has the function being physically separated between positive pole and negative pole and guarantees that sodium ion is between positive pole and negative pole
The function of the migration path of movement.In addition to the foregoing materials, various porous chipses can be used for barrier film.
Fuse salt is at least to contain sodium ion as cation and to contain the organic or inorganic anion salt as anion.
Fuse salt is impregnated into by positive pole, negative pole and the hole being placed in the electrode group that barrier film therebetween is constituted, and is used as in the molten state
Electrolyte.That is, the electrolyte of molten salt electrolyte battery mainly (is being also referred to as equal to or higher than at a temperature of fusing point by ionic substance
" ionic liquid ") constitute.According to the purposes of molten salt electrolyte battery, the fusing point of fuse salt can be selected.
Moisture We in moisture Wp in positive pole, the moisture Wn in negative pole, fuse salt and the moisture in barrier film
Any one in content Ws is the moisture measured by Karl_Fischer method.In positive pole and negative pole, respective moisture is
Total moisture in current collector and active material layer.Specifically, by positive pole, negative pole, fuse salt and barrier film
At least one sample is put in the sample cell (cell) of determination of moisture device together with catholyte, and surveys moisture
Fixed.
Catholyte contains alcohol, alkali, sulfur dioxide or iodide ion.Karl_Fischer method is divided into volumetric precipitation method and coulomb to drip
Determine method, but be used herein as the coulometric titration with high analyte precision.Furthermore it is possible to by commercially available karl Fischer moisture titration
(" MKC-610 " that such as manufactured by capital of a country electronics industry Co., Ltd.) is used as determination of moisture device.
By sample being put in the sample cell of the determination of moisture device of full fresh catholyte in nitrogen atmosphere,
The moisture of each parts is measured.For the sample of positive pole, negative pole or barrier film, the weight of sample can at 0.05g～
In the range of 5g.For the sample of fuse salt, the weight of sample can be in the range of 0.05g～3g.Can be equal to being higher than
Fusing point or less than the moisture in fuse salt being measured at a temperature of fusing point.
By battery being taken apart and taken out fuse salt and the moisture of fuse salt being measured, or impregnated by taking-up
There is the barrier film of fuse salt and the moisture of barrier film is measured, can be to moisture We1 in the fuse salt in battery
It is measured.When the moisture of the barrier film being impregnated with fuse salt is measured, by use contain in the sample every
The weight of film and the weight of fuse salt, can be converted to the moisture in fuse salt by the moisture in barrier film.
It follows that each parts are specifically described by an example based on molten salt electrolyte battery.
[positive pole]
Fig. 1 is the front elevation of the positive pole according to one embodiment of the present invention, and Fig. 2 is the horizontal stroke that the line II-II along Fig. 1 takes
Sectional view.
Positive pole 2 comprises cathode collector 2a and anode active material layer 2b being fixed in cathode collector 2a.Positive pole is lived
Property material layer 2b contains the positive electrode active materials as neccessary composition and can be possibly together with the one-tenth optionally such as binding agent, conductive agent
Point.
The non-woven fabrics that by metal forming, can be made up of metallic fiber, metal porous etc. as cathode collector 2a.In view of
Stability under anodic potentials, the metal constituting cathode collector is preferably aluminum or aluminum alloy, but is not particularly limited.It is used as
The thickness of the metal forming of cathode collector is such as 10 μm～50 μm, and the thickness of metallic fiber nonwoven fabric or metal porous is
Such as 100 μm～600 μm.Furthermore it is possible to form current collection conductor strip 2c in cathode collector 2a.Conductor strip 2c can be such as figure
Form as one with cathode collector shown in 1 and maybe by welding etc., the conductor strip independently formed can be connected to positive pole current collection
Device.
From the viewpoint of heat stability and electrochemical stability, preferably the transistion metal compound containing sodium is used as positive pole
Active material.Preferably will there is the compound of the layer structure allowing sodium to come in and go out at interlayer as the transition metal compound containing sodium
Thing, but be not particularly limited.
Such as, the transistion metal compound containing sodium is preferably selected from chromous acid sodium (NaCrO2) and ferrum sodium manganate (Na2/ 3Fe1/3Mn2/3O2At least one in).It addition, Cr or Na of chromous acid sodium can be replaced by other element portions, and ferrimanganic acid
Fe, Mn or Na of sodium can be replaced by other element portions.The example of the compound that can use includes Na1-xM1 xCr1-yM2 yO2
(0≤x≤2/3,0≤y≤2/3, M1And M2The metallic element being each independently in addition to Cr and Na, for example, selected from Ni, Co,
At least one in Mn, Fe and Al) and Na2/3-xM3 xFe1/3-yMn2/3-zM4 y+zO2(0≤x≤1/3,0≤y≤1/3,0≤z≤1/
3, M3And M4The metallic element being each independently in addition to Fe, Mn and Na, for example, at least in Ni, Co, Al and Cr
Kind).Other examples that can use include NaMnF3、Na2FePO4F、NaVPO4F、NaCoPO4、NaNiPO4、NaMnPO4、
NaMn1.5Ni0.5O4、NaMn0.5Ni0.5O2、TiS2、FeF3Deng.Positive electrode active materials can be used alone or can be with polytype
Be applied in combination.It addition, M1And M3Respectively occupy the element in Na site, M2For occupying the element in Cr site, M4For occupy Fe or
The element in Mn site.
