CN115832625A - Flame retardant and secondary battery comprising same - Google Patents
Flame retardant and secondary battery comprising same Download PDFInfo
- Publication number
- CN115832625A CN115832625A CN202111461258.8A CN202111461258A CN115832625A CN 115832625 A CN115832625 A CN 115832625A CN 202111461258 A CN202111461258 A CN 202111461258A CN 115832625 A CN115832625 A CN 115832625A
- Authority
- CN
- China
- Prior art keywords
- flame retardant
- positive
- secondary battery
- ltoreq
- positive pole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003063 flame retardant Substances 0.000 title claims abstract description 113
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 109
- -1 Alkyl radical Chemical class 0.000 claims abstract description 42
- 239000000178 monomer Substances 0.000 claims abstract description 35
- 150000005840 aryl radicals Chemical class 0.000 claims abstract description 10
- 229920000570 polyether Polymers 0.000 claims abstract description 7
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 4
- 125000003118 aryl group Chemical group 0.000 claims abstract description 4
- 238000002955 isolation Methods 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 27
- 239000007774 positive electrode material Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 20
- 239000011248 coating agent Substances 0.000 claims description 18
- 238000000576 coating method Methods 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910013716 LiNi Inorganic materials 0.000 claims description 15
- 229910019142 PO4 Inorganic materials 0.000 claims description 13
- 239000010452 phosphate Substances 0.000 claims description 11
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000011149 active material Substances 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 125000001246 bromo group Chemical group Br* 0.000 claims description 3
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 3
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001301 oxygen Substances 0.000 abstract description 7
- 230000020169 heat generation Effects 0.000 abstract 1
- 239000010410 layer Substances 0.000 description 39
- 238000002485 combustion reaction Methods 0.000 description 23
- 238000004880 explosion Methods 0.000 description 20
- 239000000463 material Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000011230 binding agent Substances 0.000 description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 14
- 230000004044 response Effects 0.000 description 14
- 239000011572 manganese Substances 0.000 description 13
- 235000021317 phosphate Nutrition 0.000 description 12
- 239000002131 composite material Substances 0.000 description 11
- 230000008569 process Effects 0.000 description 11
- 239000004114 Ammonium polyphosphate Substances 0.000 description 10
- 235000019826 ammonium polyphosphate Nutrition 0.000 description 10
- 229920001276 ammonium polyphosphate Polymers 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 238000012360 testing method Methods 0.000 description 10
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 9
- 229910001416 lithium ion Inorganic materials 0.000 description 9
- 230000014759 maintenance of location Effects 0.000 description 9
- 150000003254 radicals Chemical class 0.000 description 9
- 239000004698 Polyethylene Substances 0.000 description 8
- 239000000654 additive Substances 0.000 description 8
- 239000006258 conductive agent Substances 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229920000573 polyethylene Polymers 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 7
- 229910000572 Lithium Nickel Cobalt Manganese Oxide (NCM) Inorganic materials 0.000 description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 239000002033 PVDF binder Substances 0.000 description 6
- 239000004743 Polypropylene Substances 0.000 description 6
- 238000007600 charging Methods 0.000 description 6
- 238000007599 discharging Methods 0.000 description 6
- 239000011267 electrode slurry Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229920001707 polybutylene terephthalate Polymers 0.000 description 6
- 229920001155 polypropylene Polymers 0.000 description 6
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 5
- 239000007773 negative electrode material Substances 0.000 description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 description 4
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 4
- 239000006230 acetylene black Substances 0.000 description 4
- 239000011247 coating layer Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 229920000139 polyethylene terephthalate Polymers 0.000 description 4
- 239000005020 polyethylene terephthalate Substances 0.000 description 4
- 229920000137 polyphosphoric acid Polymers 0.000 description 4
- 229920002451 polyvinyl alcohol Polymers 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229920003048 styrene butadiene rubber Polymers 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 239000010405 anode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229920003023 plastic Polymers 0.000 description 3
- 239000004033 plastic Substances 0.000 description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 3
- 239000002861 polymer material Substances 0.000 description 3
- 239000004926 polymethyl methacrylate Substances 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 229920001897 terpolymer Polymers 0.000 description 3
- 238000004804 winding Methods 0.000 description 3
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- KKUKTXOBAWVSHC-UHFFFAOYSA-N Dimethylphosphate Chemical compound COP(O)(=O)OC KKUKTXOBAWVSHC-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- 229920002845 Poly(methacrylic acid) Polymers 0.000 description 2
- 239000004642 Polyimide Substances 0.000 description 2
- 229920000388 Polyphosphate Polymers 0.000 description 2
- 239000004793 Polystyrene Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 229920002125 Sokalan® Polymers 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 238000001467 acupuncture Methods 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 229920003123 carboxymethyl cellulose sodium Polymers 0.000 description 2
- 229940063834 carboxymethylcellulose sodium Drugs 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 239000003273 ketjen black Substances 0.000 description 2
- 238000003475 lamination Methods 0.000 description 2
- 229910021437 lithium-transition metal oxide Inorganic materials 0.000 description 2
- DVATZODUVBMYHN-UHFFFAOYSA-K lithium;iron(2+);manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[Fe+2].[O-]P([O-])([O-])=O DVATZODUVBMYHN-UHFFFAOYSA-K 0.000 description 2
- ILXAVRFGLBYNEJ-UHFFFAOYSA-K lithium;manganese(2+);phosphate Chemical compound [Li+].[Mn+2].[O-]P([O-])([O-])=O ILXAVRFGLBYNEJ-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- TZIHFWKZFHZASV-UHFFFAOYSA-N methyl formate Chemical compound COC=O TZIHFWKZFHZASV-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000010450 olivine Substances 0.000 description 2
- 229910052609 olivine Inorganic materials 0.000 description 2
- 238000009783 overcharge test Methods 0.000 description 2
- BNMMXDHVMLZQGP-UHFFFAOYSA-N phosphono prop-2-eneperoxoate Chemical compound OP(O)(=O)OOC(=O)C=C BNMMXDHVMLZQGP-UHFFFAOYSA-N 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 2
- 229920002401 polyacrylamide Polymers 0.000 description 2
- 229920001721 polyimide Polymers 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 239000001205 polyphosphate Substances 0.000 description 2
- 235000011176 polyphosphates Nutrition 0.000 description 2
- 238000000197 pyrolysis Methods 0.000 description 2
- 238000011076 safety test Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 239000002210 silicon-based material Substances 0.000 description 2
- 239000002356 single layer Substances 0.000 description 2
- 239000000661 sodium alginate Substances 0.000 description 2
- 235000010413 sodium alginate Nutrition 0.000 description 2
- 229940005550 sodium alginate Drugs 0.000 description 2
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 2
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- 239000011366 tin-based material Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- ZZXUZKXVROWEIF-UHFFFAOYSA-N 1,2-butylene carbonate Chemical compound CCC1COC(=O)O1 ZZXUZKXVROWEIF-UHFFFAOYSA-N 0.000 description 1
- HNAGHMKIPMKKBB-UHFFFAOYSA-N 1-benzylpyrrolidine-3-carboxamide Chemical compound C1C(C(=O)N)CCN1CC1=CC=CC=C1 HNAGHMKIPMKKBB-UHFFFAOYSA-N 0.000 description 1
- MBDUIEKYVPVZJH-UHFFFAOYSA-N 1-ethylsulfonylethane Chemical compound CCS(=O)(=O)CC MBDUIEKYVPVZJH-UHFFFAOYSA-N 0.000 description 1
- YBJCDTIWNDBNTM-UHFFFAOYSA-N 1-methylsulfonylethane Chemical compound CCS(C)(=O)=O YBJCDTIWNDBNTM-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- UHOPWFKONJYLCF-UHFFFAOYSA-N 2-(2-sulfanylethyl)isoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(CCS)C(=O)C2=C1 UHOPWFKONJYLCF-UHFFFAOYSA-N 0.000 description 1