Binding agent plays bonding positive electrode active materials and positive electrode active materials is fixed to the effect of cathode collector.Can make
The example of binding agent include fluororesin, polyamide, polyimides, polyamidoimide etc..The fluororesin that can use
Example includes that polyvinylidene fluoride, politef, tetrafluoraoethylene-hexafluoropropylene copolymer, vinylidene fluoride-hexafluoropropene are common
Polymers etc..Positive electrode active materials based on 100 mass parts, the amount of binding agent is preferably 1 mass parts～10 mass parts and more preferably 3
Mass parts～5 mass parts.
The example of the conductive agent contained in positive pole includes graphite, white carbon black, carbon fiber etc..Wherein, because by using less
Amount is easy with forming conductive path, so white carbon black is particularly preferred.The example of white carbon black include acetylene black, Ketjen black,
Heat is black.Positive electrode active materials based on 100 mass parts, the amount of conductive agent is preferably 5 mass parts～15 mass parts and more preferably 5
Mass parts～10 mass parts.
[negative pole]
Fig. 3 is the front elevation of the negative pole according to one embodiment of the present invention, and Fig. 4 is the horizontal stroke that the line IV-IV along Fig. 3 takes
Sectional view.
Negative pole 3 comprises anode collector 3a and anode active material layer 3b being fixed in anode collector 3a.Such as, may be used
With by sodium, sodium alloy or with the metal of sodium alloying, anode active material layer 3b can be used for.Such negative pole such as comprise by
The anode collector of the first metal composition and second metal at least some of surface of covering anode collector.
In this case, the first metal be not with the metal of sodium alloying, the second metal is the metal with sodium alloying.
The non-woven fabrics by metal forming, can being made up of metallic fiber or metal porous are used as to be made up of the first metal
Anode collector.First metal is preferably aluminum, aluminium alloy, copper, copper alloy, nickel, nickel alloy etc. because such metal not with sodium
Alloying and be stable under negative pole current potential.Wherein, it is contemplated that excellent light weight, preferably aluminum and aluminium alloy.It addition, at aluminum
In alloy, the amount of metal ingredient (such as Fe, Si, Ni, Mn etc.) in addition to aluminum is preferably below 0.5 mass %.As negative pole current collection
The thickness of the metal forming of device is such as 10 μm～50 μm, and the thickness of metallic fiber nonwoven fabric or metal porous is such as 100 μ
M～600 μm.Furthermore it is possible to form current collection conductor strip 3c in anode collector 3a.Conductor strip 3c can be as shown in Figure 3
Form as one with anode collector and maybe by welding etc., the conductor strip independently formed can be connected to anode collector.
Bimetallic example includes zinc, kirsite, stannum, ashbury metal, silicon, silicon alloy etc..Wherein, it is contemplated that with fuse salt
Good wettability, preferably zinc and kirsite.The thickness of the anode active material layer being made up of the second metal is such as 0.05 μm
～1 μm.It addition, the amount of the metal ingredient in addition to zinc or stannum (such as Fe, Ni, Si, Mn etc.) is preferred in kirsite or ashbury metal
It it is below 0.5 mass %.
The example of the preferred form of negative pole comprises the anode collector and covering being made up of aluminum or aluminum alloy (the first metal)
The zinc at least some of surface of anode collector, kirsite, stannum, ashbury metal (the second metal).This negative pole have high power capacity,
Low deterioration in a long time, and show, by the moisture in control battery, the effect that bigger dendrite inhibition separates out
Really.
Can manufacture be made up of the second metal by such as the bimetallic being adhered to or be squeezed to anode collector
Anode active material layer.It addition, can be by the second Metal gasification and adhesion by gas phase process such as vacuum deposition method, sputtering method etc.
To anode collector, or bimetallic minuteness particle can be adhered to negative pole current collection by electrochemical method such as galvanoplastic etc.
Device.Thin and uniform anode active material layer can be formed by gas phase process or electro-plating method.
Anode active material layer 3b contains the negative active core-shell material as neccessary composition and can be possibly together with binding agent, conductive agent
Deng composition optionally.Can be used in negative pole using by the same instance of the material being used for positive pole constituent described
Binding agent and conductive agent.Negative active core-shell materials based on 100 mass parts, the amount of binding agent is preferably 1 mass parts～10 mass
Part and more preferably 3 mass parts～5 mass parts.Negative active core-shell materials based on 100 mass parts, the amount of conductive agent is preferably 5 mass
Part～15 mass parts and more preferably 5 mass parts～10 mass parts.