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 229920001661 Chitosan Polymers 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- JGFBQFKZKSSODQ-UHFFFAOYSA-N Isothiocyanatocyclopropane Chemical compound S=C=NC1CC1 JGFBQFKZKSSODQ-UHFFFAOYSA-N 0.000 description 1
- 229910015643 LiMn 2 O 4 Inorganic materials 0.000 description 1
- 229910012619 LiNi0.5Co0.25Mn0.25O2 Inorganic materials 0.000 description 1
- 229910002991 LiNi0.5Co0.2Mn0.3O2 Inorganic materials 0.000 description 1
- 229910011328 LiNi0.6Co0.2Mn0.2O2 Inorganic materials 0.000 description 1
- 229910015872 LiNi0.8Co0.1Mn0.1O2 Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- RJUFJBKOKNCXHH-UHFFFAOYSA-N Methyl propionate Chemical compound CCC(=O)OC RJUFJBKOKNCXHH-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- 229910001128 Sn alloy Inorganic materials 0.000 description 1
- 229920006172 Tetrafluoroethylene propylene Polymers 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical class [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- VIEVWNYBKMKQIH-UHFFFAOYSA-N [Co]=O.[Mn].[Li] Chemical compound [Co]=O.[Mn].[Li] VIEVWNYBKMKQIH-UHFFFAOYSA-N 0.000 description 1
- QTHKJEYUQSLYTH-UHFFFAOYSA-N [Co]=O.[Ni].[Li] Chemical compound [Co]=O.[Ni].[Li] QTHKJEYUQSLYTH-UHFFFAOYSA-N 0.000 description 1
- UMVBXBACMIOFDO-UHFFFAOYSA-N [N].[Si] Chemical class [N].[Si] UMVBXBACMIOFDO-UHFFFAOYSA-N 0.000 description 1
- FBDMTTNVIIVBKI-UHFFFAOYSA-N [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] Chemical compound [O-2].[Mn+2].[Co+2].[Ni+2].[Li+] FBDMTTNVIIVBKI-UHFFFAOYSA-N 0.000 description 1
- 230000004308 accommodation Effects 0.000 description 1
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- NDPGDHBNXZOBJS-UHFFFAOYSA-N aluminum lithium cobalt(2+) nickel(2+) oxygen(2-) Chemical class [Li+].[O--].[O--].[O--].[O--].[Al+3].[Co++].[Ni++] NDPGDHBNXZOBJS-UHFFFAOYSA-N 0.000 description 1
- 239000006183 anode active material Substances 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- OBNCKNCVKJNDBV-UHFFFAOYSA-N butanoic acid ethyl ester Natural products CCCC(=O)OCC OBNCKNCVKJNDBV-UHFFFAOYSA-N 0.000 description 1
- PWLNAUNEAKQYLH-UHFFFAOYSA-N butyric acid octyl ester Natural products CCCCCCCCOC(=O)CCC PWLNAUNEAKQYLH-UHFFFAOYSA-N 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 125000002057 carboxymethyl group Chemical group [H]OC(=O)C([H])([H])[*] 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000001186 cumulative effect Effects 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- VUPKGFBOKBGHFZ-UHFFFAOYSA-N dipropyl carbonate Chemical compound CCCOC(=O)OCCC VUPKGFBOKBGHFZ-UHFFFAOYSA-N 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940093499 ethyl acetate Drugs 0.000 description 1
- CYEDOLFRAIXARV-UHFFFAOYSA-N ethyl propyl carbonate Chemical compound CCCOC(=O)OCC CYEDOLFRAIXARV-UHFFFAOYSA-N 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- ZYMKZMDQUPCXRP-UHFFFAOYSA-N fluoro prop-2-enoate Chemical compound FOC(=O)C=C ZYMKZMDQUPCXRP-UHFFFAOYSA-N 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229910000625 lithium cobalt oxide Inorganic materials 0.000 description 1
- 229910002102 lithium manganese oxide Inorganic materials 0.000 description 1
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 description 1
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 description 1
- 229910001486 lithium perchlorate Inorganic materials 0.000 description 1
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 description 1
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 description 1
- BFZPBUKRYWOWDV-UHFFFAOYSA-N lithium;oxido(oxo)cobalt Chemical compound [Li+].[O-][Co]=O BFZPBUKRYWOWDV-UHFFFAOYSA-N 0.000 description 1
- VLXXBCXTUVRROQ-UHFFFAOYSA-N lithium;oxido-oxo-(oxomanganiooxy)manganese Chemical compound [Li+].[O-][Mn](=O)O[Mn]=O VLXXBCXTUVRROQ-UHFFFAOYSA-N 0.000 description 1
- URIIGZKXFBNRAU-UHFFFAOYSA-N lithium;oxonickel Chemical compound [Li].[Ni]=O URIIGZKXFBNRAU-UHFFFAOYSA-N 0.000 description 1
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 description 1
- 238000004949 mass spectrometry Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 229940017219 methyl propionate Drugs 0.000 description 1
- KKQAVHGECIBFRQ-UHFFFAOYSA-N methyl propyl carbonate Chemical compound CCCOC(=O)OC KKQAVHGECIBFRQ-UHFFFAOYSA-N 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 235000010981 methylcellulose Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 description 1
- UUIQMZJEGPQKFD-UHFFFAOYSA-N n-butyric acid methyl ester Natural products CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- CMPQUABWPXYYSH-UHFFFAOYSA-N phenyl phosphate Chemical compound OP(O)(=O)OC1=CC=CC=C1 CMPQUABWPXYYSH-UHFFFAOYSA-N 0.000 description 1
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002961 polybutylene succinate Polymers 0.000 description 1
- 239000004631 polybutylene succinate Substances 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 229940090181 propyl acetate Drugs 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 239000012048 reactive intermediate Substances 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 1
- HSFQBFMEWSTNOW-UHFFFAOYSA-N sodium;carbanide Chemical group [CH3-].[Na+] HSFQBFMEWSTNOW-UHFFFAOYSA-N 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- KKEYFWRCBNTPAC-UHFFFAOYSA-L terephthalate(2-) Chemical compound [O-]C(=O)C1=CC=C(C([O-])=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-L 0.000 description 1
- QHGNHLZPVBIIPX-UHFFFAOYSA-N tin(ii) oxide Chemical class [Sn]=O QHGNHLZPVBIIPX-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XHGIFBQQEGRTPB-UHFFFAOYSA-N tris(prop-2-enyl) phosphate Chemical compound C=CCOP(=O)(OCC=C)OCC=C XHGIFBQQEGRTPB-UHFFFAOYSA-N 0.000 description 1
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Secondary Cells (AREA)
Abstract
The present application provides a flame retardant comprising: first monomer unit
Second monomer unit
A third monomer unit
Wherein m is more than or equal to 10 and less than or equal to 10000, n is more than or equal to 1 and less than or equal to 1000 1 、X 2 Are each independently selected from-CH 2 ‑、‑CH 2 ‑O‑、‑C(＝O)‑O‑、‑NH‑、‑Si(‑O‑) 3 One of (1); r 1 Is C 1 ‑C 10 Alkyl radical, C 1 ‑C 10 Aryl radical, C 1 ‑C 10 One of polyethers; y is C 1 ‑C 10 Alkyl or C 1 ‑C 10 An aromatic group. The application provides a novel flame retardant, which can be used on a battery isolation film and can solve the safety problem of batteries caused by inflammable electrolyte, high-temperature oxygen release of a positive electrode, heat generation due to crosstalk of the positive electrode and the negative electrode and the like.
Description
Technical Field
The application relates to the technical field of batteries, in particular to a flame retardant, a separation film containing the same and a secondary battery.
Background
In recent years, the application range of secondary batteries has become wider and wider, and the secondary batteries are widely applied to energy storage power supply systems such as hydraulic power, thermal power, wind power and solar power stations, and a plurality of fields such as electric tools, electric bicycles, electric motorcycles, electric automobiles, military equipment and aerospace.
The safety performance of the secondary battery is always highly regarded by the industry, and therefore, how to improve the safety performance of the battery is still a problem to be solved urgently.
Disclosure of Invention
In order to achieve the above object, the present application provides in a first aspect a flame retardant comprising: first monomer unit
Second monomer unit
A third monomer unit
Wherein the first monomer unit and the third monomer unit are connected through the second monomer unit, m is more than or equal to 10 and less than or equal to 10000, n is more than or equal to 1 and less than or equal to 1000 1 、X 2 Are each independently selected from-CH 2 -、-CH 2 -O-、-C(＝O)-O-、-NH-、-Si(-O-) 3 One of (1); r 1 Is C 1 -C 10 Alkyl radical, C 1 -C 10 Aryl radical, C 1 -C 10 One of polyethers; y is C 1 -C 10 Alkyl or C 1 -C 10 An aromatic group. Therefore, the novel flame retardant is prepared, can be decomposed at high temperature to generate high-polymer polyphosphoric acid, a compact isolation layer is formed on the surface of the combustible to separate oxygen and combustible gas,combustion is prevented; meanwhile, the small-molecule phosphate branched chain can capture reactive intermediates H.O.free radicals after pyrolysis, so that the combustion chain reaction is interrupted, and the combustion reaction is prevented from continuing.
In any embodiment, 200. Ltoreq. M.ltoreq.2000 in the first monomer unit.
In any embodiment, 1. Ltoreq. N.ltoreq.100 in the third monomer unit.
Different molecular weights of the flame retardant are adjusted, and the thermal response temperature can be controllably adjusted within 150-400 ℃, so that the flame retardant is adapted to various anode materials, the released active oxygen is captured in time, and the thermal runaway of the battery is prevented.
In any embodiment, the flame retardant particle size Dv50 is in the range of 50nm to 10 μm, optionally 200nm to 2 μm. The particle size of the flame retardant which is sold in the market at present is larger, the flame retardant is difficult to be applied to a coating of a battery material, and the particle size of the flame retardant prepared by the method is moderate, so that the flame retardant can be well applied to an isolating membrane of a secondary battery.
In any embodiment, 1500. Ltoreq. M.ltoreq.2000, 80. Ltoreq. N.ltoreq.100.
In any embodiment, 600 ≦ m <1000,30 ≦ n <50.
In any embodiment, 200 ≦ m <600,1 ≦ n <30.
In any embodiment, 1000 ≦ m <1500,50 ≦ n <80.
The second aspect of the present application also provides a method for preparing a flame retardant, comprising the steps of:
(1) Providing raw materials: a first raw material, a second raw material, and a third raw material, wherein,
the first raw material has a structure shown in a formula I,
the structural formula of the second raw material is-R 1 -X 1 -R 2 -, in which X 1 、X 2 Each independently selected from-CH 2 -、-CH 2 -O-、-C(＝O)-O-、-NH-、-Si(-O-) 3 ；R 1 Is selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Aryl radical, C 1 -C 10 One of polyethers;
the structure of the third raw material is shown as a formula II,
(2) Reacting the first raw material, the second raw material and the third raw material at the temperature of 20-150 ℃;
(3) And washing and drying to obtain the flame retardant.
A third aspect of the present application provides a secondary battery comprising the flame retardant provided in the first aspect of the present application or the flame retardant prepared according to the preparation method provided in the second aspect of the present application.
In some embodiments, the secondary battery includes a positive electrode sheet, a negative electrode sheet, and a separator, and the flame retardant is applied to at least one of the positive electrode sheet, the negative electrode sheet, or the separator.
In some embodiments, the secondary battery comprises a positive pole piece, the positive pole piece comprises a positive pole current collector and a positive pole film layer formed on the surface of the positive pole current collector, the positive pole film layer comprises a positive pole active material, the positive pole active material comprises lithium-containing phosphate, and the secondary battery comprises a flame retardant with the m being more than or equal to 1500 and less than or equal to 2000 and the n being more than or equal to 80 and less than or equal to 100.
In some embodiments, the secondary battery includes a positive electrode sheet including a positive electrode current collector and a positive electrode film layer formed on a surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material including LiNi x Co y Mn 1-x-y O 2 Or lithium cobaltate, the secondary battery comprises m of 600 ≤ m<1000,30≤n<50, wherein x is more than or equal to 0.6 and less than or equal to 0.8 and x+y<1。
In some embodiments, the secondary battery includes a positive electrode sheet including a positive electrode current collector and a positive electrode film layer formed on a surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material including LiNi x Co y Mn 1-x-y O 2 The secondary battery comprises m of 200 ≤ m<600,1≤n<30, wherein x is not less than 0.8 and x + y<1。
In some embodiments, the secondary battery includes a positive electrode sheet including a positive electrode current collector and a positive electrode film layer formed on a surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material including LiNi x Co y Mn 1-x-y O 2 The secondary battery comprises m of 1000 ≤ m<1500,50≤n<80, wherein, 0<x is less than or equal to 0.6 and x + y<1。
A fourth aspect of the present application provides a separator comprising a porous substrate; and a coating layer disposed on at least one surface of the porous substrate, the coating layer comprising the flame retardant provided in the first aspect of the present application or the flame retardant prepared according to the preparation method provided in the second aspect of the present application.
A fifth aspect of the present application provides an electric device including the secondary battery of the fourth aspect of the present application.
Drawings
Fig. 1 is a schematic view of the mechanism of action of a flame retardant according to an embodiment of the present application.
Fig. 2 is a schematic view of a secondary battery according to an embodiment of the present application.
Fig. 3 is an exploded view of the secondary battery according to the embodiment of the present application shown in fig. 2.
Fig. 4 is a schematic view of a battery module according to an embodiment of the present application.
Fig. 5 is a schematic view of a battery pack according to an embodiment of the present application.
Fig. 6 is an exploded view of the battery pack according to the embodiment of the present application shown in fig. 5.
Fig. 7 is a schematic diagram of an electric device in which the secondary battery according to the embodiment of the present application is used as a power source.
Description of reference numerals:
1, a battery pack; 2, putting the box body on the box body; 3, discharging the box body; 4 a battery module; 5 a secondary battery; 51 a housing; 52 an electrode assembly; 53 Top Cap Assembly
Detailed Description
Embodiments of the separator, the positive electrode sheet, the negative electrode sheet, the electrolyte, the secondary battery, the battery module, the battery pack, and the electric device according to the present invention are specifically disclosed below in detail with reference to the drawings as appropriate. But a detailed description thereof will be omitted. For example, detailed descriptions of already known matters and repetitive descriptions of actually the same configurations may be omitted. This is to avoid unnecessarily obscuring the following description, and to facilitate understanding by those skilled in the art. The drawings and the following description are provided for those skilled in the art to fully understand the present application, and are not intended to limit the subject matter recited in the claims.
The "ranges" disclosed herein are defined in terms of lower limits and upper limits, with a given range being defined by a selection of one lower limit and one upper limit that define the boundaries of the particular range. Ranges defined in this manner may or may not include endpoints and may be arbitrarily combined, i.e., any lower limit may be combined with any upper limit to form a range. For example, if ranges of 60-120 and 80-110 are listed for a particular parameter, it is understood that ranges of 60-110 and 80-120 are also contemplated. Furthermore, if the minimum range values 1 and 2 are listed, and if the maximum range values 3,4, and 5 are listed, the following ranges are all contemplated: 1-3, 1-4, 1-5, 2-3, 2-4 and 2-5. In this application, unless otherwise stated, the numerical range "a-b" represents a shorthand representation of any combination of real numbers between a and b, where a and b are both real numbers. For example, a numerical range of "0 to 5" indicates that all real numbers between "0 to 5" have been listed herein, and "0 to 5" is only a shorthand representation of the combination of these numbers. In addition, when a parameter is an integer of 2 or more, it is equivalent to disclose that the parameter is, for example, an integer of 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, or the like.
All embodiments and alternative embodiments of the present application may be combined with each other to form new solutions, if not specifically stated.
All technical and optional features of the present application may be combined with each other to form new solutions, if not specifically mentioned.
All steps of the present application may be performed sequentially or randomly, preferably sequentially, if not specifically stated. For example, the method comprises steps (a) and (b), meaning that the method may comprise steps (a) and (b) performed sequentially, and may also comprise steps (b) and (a) performed sequentially. For example, reference to the process further comprising step (c) means that step (c) may be added to the process in any order, for example, the process may comprise steps (a), (b) and (c), may also comprise steps (a), (c) and (b), may also comprise steps (c), (a) and (b), etc.
The terms "comprises" and "comprising" as used herein mean either open or closed unless otherwise specified. For example, the terms "comprising" and "comprises" may mean that other components not listed may also be included or included, or that only listed components may be included or included.
In this application, the term "or" is inclusive, if not otherwise specified. For example, the phrase "a or B" means "a, B, or both a and B. More specifically, either of the following conditions satisfies the condition "a or B": a is true (or present) and B is false (or not present); a is false (or not present) and B is true (or present); or both a and B are true (or present).
[ flame retardant ]
One embodiment of the present application provides a flame retardant comprising:
first monomer unit
Second monomer unit
A third monomer unit
Wherein the first monomer unit and the third monomer unit are connected through the second monomer unit, m is more than or equal to 10 and less than or equal to 10000, n is more than or equal to 1 and less than or equal to 1000 1 、X 2 Each independently selected from-CH 2 -、-CH 2 -O-、-C(＝O)-O-、-NH-、-Si(-O-) 3 ；R 1 Is selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Aryl radical, C 1 -C 10 One of polyethers; y is selected from C 1 -C 10 Alkyl or C 1 -C 10 An aromatic group.
Fig. 1 is a schematic diagram of an action mechanism of a flame retardant according to an embodiment of the present invention, and the flame retardant has a structure that a polyphosphoric acid amine main chain and a phosphate ester branched chain are adopted, so that a dense oxide layer can be formed on the surface of a combustible, and simultaneously, a meteorological free radical is generated at a high temperature, a reactive free radical in a combustion chain reaction is captured, the combustion chain reaction is interrupted, and the combustion is prevented from continuing.
In some embodiments, 200. Ltoreq. M.ltoreq.2000 in the first monomer unit. The high molecular weight amine polyphosphate backbone can be decomposed at high temperature to produce high molecular weight polyphosphoric acid, ammonia gas, and water. The polyphosphoric acid with high molecular weight can generate a layer of compact isolation layer on the surface of the combustible to block the transfer of oxygen, combustible gas and heat, thereby breaking the three burning factors of 'fire triangle' and preventing burning; in addition, the generated non-combustible gas such as ammonia gas, water and the like can take away a part of heat and dilute the concentration of oxygen and combustible gas in the air.