From the viewpoint of heat stability and electrochemical stability, preferably by graphited to the titanium compound containing sodium and difficulty carbon
(hard carbon) etc. are used as to constitute the negative active core-shell material of anode active material layer.Titanium compound containing sodium is preferably sodium titanate, more
Body ground, is preferably used selected from Na2Ti3O7And Na4Ti5O12In at least one.Furthermore it is possible to by other element to metatitanic acid
Ti or Na of sodium carries out part replacement.The example of the compound that can use includes Na2-xM5 xTi3-yM6 yO7(0≤x≤3/2,0≤
Y≤8/3, M5And M6The most independent is the metallic element in addition to Ti and Na, for example, in Ni, Co, Mn, Fe, Al and Cr
At least one) and Na4-xM7 xTi5-yM8 yO12(0≤x≤11/3,0≤y≤14/3, M7And M8The most independent is in addition to Ti and Na
Metallic element, for example, at least one in Ni, Co, Mn, Fe, Al and Cr).Titanium compound containing sodium can individually make
With or can be applied in combination with polytype.Titanium compound containing sodium can be applied in combination by carbon graphited with difficulty.It addition, M5
And M7Respectively occupy the element in Na site, M6And M8Respectively occupy the element in Ti site.
Even if difficult graphited carbon is by carrying out heating the material with carbon element not growing graphite-structure in an inert atmosphere, and
Represent containing being arranged in the small graphite crystal of any direction and there is at crystal interlayer the material of nanoscale hole.Due to conduct
A diameter of 0.95 angstrom of representative alkali-metal sodium ion, so hole is preferably dimensioned to be substantially greater than this diameter.From
From the viewpoint of strengthening the side reaction of negative active core-shell material filling property in negative pole and suppression and electrolyte, difficult graphited
The mean diameter of carbon (in volume particle size distribution particle diameter) at 50% cumulative volume can be such as 3 μm～20 μm, and excellent
Elect 5 μm～15 μm as.From the viewpoint of guaranteeing the side reaction that sodium ion is acceptable and suppression is with electrolyte, difficult graphited
The specific surface area of carbon can be such as 1m2/ g～10m2/ g, preferably 3m2/ g～8m2/g.Difficult graphited carbon can individually make
With or can be applied in combination with polytype.
[electrolyte (fuse salt)]
Electrolyte (fuse salt) will be used as equal to or higher than the salt becoming ionic liquid at a temperature of fusing point.Electrolyte is extremely
Contain following salt less, described salt contain in molten salt electrolyte battery be used as carrier sodium ion as cation.Can use
The example of salt includes by N (SO2X1)(SO2X2) M (wherein X1And X2It is each independently fluorine atom or there is 1～8 carbon atom
Fluoroalkyl, and M is alkali metal or has nitrogenous heterocyclic organic cation) compound that represents.N(SO2X1)(SO2X2)·M
Including at least N (SO2X1)(SO2X2)·Na。
By X1And X2Represent fluoroalkyl can be the alkyl that some of them hydrogen atom is replaced by fluorine atoms can be maybe wherein
The perfluoroalkyl that all hydrogen atom is all replaced by fluorine atoms.From the viewpoint of reducing viscosity of il, X1And X2In at least
One is preferably perfluoroalkyl, and X1And X2Both are more preferably perfluoroalkyl.Electricity can be suppressed by having 1～8 carbon atom
Solve the rising of matter fusing point and thus advantageously form low viscosity ionic liquid.Especially, from the sight manufacturing low viscosity ionic liquid
From the point of view of Dian, perfluoroalkyl preferably has 1～3 carbon atom and more preferably 1～2 carbon atom.Specifically, X1And X2Can be respective
Independently be trifluoromethyl, pentafluoroethyl group, heptafluoropropyl etc..
By N (SO2X1)(SO2X2) instantiation of double sulfimide aniones that represents includes that double (fluorine sulphonyl) imines is cloudy
Ion (FSA-), double (trimethyl fluoride sulfonyl) imines anion (TFSA-), double (pentafluoroethyl group sulphonyl) imines anion, fluorine sulphonyl
Trifluoromethanesulp-onyl-onyl imide anion (N (FSO2)(CF3SO2)) etc..
The alkali-metal example in addition to sodium represented by M includes potassium, lithium, rubidium and caesium.Wherein potassium is preferred.
Can will have pyrrolidineSkeleton, imidazolesSkeleton, pyridineSkeleton, piperidinesThe cation of skeleton etc. is used as
By what M represented, there is nitrogenous heterocyclic organic cation.Especially, it is contemplated that there is pyrrolidineThe cation of skeleton can be with shape
Become there is the fuse salt of low melting point and the most at high temperature stablize this point, preferably there is pyrrolidineThe cation of skeleton.
There is pyrrolidineThe organic cation of skeleton is represented by such as formula (1):
[chemical formula 1]
Wherein R1And R2It is each independently the alkyl with 1～8 carbon atom.Permissible by having 1～8 carbon atom
Suppress the rising of electrolyte fusing point and thus advantageously form low viscosity ionic liquid.Especially, from manufacturing low viscosity ionic liquid
From the viewpoint of body, alkyl preferably has 1～3 carbon atom and more preferably 1 or 2 carbon atom.Specifically, R1And R2Can be each
From standing alone as methyl, ethyl, propyl group, isopropyl etc..
There is pyrrolidineThe instantiation of the organic cation of skeleton includes methyl-propyl pyrrolidineCation, ethyl
Propyl pyrrole alkaneCation, eryptopyrrole alkaneCation, dimethyl pyrrolidineCation and diethyl pyrrolidineCation etc..These can be used alone or are applied in combination with polytype.Wherein, from high heat stability and electrochemistry
From the viewpoint of stability, methyl-propyl pyrrolidineCation (Py13+) it is particularly preferred.
The instantiation of fuse salt includes sodium ion and FSA-Salt (NaFSA), sodium ion and TFSA-Salt (NaTFSA),
Py13+And FSA-Salt (Py13FSA), Py13+And TFSA-Salt (Py13TFSA) etc..
Fuse salt preferably has alap fusing point.From the viewpoint of the fusing point reducing fuse salt, it is preferably used two
Plant the mixture of above salt.Such as, when using the first salt of sodium and double sulfimide aniones, preferably with the first
The compound mode of salt uses the second salt of the cation in addition to sodium and double sulfimide aniones.Form the first salt and second
The double sulfimide aniones planting salt can be identical or different.
The example of the cation in addition to sodium that can use include potassium ion, cesium ion, lithium ion, magnesium ion, calcium ion,
Above-mentioned organic cation etc..These cationes can be used alone or are applied in combination with two or more.
When by NaFSA, NaTFSA etc. as the first salt, preferably by potassium ion and FSA-Salt (KFSA), potassium ion
With TFSA-Salt (KTFSA) etc. as the second salt.More specifically, it is preferable to use the mixture of NaFSA and KFSA or NaTFSA
Mixture with KTFSA.In such case, it is contemplated that the fusing point of electrolyte and putting down between viscosity and ionic conductivity
Weighing apparatus, the first salt is such as 40/60～70/30 to the mol ratio (the first salt/the second salt) of the second salt, preferably 45/
55～65/35, and more preferably 50/50～60/40.
When the salt of Py13 is used as the first salt, even if this salt has low melting point and the most also has low viscosity.
But, by using sodium salt, potassium salt etc. as the second salt combined with the first salt, reduce further fusing point.When inciting somebody to action
When Py13FSA, Py13TFSA etc. are as the first salt, preferably by NaFSA, NaTFSA etc. as the second salt.More specifically, it is excellent
Choosing uses mixture or the mixture of Py13TFSA and NaTFSA of Py13FSA and NaFSA.In such case, it is contemplated that it is electric
Solve fusing point and the balance between viscosity and ionic conductivity of matter, the first salt to the mol ratio of the second salt (the first salt/
The second salt) it is such as 97/3～80/20, preferably 95/5～85/15.
In addition to above-described salt, electrolyte can contain various additives.But, from guaranteeing that ionic conductivity and heat are steady
From the viewpoint of qualitative, fuse salt is preferably to fill 90 mass % of electrolyte in the battery～100 mass % and more preferably
The ratio of 95 mass %～100 mass % occupies electrolyte.
[barrier film]
Can consider that the material of barrier film is selected by the operating temperature of battery, but from the side reaction of suppression and electrolyte
From the point of view of viewpoint, glass fibre, silica containing polyolefin, fluororesin, aluminium oxide, polyphenylene sulfide (PPS) etc. are preferably used.Special
Not, it is contemplated that its cheapness and high-fire resistance, preferably glass fibre non-woven.Furthermore, it is contemplated that the thermostability of excellence, preferably
Silica containing polyolefin and aluminium oxide.In addition, it is contemplated that thermostability and corrosion resistance, preferably fluororesin and PPS.Especially
Ground, the PPS fluorine toleration to containing in fuse salt is excellent.
What silica containing polyolefin represented is the polyene integrated with SiO 2 powder to improve heat stability
Hydrocarbon, by forming polyolefinic and the most uniaxially or bidirectionally to this sheet carrying out stretching to manufacture have loose structure
Barrier film.At least one selected from polyethylene and polypropylene in is preferably used as polyolefin.
In view of excellent thermostability, particularly preferred politef (PTFE) is as fluororesin.By fluororesin or PPS system
The barrier film become can include the non-woven fabrics being made up of fluororesin fiber or PPS fiber or have porous by what drawing process was formed
The thin film of structure.Especially, it is contemplated that high porosity and do not suppress ionic conductivity, preferably non-woven fabrics.
Below some preferred specific configurations of barrier film are illustrated.
The thickness of the barrier film being made up of glass fibre is 20 μm～500 μm and more preferably 20 μm～50 μm.This is because
Thickness in the range of this can suppress internal short-circuit effectively, and can suppress to occupy the volume integral of the barrier film of electrode group
Number, thus can obtain high capacity density.On the other hand, the barrier film being made up of glass fibre has relatively large aperture and high hole
Gap rate.Therefore, from the viewpoint of being effectively prevented internal short-circuit, the compressive load being applied on the thickness direction of barrier film is preferred
For relatively low and preferably 0.1MPa～1MPa.
The thickness of the barrier film being made up of silica containing polyolefin is 10 μm～500 μm and more preferably 20 μm～50 μ
m.This is because, described barrier film is owing to aperture is little and porosity is low compared with the barrier film being made up of glass fibre, it is advantageous to be
Relative thin.It addition, the compressive load being applied on the thickness direction of barrier film be made up of silica containing polyolefin is preferred
For 0.1MPa～14MPa and more preferably 0.1MPa～3MPa.This is because by applying this compressive load, in can reducing
Resistance, and the generation of internal short-circuit can be more efficiently prevented from.