In some embodiments, 1. Ltoreq. N.ltoreq.100 in the third monomer unit. The small molecular phosphate branched chain can generate gas-phase free radical PO after pyrolysis 2 ·、PO·、(PO 3 Y) n Etc. capturing the combustion chain reaction active intermediate H, O.free radical to generate chemically stable H 3 PO 4 、P 2 O 5 、H(PO 3 Y) n And the like. Thereby interrupting the combustion chain reaction and preventing the combustion reaction from continuing to occur.
In some embodiments, the flame retardant has an average particle size Dv50 of 50nm to 10 μm, optionally 200nm to 2 μm. The flame retardant with smaller particle size can be applied to a coating of a battery material, the ammonium polyphosphate molecular chain is opened in the crosslinking process, the particle size is reduced, the flame retardant particles with proper particle size are prepared, the preparation process is simple, and the cost is low.
In some embodiments, 1500. Ltoreq. M.ltoreq.2000, 80. Ltoreq. N.ltoreq.100. When the molecular weight of the first monomer unit and the molecular weight of the third monomer unit are controlled within the range, the thermal response temperature of the obtained flame retardant is 350-450 ℃, and the flame retardant can be adapted to a lithium iron phosphate anode material system. The thermal response temperature is that the flame retardant is decomposed to generate PO 2 ·、PO·、(PO 3 Y) n Temperature of the free radical.
In some embodiments, 600 ≦ m ≦ 1000,30 ≦ n ≦ 50. When the molecular weight of the first monomer unit and the molecular weight of the third monomer unit are controlled within the range, the obtained flame retardant has the thermal response temperature of 220-259 ℃, and can be adapted to LiNi x Co y Mn 1-x-y O 2 The positive electrode material system is characterized in that x is 0.6-0.8, and x + y is less than 1.
In some embodiments, 200 ≦ m ≦ 600,1 ≦ n ≦ 30. When the molecular weight of the first monomer unit and the molecular weight of the third monomer unit are controlled within the range, the obtained flame retardant has the thermal response temperature of 180-219 ℃, and can be adapted to LiNi x Co y Mn 1-x-y O 2 The positive electrode material system is characterized in that x is 0.8-0.98, and x + y is less than 1.
In some embodiments, 1000. Ltoreq. M.ltoreq.1500, 50. Ltoreq. N.ltoreq.80. When the molecular weight of the first monomer unit and the molecular weight of the third monomer unit are controlled within the range, the obtained flame retardant has the thermal response temperature of 260-349 ℃, and can be adapted to LiNi x Co y Mn 1-x-y O 2 The positive electrode material system is characterized in that x is 0.3-0.6, and x + y is less than 1.
[ method for producing flame retardant ]
One embodiment of the present application provides a method for preparing a flame retardant, comprising the steps of:
(1) Providing raw materials: a first raw material, a second raw material, and a third raw material, wherein,
the first raw material has a structure shown in a formula I,
the structural formula of the second raw material is-R 1 -X 1 -R 2 -, in which X 1 、X 2 Each independently selected from-CH 2 -、-CH 2 -O-、-C(＝O)-O-、-NH-、-Si(-O-) 3 ；R 1 Is selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Aryl radical, C 1 -C 10 One of polyethers;
the structure of the third raw material is shown as a formula II,
(2) Reacting the first raw material, the second raw material and the third raw material at the temperature of 20-150 ℃;
(3) Washing and drying to obtain the flame retardant.
[ Secondary Battery ]
A secondary battery is also called a rechargeable battery or a secondary battery, and refers to a battery that can be continuously used by activating an active material by means of charging after the battery is discharged. In general, a secondary battery includes a positive electrode tab, a negative electrode tab, a separator, and an electrolyte. In the process of charging and discharging the battery, active ions (such as lithium ions) are inserted and extracted back and forth between the positive pole piece and the negative pole piece. The isolating membrane is arranged between the positive pole piece and the negative pole piece, mainly plays a role in preventing the short circuit of the positive pole and the negative pole, and can enable active ions to pass through. The electrolyte is arranged between the positive pole piece and the negative pole piece and mainly plays a role in conducting active ions.
In some embodiments, a secondary battery includes a flame retardant provided by the first aspect of the present application or a flame retardant made according to the method of making provided by the second aspect of the present application.
In some embodiments, the secondary battery comprises a positive electrode sheet, a negative electrode sheet, and a separator, and the flame retardant is applied to at least one of the positive electrode sheet, the negative electrode sheet, or the separator.
In some embodiments, the secondary battery comprises a positive pole piece, the positive pole piece comprises a positive pole current collector and a positive pole film layer formed on the surface of the positive pole current collector, the positive pole film layer comprises a positive pole active material, the positive pole active material comprises lithium-containing phosphate, and the secondary battery comprises a flame retardant with the m being more than or equal to 1500 and less than or equal to 2000 and the n being more than or equal to 80 and less than or equal to 100.
In some embodiments, the secondary battery includes a positive electrode sheet including a positive electrode current collector and a positive electrode film layer formed on a surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material including LiNi x Co y Mn 1-x-y O 2 Or lithium cobaltate, the secondary battery comprises m of 600 ≤ m<1000,30≤n<50 of a flame retardant, wherein x is 0.6-0.8 and x + y<1。
In some embodiments, the secondary battery includes a positive electrode sheet including a positive electrode current collector and a positive electrode film layer formed on a surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material including LiNi x Co y Mn 1-x-y O 2 The secondary battery comprises m of 200 ≤ m<600,1≤n<30, wherein x is not less than 0.8 and x + y<1。
In some embodiments, the secondary battery includes a positive electrode sheet including a positive electrode current collector and a positive electrode film layer formed on a surface of the positive electrode current collector, the positive electrode film layer including a positive electrode active material including LiNi x Co y Mn 1-x-y O 2 The secondary battery comprises m of 1000 ≤ m<1500,50≤n<80, wherein, 0<x is less than or equal to 0.6 and x + y<1。
[ separator ]
One embodiment of the present application provides a separator comprising a porous substrate, optionally a polyolefin-based porous polymer; and at least one surface flame-retardant coating layer disposed on the organic microporous substrate, the flame-retardant coating layer including a flame retardant and a binder. A secondary battery flame-retardant diaphragm comprises an organic microporous diaphragm base material, wherein at least one surface of the base material is provided with a flame-retardant coating, and the porous base film is made of at least one of polyolefin porous polymers, polytetrafluoroethylene, polyvinylidene fluoride-hexafluoropropylene copolymer, polyvinyl chloride, polyethylene glycol terephthalate, polybutylene terephthalate, polymethyl methacrylate, polyacrylonitrile, polyimide, polyvinylpyrrolidone, polyethylene oxide, polyvinyl alcohol or a blending and copolymerization system derived from the polymers; the flame-retardant coating comprises 60-99 parts by mass of a novel flame retardant and 1-40 parts by mass of a binder, wherein the binder is a water-based binder or an organic binder; the water system binder is at least one of sodium methyl cellulose, styrene-butadiene rubber, gelatin, polyvinyl alcohol and polyacrylate terpolymer latex; the organic binder is at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene and polymethyl methacrylate. The thickness of the flame-retardant layer is 0.5 μm to 10 μm, preferably 2 μm to 5 μm.
In some embodiments, the separator may be a single-layer film or a multi-layer composite film, and is not particularly limited. When the separator is a multilayer composite film, the materials of the respective layers may be the same or different, and are not particularly limited.
The application scenario of the flame retardant provided by the application includes but is not limited to a positive electrode, a negative electrode or a separation film of a battery, and preferably, the flame retardant is applied to the separation film as a flame retardant coating to prepare a novel separation film with a flame retardant effect.
[ Positive electrode sheet ]
The positive electrode sheet generally includes a positive electrode current collector and a positive electrode film layer disposed on at least one surface of the positive electrode current collector, and the positive electrode film layer includes a positive electrode active material.
As an example, the positive electrode current collector has two surfaces opposite in its own thickness direction, and the positive electrode film layer is disposed on either or both of the two surfaces opposite to the positive electrode current collector.