The thickness of the barrier film being made up of PTFE is 10 μm～500 μm and more preferably 20 μm～50 μm.This is because, by
The barrier film that PTFE makes is preferably relative thin because aperture is little and porosity is low.It addition, be applied to the barrier film being made up of PTFE
Thickness direction on compressive load be preferably 0.1MPa～14MPa and more preferably 0.1MPa～5MPa.This is because PTFE
There is high thermostability and excellent mechanical strength, even if therefore when applying relatively high compressive load, it is also possible to effectively
Prevent the generation of internal short-circuit.
The porosity of barrier film can derive from the pore-size distribution by using mercury porosimeter to measure.Can be by containing hole
The volume of sample and the cumulative volume in hole calculate porosity.Porosity can be such as in the range of 50%～90%.
[electrode group]
Wherein the electrode group containing positive pole and negative pole and electrolyte are placed under the state in battery case use molten
Melt salt battery.By barrier film being placed between positive pole and negative pole and described positive pole and described negative pole being stacked or wind and shape
Become electrode group.In this case, use the battery case being made of metal, and make one in positive pole and negative pole to lead with battery case
Logical so that a part for battery case can be used as the first outside terminal.On the other hand, by using conductor strip by positive pole and to bear
Another in extremely is connected to the second outside terminal, it is led from battery case when making the second terminal insulate with battery case
Go out.
It follows that the structure of molten salt electrolyte battery according to the embodiment of the present invention is illustrated with reference to accompanying drawing.But,
The structure of the molten salt electrolyte battery according to the present invention is not limited to the structure of following description.
Fig. 5 is the perspective view of wherein molten salt electrolyte battery by battery case part incised notch, and Fig. 6 is that the line VI-VI along Fig. 5 takes
Longitudinal cross-section schematic diagram.
Molten salt electrolyte battery 100 is provided with stacked electrode group 11, electrolyte (not shown) and disposes the square of these parts
Aluminum production cell shell 10.Battery case 10 comprises the cap having end container body 12 and this upper opening of closing with upper opening
13.When the assembling of molten salt electrolyte battery 100, it is initially formed in the container body 12 of electrode group 11 and insertion battery case 10.Then,
Carry out the electrolyte of molten condition injecting container body 12 and making electrolyte-impregnated arrive the composition barrier film 1 of electrode group 11, positive pole 2
With the step in the hole of negative pole 3.Or, with the electrolyte (ionic liquid) of the heating of molten condition, electrode group can be carried out
Dipping, then can be placed in the electrode group containing electrolyte in container body 12.
External positive terminals 14 is positioned close to the side of cap 13, thus wears when conducting electricity with battery case 10
Cross cap 13, outside negative terminal 15 is positioned close to the opposite side of cap 13, thus in the state insulated with battery case 10
Under through cap 13.It addition, in order to discharge the gas generated in battery case 10 when internal pressure increases, relief valve 16 is arranged
Center at cap 13.
Stacked electrode group 11 comprise multiple positive pole 2, multiple negative pole 3 and be each placed between positive pole 2 and negative pole 3 multiple
Barrier film 1, its any one be respectively provided with rectangular sheet structure.In figure 6, barrier film 1 is formed as bag-shaped, thus surrounds positive pole 2, but every
The shape of film 1 is not particularly limited.Multiple positive poles 2 and multiple negative pole 3 are alternately arranged by the stacking direction in electrode group 11
Row.
Furthermore it is possible to form positive wire sheet 2a in an end of each positive pole 2.Positive wire sheet by multiple positive poles 2
2a carries out harness and is connected to the external positive terminals 14 being arranged on the cap 13 of battery case 10, and the multiple positive pole of result 2 is with flat
Line mode connects.Likewise it is possible to form cathode conductor sheet 3a in an end of each negative pole 3.The negative pole of multiple negative poles 3 is led
Line sheet 3a carries out harness and is connected to the outside negative terminal 15 being arranged on the cap 13 of battery case 10, the multiple negative pole of result 3
Connect in parallel.Preferably at the left and right of the end face of electrode group 11 to the bundle of positive wire sheet 2a with cathode conductor sheet 3a's
Restraint and be configured thus avoid both to contact having spaced mode therebetween.
External positive terminals 14 and outside negative terminal 15 each have column and in the part being at least exposed to outside
There is helicla flute.Nut 7 is embedded the helicla flute of each terminal and by rotating nut 7, nut 7 is fixed to cap 13.Additionally,
The part within battery case that is housed inside at each terminal arranges flange part 8 so that by rotating nut 7 by packing ring 9 by convex
Edge 8 is fixed to the inner surface of cap 13.
It follows that the present invention is carried out more specific description based on embodiment.But, the invention is not restricted to following enforcement
Example.
<<embodiment 1>>
(formation of positive pole)
By by the NaCrO with 10 μm mean diameters of 85 mass parts2(positive electrode active materials), the acetylene of 10 mass parts
The polyvinylidene fluoride (binding agent) of black (conductive agent) and 5 mass parts is dispersed in N-methyl-pyrrolidon (NMP) and is just prepared for
Pole thickener.It is applied to gained positive pole thickener to have on two surfaces of the aluminium foil of 20 μ m thick, is sufficiently dried, then
Carrying out rolling thus form the positive pole with 180 μm gross thickness, described positive pole is each formed with having 80 μ on two surface
The positive-electrode mixture layer of m thickness.