In some embodiments, the positive electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, aluminum foil may be used. The composite current collector may include a polymer material base layer and a metal layer formed on at least one surface of the polymer material base layer. The composite current collector may be formed by forming a metal material (aluminum, aluminum alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a polymer base material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the positive active material may employ a positive active material for a battery, which is well known in the art. As an example, the positive electrode active material may include at least one of the following materials: olivine structured lithium-containing phosphates, lithium transition metal oxides and their respective modified compounds. However, the present application is not limited to these materials, and other conventional materials that can be used as a positive electrode active material of a battery may be used. These positive electrode active materials may be used alone or in combination of two or more. Among them, examples of the lithium transition metal oxide may include, but are not limited to, lithium cobalt oxide (e.g., liCoO) 2 ) Lithium nickel oxide (e.g., liNiO) 2 ) Lithium manganese oxide (e.g., liMnO) 2 、LiMn 2 O 4 ) Lithium nickel cobalt oxide, lithium manganese cobalt oxide, lithium nickel manganese oxide, lithium nickel cobalt manganese oxide (e.g., liNi) 1/3 Co 1/3 Mn 1/3 O 2 (may also be abbreviated as NCM) 333 )、LiNi 0.5 Co 0.2 Mn 0.3 O 2 (may also be abbreviated as NCM) 523 )、LiNi 0.5 Co 0.25 Mn 0.25 O 2 (may also be abbreviated as NCM) 211 )、LiNi 0.6 Co 0.2 Mn 0.2 O 2 (may also be abbreviated as NCM) 622 )、LiNi 0.8 Co 0.1 Mn 0.1 O 2 (may also be abbreviated as NCM) 811 ) Lithium nickel cobalt aluminum oxides (e.g., liNi) 0.85 Co 0.15 Al 0.05 O 2 ) And modified compounds thereof, and the like. Examples of olivine structured lithium-containing phosphates may include, but are not limited to, lithium iron phosphate (e.g., liFePO) 4 (also referred to as LFP for short)), a composite material of lithium iron phosphate and carbon, and lithium manganese phosphate (e.g., liMnPO) 4 ) At least one of a composite material of lithium manganese phosphate and carbon, lithium iron manganese phosphate, and a composite material of lithium iron manganese phosphate and carbon.
In some embodiments, the positive electrode film layer further optionally includes a binder. As an example, the binder may include at least one of polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), vinylidene fluoride-tetrafluoroethylene-propylene terpolymer, vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, tetrafluoroethylene-hexafluoropropylene copolymer, and fluoroacrylate resin.
In some embodiments, the positive electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may include at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the positive electrode sheet may be prepared by: dispersing the above components for preparing the positive electrode sheet, such as the positive active material, the conductive agent, the binder and any other components, in a solvent (such as N-methylpyrrolidone) to form a positive electrode slurry; and coating the positive electrode slurry on a positive electrode current collector, and drying, cold pressing and the like to obtain the positive electrode piece.
[ negative electrode sheet ]
The negative pole piece includes the negative pole mass flow body and sets up the negative pole rete on the negative pole mass flow body at least one surface, the negative pole rete includes negative pole active material.
As an example, the negative electrode current collector has two surfaces opposite in its own thickness direction, and the negative electrode film layer is disposed on either or both of the two surfaces opposite to the negative electrode current collector.
In some embodiments, the negative electrode current collector may employ a metal foil or a composite current collector. For example, as the metal foil, copper foil can be used. The composite current collector may include a polymer base layer and a metal layer formed on at least one surface of the polymer base material. The composite current collector may be formed by forming a metal material (copper, copper alloy, nickel alloy, titanium alloy, silver alloy, etc.) on a base material of a polymer material (e.g., a base material of polypropylene (PP), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polystyrene (PS), polyethylene (PE), etc.).
In some embodiments, the negative active material may employ a negative active material for a battery known in the art. As an example, the anode active material may include at least one of the following materials: artificial graphite, natural graphite, soft carbon, hard carbon, silicon-based materials, tin-based materials, lithium titanate and the like. The silicon-based material may be selected from at least one of elemental silicon, silicon oxy-compounds, silicon-carbon compounds, silicon-nitrogen compounds, and silicon alloys. The tin-based material may be selected from at least one of elemental tin, tin oxide compounds, and tin alloys. However, the present application is not limited to these materials, and other conventional materials that can be used as a battery negative active material may also be used. These negative electrode active materials may be used alone or in combination of two or more.
In some embodiments, the anode film layer further optionally includes a binder. As an example, the binder may be selected from at least one of Styrene Butadiene Rubber (SBR), polyacrylic acid (PAA), sodium Polyacrylate (PAAs), polyacrylamide (PAM), polyvinyl alcohol (PVA), sodium Alginate (SA), polymethacrylic acid (PMAA), and carboxymethyl chitosan (CMCS).
In some embodiments, the negative electrode film layer further optionally includes a conductive agent. As an example, the conductive agent may be selected from at least one of superconducting carbon, acetylene black, carbon black, ketjen black, carbon dots, carbon nanotubes, graphene, and carbon nanofibers.
In some embodiments, the negative electrode film layer may further optionally include other additives, such as a thickener (e.g., sodium carboxymethyl cellulose (CMC-Na)), and the like.
In some embodiments, the negative electrode sheet can be prepared by: dispersing the components for preparing the negative electrode plate, such as a negative electrode active material, a conductive agent, a binder and any other components, in a solvent (such as deionized water) to form negative electrode slurry; and coating the negative electrode slurry on a negative electrode current collector, and drying, cold pressing and the like to obtain the negative electrode pole piece.
[ electrolyte ]
The kind of the electrolyte is not particularly limited and may be selected as desired. For example, the electrolyte may be liquid, gel, or all solid.
In some embodiments, the electrolyte is liquid and includes an electrolyte salt and a solvent.
In some embodiments, the electrolyte salt may be selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium bis-fluorosulfonylimide, lithium bis-trifluoromethanesulfonylimide, lithium trifluoromethanesulfonate, lithium difluorophosphate, lithium difluorooxalato borate, lithium dioxaoxalato borate, lithium difluorodioxaoxalato phosphate, and lithium tetrafluorooxalato phosphate.
In some embodiments, the solvent may be selected from at least one of ethylene carbonate, propylene carbonate, ethyl methyl carbonate, diethyl carbonate, dimethyl carbonate, dipropyl carbonate, methyl propyl carbonate, ethyl propyl carbonate, butylene carbonate, fluoroethylene carbonate, methyl formate, methyl acetate, ethyl acetate, propyl acetate, methyl propionate, ethyl propionate, propyl propionate, methyl butyrate, ethyl butyrate, 1, 4-butyrolactone, sulfolane, dimethylsulfone, methylethylsulfone, and diethylsulfone.
In some embodiments, the electrolyte further optionally includes an additive. By way of example, the additives may include a negative electrode film-forming additive, a positive electrode film-forming additive, and may further include additives capable of improving certain properties of the battery, such as additives that improve the overcharge properties of the battery, additives that improve the high-or low-temperature properties of the battery, and the like.
In some embodiments, the positive electrode tab, the negative electrode tab, and the separator may be manufactured into an electrode assembly through a winding process or a lamination process.
In some embodiments, the secondary battery may include an exterior package. The exterior package may be used to enclose the electrode assembly and the electrolyte.
In some embodiments, the outer package of the secondary battery may be a hard case, such as a hard plastic case, an aluminum case, a steel case, or the like. The outer package of the secondary battery may also be a pouch, such as a pouch-type pouch. The material of the soft bag may be plastic, and examples of the plastic include polypropylene, polybutylene terephthalate, polybutylene succinate, and the like.
The shape of the secondary battery is not particularly limited, and may be a cylindrical shape, a square shape, or any other arbitrary shape. For example, fig. 2 is a secondary battery 5 of a square structure as an example.
In some embodiments, referring to fig. 3, the overwrap may include a housing 51 and a cover plate 53. The housing 51 may include a bottom plate and a side plate connected to the bottom plate, and the bottom plate and the side plate enclose to form an accommodating cavity. The housing 51 has an opening communicating with the accommodating chamber, and a cover plate 53 can be provided to cover the opening to close the accommodating chamber. The positive electrode tab, the negative electrode tab, and the separator may be formed into the electrode assembly 52 through a winding process or a lamination process. An electrode assembly 52 is enclosed within the receiving cavity. The electrolyte is impregnated into the electrode assembly 52. The number of electrode assemblies 52 contained in the secondary battery 5 may be one or more, and those skilled in the art can select them according to the actual needs.
In some embodiments, the secondary batteries may be assembled into a battery module, and the number of the secondary batteries contained in the battery module may be one or more, and the specific number may be selected by those skilled in the art according to the application and capacity of the battery module.
Fig. 4 is a battery module 4 as an example. Referring to fig. 4, in the battery module 4, a plurality of secondary batteries 5 may be arranged in series along the longitudinal direction of the battery module 4. Of course, the arrangement may be in any other manner. The plurality of secondary batteries 5 may be further fixed by a fastener.
Alternatively, the battery module 4 may further include a case having an accommodation space in which the plurality of secondary batteries 5 are accommodated.
In some embodiments, the battery modules may be assembled into a battery pack, and the number of the battery modules contained in the battery pack may be one or more, and the specific number may be selected by one skilled in the art according to the application and the capacity of the battery pack.
Fig. 5 and 6 are a battery pack 1 as an example. Referring to fig. 5 and 6, a battery pack 1 may include a battery case and a plurality of battery modules 4 disposed in the battery case. The battery box comprises an upper box body 2 and a lower box body 3, wherein the upper box body 2 can be covered on the lower box body 3 and forms a closed space for accommodating the battery module 4. A plurality of battery modules 4 may be arranged in any manner in the battery box.
In addition, this application still provides a power consumption device, power consumption device includes at least one in secondary battery, battery module or the battery package that this application provided. The secondary battery, the battery module, or the battery pack may be used as a power source of the electric device, and may also be used as an energy storage unit of the electric device. The powered device may include a mobile device (e.g., a mobile phone, a laptop computer, etc.), an electric vehicle (e.g., a pure electric vehicle, a hybrid electric vehicle, a plug-in hybrid electric vehicle, an electric bicycle, an electric scooter, an electric golf cart, an electric truck, etc.), an electric train, a ship, a satellite, an energy storage system, etc., but is not limited thereto.
As the electricity-using device, a secondary battery, a battery module, or a battery pack may be selected according to the use requirement thereof.
Fig. 7 is an electric device as an example. The electric device is a pure electric vehicle, a hybrid electric vehicle or a plug-in hybrid electric vehicle and the like. In order to meet the demand of the electric device for high power and high energy density of the secondary battery, a battery pack or a battery module may be used.
[ examples ]
Hereinafter, examples of the present application will be described. The following description of the embodiments is merely exemplary in nature and is in no way intended to limit the present disclosure. The examples, where specific techniques or conditions are not indicated, are to be construed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
Preparation of flame retardants
50 parts by mass of ammonium polyphosphate, 8 parts by mass of gamma-methacryloxypropyltrimethylsilane and 500 parts by mass of N, N-dimethylformamide are mixed uniformly and reacted at 70 ℃ for 5 hours. Then, adding 25 parts by mass of phosphoric acid acrylate, 2 parts by mass of azodiisobutyronitrile and 1 part by mass of vanadium pentoxide, uniformly mixing, reacting at 65 ℃ for 8 hours, washing and drying to obtain the flame retardant.
Preparation of the separator
And (2) dissolving 80 parts by mass of the flame retardant and 20 parts by mass of polyvinylidene fluoride in N-methyl pyrrolidone, uniformly mixing, coating on the single-layer surface of the porous polyethylene diaphragm, and drying to remove the solvent to obtain the isolating membrane.
Preparation of positive pole piece
Dissolving a positive electrode active material NCM523, a conductive agent acetylene black and a binder polyvinylidene fluoride (PVDF) in a solvent N-methylpyrrolidone (NMP) according to a weight ratio of 96.5; and then uniformly coating the positive electrode slurry on a positive electrode current collector, and then drying, cold pressing and cutting to obtain the positive electrode piece.
Preparation of negative pole piece
Dissolving active substance artificial graphite, a conductive agent acetylene black, a binder Styrene Butadiene Rubber (SBR) and a thickener carboxymethylcellulose sodium (CMC) in solvent deionized water according to a weight ratio of 95; and then uniformly coating the negative electrode slurry on a copper foil of a negative current collector, drying to obtain a negative electrode diaphragm, and performing cold pressing and slitting to obtain a negative electrode plate.
Preparation of the electrolyte
Mixing carbonic acidEthylene (EC), ethyl Methyl Carbonate (EMC), diethyl carbonate (DEC) were mixed in a volume ratio of 1 6 And uniformly dissolving the electrolyte in the solution to obtain the electrolyte. In the electrolyte, liPF 6 The concentration of (2) is 1mol/L.
Preparation of secondary battery
Stacking and winding the positive pole piece, the isolating membrane and the negative pole piece in sequence to obtain an electrode assembly; and (3) putting the electrode assembly into an outer package, adding the prepared electrolyte, and carrying out processes of packaging, standing, formation, aging and the like to obtain the secondary battery.
Examples 2-4 were prepared similarly to example 1, except that the flame retardant and release film were prepared differently.
Example 2
Preparation of flame retardant
60 parts by mass of ammonium polyphosphate, 5 parts by mass of gamma-aminopropyltriethoxysilane and 2000 parts by mass of water: ethanol =1:10, mixing evenly, and reacting for 3 hours at 60 ℃. Then adding 20 parts by mass of dimethyl phosphate and 2 parts by mass of alumina, uniformly mixing, reacting for 5 hours at 70 ℃, washing and drying to obtain the novel flame retardant.
Preparation of the separator
Dissolving 85 parts by mass of the novel flame retardant and 15 parts by mass of sodium carboxymethyl cellulose in water: ethanol =1:1, uniformly mixing, coating the two surfaces of the mixed solution on a porous polypropylene diaphragm, drying and removing the solvent to obtain the lithium ion battery flame-retardant diaphragm.
Example 3
Preparation of flame retardants
70 parts by mass of ammonium polyphosphate, 2 parts by mass of adipic acid and 1000 parts by mass of N-methylpyrrolidone solution are uniformly mixed and reacted for 2 hours at 50 ℃. Then adding 40 parts by mass of phenylphosphoric acid and 5 parts by mass of sulfuric acid, uniformly mixing, reacting for 6 hours at 100 ℃, washing and drying to obtain the novel flame retardant.
Preparation of the separator
And (2) dissolving 70 parts by mass of the novel flame retardant and 30 parts by mass of styrene butadiene rubber in an acetone solution, uniformly mixing, coating the two surfaces of the porous polyimide diaphragm with the mixture, and drying to remove the solvent to obtain the lithium ion battery flame-retardant diaphragm.
Example 4
Preparation of flame retardants
30 parts by mass of ammonium polyphosphate, 10 parts by mass of butadiene, 50 parts by mass of triallyl phosphate, 5 parts by mass of copper oxide, 5 parts by mass of benzoyl peroxide and 6000 parts by mass of chloroform are mixed uniformly and reacted at 80 ℃ for 12 hours. And washing and drying to obtain the novel flame retardant.
Preparation of the separator
And dissolving 75 parts by mass of the novel flame retardant and 25 parts by mass of polymethyl methacrylate in an N, N-dimethylformamide solution, uniformly mixing, coating a single surface of the mixture on a porous polyethylene diaphragm, and drying to remove the solvent to obtain the lithium ion battery flame-retardant diaphragm.
Comparative example 1
The remaining portions of the battery were the same as in examples 1-4, except that the separator was changed to one prepared by coating amine polyphosphate on the surface of a commercial polyethylene separator.
Comparative example 2
The remaining portions of the battery were the same as in examples 1-4, except that the separator was changed to one prepared by coating a phosphoric acid acrylate on the surface of a commercial polyethylene separator.
Experimental example 1
(1) Particle size measurement
In the present application, the Dv50 of a flame retardant is a term well known in the art and can be tested using methods known in the art. For example, by direct testing with a laser diffraction particle size distribution measuring instrument (e.g., a MalvernMastersizer 3000 laser particle sizer) in accordance with GB/T19077.1-2016. Dv50 refers to the particle size at which 50% of the cumulative volume percent of the material particles or powder is obtained.
Table 1 particle size testing
| Sample (I) | Particle diameter Dv50 |
| Example 1 | 500nm |
| Example 2 | 60nm |
| Example 3 | 9μm |
| Example 4 | 1.8μm |
| Comparative example 1 | 10μm |
| Comparative example 2 | 8μm |
The particle size of the flame retardant which is sold in the market at present is larger, generally about 10 mu m, and the larger particle size makes the flame retardant difficult to be applied to a coating of a battery material.
(2) Acupuncture experiment
The lithium ion batteries manufactured in examples 1 to 4 and comparative examples 1 to 2 were charged to an upper limit voltage of 4.35V at a current of 0.5C, and then were subjected to constant voltage charging at a corresponding off-voltage, and the off-current was 0.2C. The test was terminated by completely penetrating the center of the battery at a speed of 50mm/s using a steel needle having a diameter of 3mm, maintaining the penetrated state for 1 hour or reducing the surface temperature of the battery to 50 ℃ after thermal runaway occurred.
(3) Hot box experiment
The lithium ion batteries prepared in examples 1-4 and comparative examples 1-2 were placed in a drying oven and heated to 160 ℃ at a heating rate of 5 ℃/min and held for 30min.
(4) Overcharge test
The lithium ion batteries prepared in examples 1 to 4 and comparative examples 1 to 2 were charged to 120% SOC at 0.5C, and observed for 1h.