Positive pole is cut into the rectangular shape of the size with 100mm × 100mm, and prepares 10 positive poles.It addition, respectively
Current collection conductor strip is formed at one side on one side of positive pole.But, in these 10 positive poles is only at one table
The electrode of positive-electrode mixture layer is formed on face.
(formation of negative pole)
By zinc-plated on two surfaces of aluminium foil (the first metal) with 10 μ m thick each self-forming to have 100nm thick
The zinc layers (the second metal) of degree, thus form the negative pole with 10.2 μm gross thickness.
Negative pole is cut into the rectangular shape of the size with 105mm × 105mm, and prepares 10 negative poles.It addition, respectively
Current collection conductor strip is formed at one side on one side of negative pole.But, in these 10 negative poles is only at one table
The electrode of negative electrode mix layer is formed on face.
(barrier film)
Prepare that there is 50 μ m thick and the barrier film being made up of silica containing polyolefin.Average pore size is 0.1 μm, and hole
Gap rate is 70%.Barrier film is cut into the rectangular shape of the size with 110mm × 110mm, and prepares 21 barrier films.
(electrolyte)
Prepare to comprise double (fluorine sulphonyl) imines sodium (NaFSA) and methyl-propyl pyrrolidineDouble (fluorine sulphonyl) imines
(Py13FSA) with the fuse salt of the mixture of the mol ratio of 1:9.This fuse salt has the fusing point of-25 DEG C.
(assembling of molten salt electrolyte battery)
First, by under the decompression of 0.3Pa, positive pole, negative pole and barrier film are dried 90 DEG C of heating carried out above.
Being dried until moisture respectively 90ppm and 45ppm in positive pole and negative pole and the moisture in barrier film is 45ppm
Till.
On the other hand, in the atmosphere with less than-50 DEG C dew point temperatures, relative to the fuse salt of 100 mass parts, by 10
The solid sodium of mass parts immerses in fuse salt, is stirred subsequently at 90 DEG C.As a result, the moisture in fuse salt is reduced
To 20ppm.
Then, barrier film is placed between each positive pole and negative pole and positive pole and negative pole are stacked so that positive wire sheet
Overlap each other, cathode conductor sheet overlaps each other, and makes the bundle of positive wire sheet and the bundle of cathode conductor sheet be arranged in the position of symmetry
Put, thus form electrode group.The electrode forming active material layer (mixture layer) on only one surface is arranged on electrode group
Each end on so that in the face of the active material layer of electrode has the polarity different from the polarity of electrode.Then, also barrier film is arranged
On the outside of each end of electrode group, it is disposed along in aluminum production cell shell with fuse salt thus completes to have as in Fig. 5 and Fig. 6
Shown in structure, the molten salt electrolyte battery with 1.8Ah nominal capacity.
(mensuration of moisture)
Before carrying out battery assembling, the moisture of each parts is individually measured.In the present embodiment, water is used
Divide determinator (MKC-610 manufactured by capital of a country electronics industry Co., Ltd.) by Karl_Fischer method (coulometric titration) to water
Content is divided to be measured.Each weight measuring sample is 3g.
[evaluating (discharge and recharge test)]
Define multiple molten salt electrolyte battery, charge and discharge cycles test before immediately a battery is taken apart, by fuse salt from
Battery takes out, then moisture We1 in fuse salt is measured.As a result, moisture We1 in fuse salt is
50ppm.It follows that another battery is maintained in the thermostatic chamber of 90 DEG C, and the current value of hour multiplying power in 0.2C multiplying power
Under, in the voltage range of 2.5V～3.5V, repeat constant current charge-discharge.Fig. 7 shows the charging and discharging curve of circulation for the first time.
As a result, even if not observing internal short-circuit in the molten salt electrolyte battery of this embodiment after 50 circulations yet, by
This obtains good charge-discharge characteristic.It addition, at the 50th circulation, the discharge capacity density of positive electrode active materials every gram is
118mAh/g。
<<embodiment 2>>
In the same manner as in the example 1 molten salt electrolyte battery assembled and evaluate, difference be by positive pole,
Moisture in negative pole and fuse salt is adjusted to 200ppm, 350ppm and 50ppm respectively, and the moisture in barrier film is adjusted
Whole for 350ppm.As a result, even if the most not observing internal short-circuit, it is thus found that obtain good charge and discharge after 50 circulations
Electrical characteristics.It addition, at the 50th circulation, the discharge capacity density of positive electrode active materials every gram is 105mAh/g.It addition, pass through
In the fuse salt immediately a battery taken apart and taken out from battery by fuse salt and record before charge and discharge cycles is tested
Moisture is 200ppm.