TABLE 2 comparison of Battery safety Performance test
| Sample (I) | Acupuncture experiment | Hot box experiment | Overcharge test |
| Example 1 | Without fire or explosion | Without fire or explosion | Without fire or explosion |
| Example 2 | Without fire or explosion | Without fire or explosion | Without fire or explosion |
| Example 3 | Without fire or explosion | Without fire or explosion | Without fire or explosion |
| Example 4 | Without fire or explosion | Without fire or explosion | Without fire or explosion |
| Comparative example 1 | Fire and explosion | Fire and explosion | Fire and explosion |
| Comparative example 2 | Fire and explosion | Fire and explosion | Fire and explosion |
Table 2 shows the comparison of the safety performance tests of the batteries, the batteries of comparative example 1 and comparative example 2 were subjected to fire and explosion in all safety tests, and the batteries equipped with the novel flame retardant modified separator passed all safety tests without fire and explosion. The novel flame retardant is provided by the application, so that free radicals can be generated in a gas phase, hydroxyl radicals generated by a combustion chain reaction are captured, and the combustion chain reaction is interrupted; and a compact heat-insulating oxygen-isolating layer can be formed in a condensed phase, so that the diffusion of heat, combustible gas and oxygen is inhibited, and three factors of combustion of a fire triangle are broken, so that the flame-retardant lithium ion battery has an excellent flame-retardant effect, and the safety of the battery is guaranteed in multiple dimensions.
Experimental example 2
The lithium ion batteries prepared in examples 5 to 8 and comparative examples 1 to 2 were placed in a battery performance test cabinet for testing.
Capacity Retention Rate test
And (3) carrying out charge and discharge tests on the battery cell by using a battery tester to evaluate the electrochemical performance of the battery cell. The charging and discharging voltage is set to be 3.0V-4.2V, the charging and discharging current is set to be 512A (1C), and the corresponding cell capacity is read when the cell is discharged to 2.5V from 3.65V after the first charging and discharging and charging and discharging circulation of the cell is performed for 500 circles. The average of the three cell capacities was taken as the cell capacity value of each example. The capacity retention rate of the cell after 500 cycles was calculated by the following formula: the cycle capacity retention rate at 500 cycles = (cell discharge capacity at 500 cycles/first cell discharge capacity) × 100%.
TABLE 3 comparison of battery cycle performance tests
| Sample(s) | Capacity retention rate at 500 cycles (%) |
| Example 1 | 86.8 |
| Example 2 | 87.4 |
| Example 3 | 87.1 |
| Example 4 | 87.5 |
| Comparative example 1 | 77.5 |
| Comparative example 2 | 30.5 |
Table 3 is a comparison of the cycling performance of the cell at 1C charge-discharge rate at room temperature. Comparative example 1 the capacity retention rate was only 77.5% at 500 cycles due to poor interface uniformity. The phosphate flame retardant of comparative example 2 had a capacity retention rate of only 30.5% at 500 cycles because it was incompatible with the electrode material and side reactions occurred in the battery. Batteries assembled using the modified separators of examples 1-4 exhibited excellent cycle performance with 500-cycle capacity retention rates above 85%. The macromolecular ammonium polyphosphate skeleton rivets the phosphate to prevent the phosphate from being dissolved in electrolyte to generate side reaction; in addition, the crosslinking process refines the ammonium polyphosphate particles, improves the interface performance between the ammonium polyphosphate particles and the electrode material, and therefore shows good cycle performance.
Experimental example 3
Thermal response temperature test
Using a thermogravimetric-mass spectrometer to measure the occurrence of PO and PO in the decomposition product by mass spectrometry at the temperature rise rate of 5 ℃/min 2 ·、(PO 3 Y) n The temperature of the radical is the thermal response temperature.
TABLE 4 thermal response temperature test results
| Sample (I) | Thermal response temperature (. Degree. C.) | Adaptive positive electrode material system |
| Example 1 | 390 | Lithium iron phosphate |
| Example 2 | 220 | LiNi x Co y Mn 1-x-y O 2 (x is more than or equal to 0.6 and less than or equal to 0.8) and lithium cobaltate |
| Example 3 | 180 | LiNi x Co y Mn 1-x-y O 2 (x≥0.8) |
| Example 4 | 260 | LiNi x Co y Mn 1-x-y O 2 (0<x≤0.6) |
| Comparative example 1 | 305 | Lithium iron phosphate and lithium manganate |
Table 4 is a comparison of the thermal response temperatures of the flame retardants. Too high or too low a thermal response temperature is not favorable for the efficacy of the flame retardant. The thermal response temperature of the examples 1-4 is changed compared with that of ammonium polyphosphate, which shows that the thermal response temperature of the flame retardant can be adjusted and controlled through the design of reaction conditions and molecular structures, so that the flame retardant can be adapted to various cathode materials.
Experimental example 4
Flame rating test
The test was carried out in a vertical combustion process in a combustion chamber. Cutting the sample into a length of 130 +/-3 mm and a width of 13 +/-0.3 mm, vertically fixing the sample on a clamp, igniting a bunsen burner at the bottom of the sample, adjusting the height of the flame to be 20 +/-2 mm, and enabling the flame to be blue. The center of the Bunsen burner is arranged at the lower end of the sample and is aligned with the center of the lower end of the sample by 10 mm. And starting timing, moving the ignition source after the flame is applied to the sample for 10s, recording the flame combustion time of the sample, and after the flame combustion of the sample is extinguished, applying the flame for 10s again according to the method and recording the flame combustion time of the sample. And (3) evaluating the flame-retardant grade of the sample according to the flame combustion condition:
v-0, stopping combustion of the vertical sample within 10s, and not allowing liquid drops to exist;
v-1, stopping combustion of a vertical sample within 30s, and not allowing liquid drops to exist;
v-2, stopping combustion of the vertical sample within 30s, and allowing liquid drops to exist;
HB vertical samples stopped burning after 30s, allowing for droplets.
TABLE 5 flame retardant rating comparison
Table 5 is a flame retardant rating comparison. Because the free radicals can be generated in the gas phase, the hydroxyl radicals of the combustion chain reaction are captured, and the combustion chain reaction is broken; and a compact heat-insulating oxygen-isolating layer can be formed in a condensed phase to inhibit the diffusion of heat, combustible gas and oxygen and break the three burning factors of a fire triangle, so that the novel flame retardant of the embodiment 1-4 has excellent flame retardant performance, and the flame retardant grade is V-0. While ammonium polyphosphate and dimethyl phosphate have only HB flame retardant rating.
According to the results, the flame retardant of the embodiment 1-4 and the battery of the embodiment 5-8 have good flame retardant effect and high capacity retention rate and can be adapted to different anode material systems under the condition of containing the novel flame retardant prepared by the application, so that the safety performance of the battery is improved, and the use scene is enlarged.
In contrast, in comparative examples 1 to 2, the barrier film had poor puncture strength, low flame retardancy grade, low capacity cycle retention rate, and no effective improvement in safety performance and general applicability in application scenes.
The present application is not limited to the above embodiments. The above embodiments are merely examples, and embodiments having substantially the same configuration as the technical idea and exhibiting the same operation and effect within the technical scope of the present application are all included in the technical scope of the present application. In addition, various modifications that can be conceived by those skilled in the art are applied to the embodiments and other embodiments are also included in the scope of the present application, in which some of the constituent elements in the embodiments are combined and constructed, without departing from the scope of the present application.
Claims (16)
1. A flame retardant, comprising:
a first monomer unit:
a second monomer unit:
a third monomer unit:
wherein the first monomer unit and the third monomer unit are connected through the second monomer unit, m is more than or equal to 10 and less than or equal to 10000, n is more than or equal to 1 and less than or equal to 1000 1 、X 2 Each independently selected from-CH 2 -、-CH 2 -O-、-C(＝O)-O-、-NH-、-Si(-O-) 3 ；R 1 Is selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Aryl radical, C 1 -C 10 One of polyethers; y is selected from C 1 -C 10 Alkyl or C 1 -C 10 An aromatic group.
2. The flame retardant of claim 1, wherein 200. Ltoreq. M.ltoreq.2000 in the first unit monomer.
3. The flame retardant of claim 1 or 2, wherein 1. Ltoreq. N.ltoreq.100 in the third unit monomer.
4. The flame retardant according to any one of claims 1 to 3,
the particle size Dv50 of the flame retardant is 50nm-10 μm, and can be 200nm-2 μm.
5. The flame retardant of claim 4, wherein 1500. Ltoreq. M.ltoreq.2000, 80. Ltoreq. N.ltoreq.100.
6. The flame retardant of claim 4,
600≤m<1000,30≤n<50。
7. the flame retardant according to claim 4,
200≤m<600,1≤n<30。
8. the flame retardant according to claim 4,
1000≤m<1500,50≤n<80。
9. the preparation method of the flame retardant is characterized by comprising the following steps:
(1) Providing raw materials: a first feedstock, a second feedstock, and a third feedstock, wherein,
the first raw material has a structure shown in a formula I,
the structural formula of the second raw material is-R 1 -X 1 -R 2 -, in which X 1 、X 2 Each independently selected from-CH 2 -、-CH 2 -O-、-C(＝O)-O-、-NH-、-Si(-O-) 3 ；R 1 Is selected from C 1 -C 10 Alkyl radical, C 1 -C 10 Aryl radical, C 1 -C 10 One of polyethers;
the structure of the third raw material is shown as a formula II,
(2) Reacting the first raw material, the second raw material and the third raw material at the temperature of 20-150 ℃;
(3) Washing and drying to obtain the flame retardant.