<<comparative example 1>>
In the same manner as in the example 1 molten salt electrolyte battery assembled and evaluate, difference be by positive pole,
Moisture in any one in negative pole and fuse salt is adjusted to 100ppm, and the moisture in barrier film is adjusted to
1000ppm.Fig. 8 shows the charging and discharging curve of circulation for the first time.It addition, pass through before charge and discharge cycles is tested immediately by an electricity
Moisture in the fuse salt that pond is taken apart and taken out from battery by fuse salt and records is 400ppm.
It is appreciated that from Fig. 8 at first time circulation, in the molten salt electrolyte battery of comparative example, there occurs internal short-circuit, by
This can not carry out discharge and recharge to battery.It addition, this battery is taken apart and the state of the barrier film between positive pole and negative pole is carried out
Confirm.It was found that grown sodium dendrite in multiple positions thus break through barrier film.
<<comparative example 2>>
In the same manner as in the example 1 molten salt electrolyte battery assembled and evaluate, difference be by positive pole,
Moisture in any one in negative pole and fuse salt is adjusted to 500ppm, and the moisture in barrier film is adjusted to
350ppm.As a result, the voltage confirming to cause due to internal short-circuit at first time circulation declines.It addition, by charge and discharge
Moisture in the fuse salt immediately a battery taken apart and taken out from battery by fuse salt and record before electricity cyclic test contains
Amount is 420ppm.
<<comparative example 3>>
In the same manner as in the example 1 molten salt electrolyte battery assembled and evaluate, difference be by positive pole,
Moisture in negative pole and electrolyte is adjusted to 200ppm, 350ppm and 100ppm respectively, and by the moisture in barrier film
It is adjusted to 500ppm.As a result, the voltage confirming to cause due to internal short-circuit at first time circulation declines.It addition, pass through
In the fuse salt immediately a battery taken apart and taken out from battery by fuse salt and record before charge and discharge cycles is tested
Moisture is 400ppm.
<<comparative example 4>>
In the same manner as in the example 1 molten salt electrolyte battery assembled and evaluate, difference be by positive pole,
Moisture in negative pole and electrolyte is adjusted to 300ppm, 400ppm and 200ppm respectively, and by the moisture in barrier film
It is adjusted to 400ppm.As a result, the voltage confirming to cause due to internal short-circuit at first time circulation declines.It addition, pass through
In the fuse salt immediately a battery taken apart and taken out from battery by fuse salt and record before charge and discharge cycles is tested
Moisture is 320ppm.
<<embodiment 3>>
The thickness preparing to have 80 μm and the barrier film be made up of glass fibre are as barrier film.Average pore size is 2 μm～3 μm,
And porosity is 70%.Barrier film is cut into the size of 110mm × 110mm, and prepares 21 barrier films.With in the same manner as in Example 1
Method molten salt electrolyte battery is assembled and evaluates, difference is to use barrier film prepared as described above, and will apply
The compressive load of the thickness direction of barrier film in the battery is adjusted to 0.3MPa.As a result, even if the most not seeing after 50 circulations
Observe internal short-circuit, it is thus found that obtain good charge-discharge characteristic.It addition, at the 50th circulation, positive electrode active materials
The discharge capacity density of every gram is 110mAh/g.
<<embodiment 4>>
Assembling molten salt electrolyte battery with method in the same manner as in Example 3 and evaluate, difference is to apply
The compressive load of the thickness direction of barrier film in the battery is adjusted to 0.5MPa.As a result, even if the most not seeing after 50 circulations
Observe internal short-circuit, it is thus found that obtain good charge-discharge characteristic.It addition, at the 50th circulation, positive electrode active materials
The discharge capacity density of every gram is 115mAh/g.
<<embodiment 5>>
Assembling molten salt electrolyte battery with method in the same manner as in Example 3 and evaluate, difference is to apply
The compressive load of the thickness direction of barrier film in the battery is adjusted to 1MPa.As a result, even if the most not observing after 50 circulations
To internal short-circuit, it is thus found that obtain good charge-discharge characteristic.It addition, at the 50th circulation, positive electrode active materials is every
Gram discharge capacity density be 114mAh/g.
<<embodiment 6>>
The thickness preparing to have 200 μm and the barrier film be made up of glass fibre are as barrier film.Average pore size is 5 μm～6 μm,
And porosity is 95%.Barrier film is cut into the size of 110mm × 110mm, and prepares 21 barrier films.With in the same manner as in Example 1
Method molten salt electrolyte battery is assembled and evaluates, difference is to use barrier film prepared as described above.But, will execute
The compressive load of the thickness direction adding barrier film in the battery is adjusted to 0.3MPa.As a result, even if also not having after 50 circulations
Observe internal short-circuit, it is thus found that obtain good charge-discharge characteristic.It addition, at the 50th circulation, positive-active material
The discharge capacity density expecting every gram is 109mAh/g.
<<embodiment 7>>
Assembling molten salt electrolyte battery with method in the same manner as in Example 6 and evaluate, difference is to apply
The compressive load of the thickness direction of barrier film in the battery is adjusted to 0.5MPa.As a result, even if the most not seeing after 50 circulations
Observe internal short-circuit, it is thus found that obtain good charge-discharge characteristic.It addition, at the 50th circulation, positive electrode active materials
The discharge capacity density of every gram is 116mAh/g.
<<embodiment 8>>
Assembling molten salt electrolyte battery with method in the same manner as in Example 6 and evaluate, difference is to apply
The compressive load of the thickness direction of barrier film in the battery is adjusted to 1MPa.As a result, even if the most not observing after 50 circulations
To internal short-circuit, it is thus found that obtain good charge-discharge characteristic.It addition, at the 50th circulation, positive electrode active materials is every
Gram discharge capacity density be 118mAh/g.
Table I summarizes the thickness of the barrier film being made up of glass fibre, compressive load and the discharge capacity in embodiment 3～8
Density.Result shown in Table I shows, when the compressive load of the thickness direction of barrier film being applied to be made up of glass fibre exists
Time in the range of 0.3MPa～1.0MPa, it is thus achieved that good flash-over characteristic, compressive load particularly preferably at 0.5MPa～
In the range of 1.0MPa.Additionally, it is appreciated that the preferred scope of compressive load is not by membrane thicknesses too much influence.
Table I
<<embodiment 9>>
In the same manner as in the example 1 molten salt electrolyte battery assembled and evaluate, difference be by positive pole,
Moisture in any one in negative pole, barrier film and fuse salt is adjusted to below 18ppm.As a result, even if after circulating at 50 times
The most do not observe internal short-circuit, it is thus found that obtain the more preferable charge-discharge characteristic than in embodiment 1.It addition, by filling
Moisture in the fuse salt immediately a battery taken apart and taken out from battery by fuse salt before discharge cycle test and record
Content is 18ppm.It addition, at the 50th circulation, the discharge capacity density of positive electrode active materials every gram is 119mAh/g.
Industrial applicibility
Molten salt electrolyte battery according to the present invention, it is suppressed that penetrate the growth of the dendrite of barrier film, no matter the negative pole therefore used
The type of material how, all inhibits internal short-circuit, and can realize the cycle characteristics of excellence.The molten salt electrolyte battery of the present invention is used
In the most household or industrial large-scale power storage device and electric vehicle or the power supply of motor vehicle driven by mixed power.
Reference
100: molten salt electrolyte battery, 1: barrier film, 2: positive pole, 2a positive wire sheet, 3: negative pole, 3a: cathode conductor sheet, 7: spiral shell
Mother, 8: flange part, 9: packing ring, 10: battery case, 11: electrode group, 12: container body, 13: cap, 14: external positive terminals,
15: outside negative terminal, 16: relief valve.
Claims (3)
1. a molten salt electrolyte battery, comprises: positive pole, negative pole, the barrier film being placed between described positive pole and described negative pole and electrolysis
Matter,
Wherein said electrolyte comprises fuse salt；
Described fuse salt comprises the free N (SO of choosing2X1)(SO2X2) at least one in the compound that represents of M, wherein X1And X2Respectively
From independently be fluorine atom or having the fluoroalkyl of 1～8 carbon atom, and M is alkali metal or has nitrogenous heterocyclic organic sun
Ion, described compound at least contains sodium ion as M；And
Moisture We1 in described fuse salt is below 300ppm in mass ratio.
Molten salt electrolyte battery the most according to claim 1, wherein said moisture We1 is below 200ppm in mass ratio.
3. the method manufacturing molten salt electrolyte battery, described method includes:
Prepare the step that moisture Wp is the positive pole of below 300ppm in mass ratio,
Prepare the step that moisture Wn is the negative pole of below 400ppm in mass ratio,
Preparing moisture We2 is below 50ppm and the fuse salt step as electrolyte at least containing sodium ion in mass ratio
Suddenly,
Prepare the step that moisture Ws is the barrier film of below 350ppm in mass ratio, and
Described barrier film is placed between described positive pole and described negative pole and described positive pole and described negative pole are stacked thus shape
Become electrode group and the step described electrode group impregnated with described fuse salt,
Wherein said fuse salt comprises the free N (SO of choosing2X1)(SO2X2) at least one in the compound that represents of M, wherein X1With
X2It is each independently fluorine atom or there is the fluoroalkyl of 1～8 carbon atom, and M is that alkali metal or have nitrogenous heterocyclic has
Machine cation, described compound at least contains sodium ion as M.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-259608 | 2012-11-28 | ||
| JP2012259608A JP2014107141A (en) | 2012-11-28 | 2012-11-28 | Molten salt battery and method of manufacturing the same |
| PCT/JP2013/077890 WO2014083951A1 (en) | 2012-11-28 | 2013-10-15 | Molten salt battery and method for manufacturing same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104838534A CN104838534A (en) | 2015-08-12 |
| CN104838534B true CN104838534B (en) | 2016-11-30 |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101489994A (en) * | 2006-07-27 | 2009-07-22 | 尼吉康株式会社 | Ionic compound |
| CN101512792A (en) * | 2006-09-07 | 2009-08-19 | 日立麦克赛尔株式会社 | Battery separator, method for manufacture thereof, and lithium secondary battery |
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101489994A (en) * | 2006-07-27 | 2009-07-22 | 尼吉康株式会社 | Ionic compound |
| CN101512792A (en) * | 2006-09-07 | 2009-08-19 | 日立麦克赛尔株式会社 | Battery separator, method for manufacture thereof, and lithium secondary battery |
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