10. A secondary battery comprising the flame retardant of any one of claims 1-8 or prepared according to the method provided in claim 9.
11. The secondary battery according to claim 10, wherein the secondary battery comprises a positive electrode sheet, a negative electrode sheet, and a separator, and the flame retardant is applied to at least one of the positive electrode sheet, the negative electrode sheet, or the separator.
12. The secondary battery according to claim 10 or 11,
the secondary battery comprises a positive pole piece, the positive pole piece comprises a positive pole current collector and a positive pole film layer formed on the surface of the positive pole current collector, the positive pole film layer comprises a positive pole active material, the positive pole active material comprises lithium-containing phosphate, and the secondary battery comprises the flame retardant disclosed in claim 5.
13. The secondary battery according to claim 10 or 11,
the secondary battery comprises a positive pole piece, the positive pole piece comprises a positive current collector and a positive film layer formed on the surface of the positive current collector, the positive film layer comprises a positive active material, and the positive active material comprises LiNi x Co y Mn 1-x- y O 2 Or lithium cobaltate, the secondary battery comprising the flame retardant of claim 6, wherein 0.6. Ltoreq. X.ltoreq.0.8 and x + y<1。
14. The secondary battery according to claim 10 or 11,
the secondary battery comprises a positive pole piece, the positive pole piece comprises a positive current collector and a positive film layer formed on the surface of the positive current collector, the positive film layer comprises a positive active material, and the positive active material comprises LiNi x Co y Mn 1-x- y O 2 The secondary battery comprising the flame retardant of claim 7, wherein x is not less than 0.8 and x + y<1。
15. The secondary battery according to claim 10 or 11,
the secondary battery comprises a positive pole piece, the positive pole piece comprises a positive current collector and a positive film layer formed on the surface of the positive current collector, the positive film layer comprises a positive active material, and the positive active material comprises LiNi x Co y Mn 1-x- y O 2 The secondary battery comprising the flame retardant of claim 8, wherein 0<x is less than or equal to 0.6 and x + y<1。
16. An isolation film characterized in that,
comprises a porous substrate; and
a coating disposed on at least one surface of the porous substrate, the coating comprising the flame retardant of claims 1-8 or comprising the flame retardant prepared according to the method of claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111461258.8A CN115832625A (en) | 2021-12-02 | 2021-12-02 | Flame retardant and secondary battery comprising same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111461258.8A CN115832625A (en) | 2021-12-02 | 2021-12-02 | Flame retardant and secondary battery comprising same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN115832625A true CN115832625A (en) | 2023-03-21 |
Family
ID=85516086
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111461258.8A Pending CN115832625A (en) | 2021-12-02 | 2021-12-02 | Flame retardant and secondary battery comprising same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115832625A (en) |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000178459A (en) * | 1998-10-08 | 2000-06-27 | Polyplastics Co | Flame-retardant resin composition |
| WO2014115538A1 (en) * | 2013-01-23 | 2014-07-31 | 株式会社豊田自動織機 | Positive electrode for lithium ion secondary battery, manufacturing method for same, and lithium ion secondary battery |
| KR20150068866A (en) * | 2013-12-12 | 2015-06-22 | 주식회사 경신전선 | Flame-retardant resin composition for extrusion, insulater prepared using the same, and electrical wire and cable thereof |
| CN105336979A (en) * | 2015-12-04 | 2016-02-17 | 深圳市沃特玛电池有限公司 | Ternary lithium battery and preparing method thereof |
| KR20180013103A (en) * | 2016-07-28 | 2018-02-07 | 주식회사 엘지화학 | Lithium secondary battery of improved safety of nail penetration |
| JP2019104910A (en) * | 2017-12-11 | 2019-06-27 | ▲広▼▲東▼▲広▼山新材料股▲ふん▼有限公司 | Reactive flame retardant, preparation method and use thereof |
| CN109970981A (en) * | 2017-12-27 | 2019-07-05 | 华为技术有限公司 | A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery |
| CN110212201A (en) * | 2019-06-13 | 2019-09-06 | 桑顿新能源科技(长沙)有限公司 | Battery core, battery pole piece and preparation method thereof, battery |
| CN111548712A (en) * | 2020-05-28 | 2020-08-18 | 山东新诺新材料有限公司 | Rapidly-cured building polyurea explosion-proof coating and preparation method thereof |
-
2021
- 2021-12-02 CN CN202111461258.8A patent/CN115832625A/en active Pending
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000178459A (en) * | 1998-10-08 | 2000-06-27 | Polyplastics Co | Flame-retardant resin composition |
| WO2014115538A1 (en) * | 2013-01-23 | 2014-07-31 | 株式会社豊田自動織機 | Positive electrode for lithium ion secondary battery, manufacturing method for same, and lithium ion secondary battery |
| KR20150068866A (en) * | 2013-12-12 | 2015-06-22 | 주식회사 경신전선 | Flame-retardant resin composition for extrusion, insulater prepared using the same, and electrical wire and cable thereof |
| CN105336979A (en) * | 2015-12-04 | 2016-02-17 | 深圳市沃特玛电池有限公司 | Ternary lithium battery and preparing method thereof |
| KR20180013103A (en) * | 2016-07-28 | 2018-02-07 | 주식회사 엘지화학 | Lithium secondary battery of improved safety of nail penetration |
| JP2019104910A (en) * | 2017-12-11 | 2019-06-27 | ▲広▼▲東▼▲広▼山新材料股▲ふん▼有限公司 | Reactive flame retardant, preparation method and use thereof |
| CN109970981A (en) * | 2017-12-27 | 2019-07-05 | 华为技术有限公司 | A kind of solid fireproof polymer, electrode slice, diaphragm and lithium secondary battery |
| CN110212201A (en) * | 2019-06-13 | 2019-09-06 | 桑顿新能源科技(长沙)有限公司 | Battery core, battery pole piece and preparation method thereof, battery |
| CN111548712A (en) * | 2020-05-28 | 2020-08-18 | 山东新诺新材料有限公司 | Rapidly-cured building polyurea explosion-proof coating and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN115810797A (en) | Lithium ion battery, battery module, battery pack and electric device | |
| CN113994513B (en) | Positive pole piece, electrochemical device comprising positive pole piece and electronic device comprising positive pole piece | |
| WO2024012166A1 (en) | Rechargeable battery and electric apparatus | |
| WO2023134340A1 (en) | Negative electrode active material, negative electrode plate, secondary battery, battery module, battery pack, and electric device thereof | |
| WO2023087996A1 (en) | Composite flame-retardant material and preparation method therefor, separator, negative electrode plate, secondary battery, and electric device | |
| WO2023206216A1 (en) | Non-aqueous electrolyte, secondary battery, battery module, battery pack, and electrical device | |
| CN115820064B (en) | Coating composition, separator, secondary battery, battery module, battery pack, and electric device | |
| CN111063932A (en) | Electrolyte solution and secondary battery | |
| WO2022165780A1 (en) | Secondary battery, and battery module, battery pack, and device comprising same | |
| CN115842125A (en) | Positive electrode material and preparation method and application thereof | |
| CN116918126A (en) | Electrolyte, secondary battery, and electricity-using device | |
| CN115832625A (en) | Flame retardant and secondary battery comprising same | |
| CN115832640A (en) | Negative pole piece and preparation method thereof, secondary battery and preparation method thereof, battery module, battery pack and electric device | |
| CN115832613A (en) | Diaphragm and preparation method thereof, secondary battery, battery module, battery pack and electric device | |
| CN116941097A (en) | Lithium supplementing method and charging and discharging method for secondary battery | |
| CN117239355B (en) | Secondary battery and electricity utilization device | |
| WO2024113081A1 (en) | Binder, electrode sheet, secondary battery, and electrical apparatus | |
| WO2024065367A1 (en) | Separator film and preparation method therefor, secondary battery, and electrical device | |
| WO2023065128A1 (en) | Negative electrode sheet, secondary battery, battery module, battery pack, and electric device | |
| EP4276996A1 (en) | Battery module, battery pack and electric device | |
| WO2023097433A1 (en) | Negative electrode plate, secondary battery, battery module, battery pack and electric apparatus | |
| CN117203798A (en) | Positive electrode plate and secondary battery comprising same | |
| CN115810707A (en) | Negative pole piece, secondary battery, battery module, battery pack and electric device | |
| KR20240021275A (en) | Binder and related separators, electrode plates, cells, battery modules, battery packs and electrical devices | |
| CN116544615A (en) | Separator, lithium secondary battery, and electricity-using device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |