CN116655685A - Lithium battery electrolyte additive, electrolyte and lithium battery - Google Patents
Lithium battery electrolyte additive, electrolyte and lithium battery Download PDFInfo
- Publication number
- CN116655685A CN116655685A CN202310467906.3A CN202310467906A CN116655685A CN 116655685 A CN116655685 A CN 116655685A CN 202310467906 A CN202310467906 A CN 202310467906A CN 116655685 A CN116655685 A CN 116655685A
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- Prior art keywords
- compound
- additive
- alkyl
- electrolyte
- mixing
- Prior art date
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 37
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 12
- 229910052744 lithium Inorganic materials 0.000 title abstract description 12
- 239000002000 Electrolyte additive Substances 0.000 title abstract description 5
- 239000000654 additive Substances 0.000 claims abstract description 72
- 230000000996 additive effect Effects 0.000 claims abstract description 71
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 30
- -1 fluorosulfonyl Chemical group 0.000 claims abstract description 28
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 25
- 125000001153 fluoro group Chemical group F* 0.000 claims abstract description 21
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 16
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims abstract description 8
- 125000003342 alkenyl group Chemical group 0.000 claims abstract description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 3
- 150000002825 nitriles Chemical class 0.000 claims abstract description 3
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 claims abstract description 3
- 150000001875 compounds Chemical class 0.000 claims description 56
- 238000002156 mixing Methods 0.000 claims description 56
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 36
- 229940126062 Compound A Drugs 0.000 claims description 33
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 33
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 21
- 239000013067 intermediate product Substances 0.000 claims description 20
- 238000002360 preparation method Methods 0.000 claims description 18
- LVTJOONKWUXEFR-FZRMHRINSA-N protoneodioscin Natural products O(C[C@@H](CC[C@]1(O)[C@H](C)[C@@H]2[C@]3(C)[C@H]([C@H]4[C@@H]([C@]5(C)C(=CC4)C[C@@H](O[C@@H]4[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@@H](O)[C@H](O[C@H]6[C@@H](O)[C@@H](O)[C@@H](O)[C@H](C)O6)[C@H](CO)O4)CC5)CC3)C[C@@H]2O1)C)[C@H]1[C@H](O)[C@H](O)[C@H](O)[C@@H](CO)O1 LVTJOONKWUXEFR-FZRMHRINSA-N 0.000 claims description 18
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 13
- 229910052736 halogen Inorganic materials 0.000 claims description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 150000002367 halogens Chemical class 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- 125000005843 halogen group Chemical group 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 4
- 150000004673 fluoride salts Chemical class 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 2
- 150000001543 aryl boronic acids Chemical class 0.000 claims description 2
- 239000002994 raw material Substances 0.000 claims description 2
- 229910052796 boron Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 36
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000203 mixture Substances 0.000 description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 19
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 18
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 18
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000002253 acid Substances 0.000 description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 9
- 229940005991 chloric acid Drugs 0.000 description 9
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 9
- 229960002089 ferrous chloride Drugs 0.000 description 9
- 125000001841 imino group Chemical group [H]N=* 0.000 description 9
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 230000001681 protective effect Effects 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000002159 abnormal effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical compound BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 8
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 8
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 8
- 238000001308 synthesis method Methods 0.000 description 8
- 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 description 6
- 239000003063 flame retardant Substances 0.000 description 6
- 125000003784 fluoroethyl group Chemical group [H]C([H])(F)C([H])([H])* 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 5
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 5
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 4
- 239000007774 positive electrode material Substances 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 150000001721 carbon Chemical group 0.000 description 3
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 125000004434 sulfur atom Chemical group 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- HBADJIUYIHIBAO-UHFFFAOYSA-N 1-(2,4-difluorophenyl)-2,4-dimethylbenzene Chemical group CC1=CC(C)=CC=C1C1=CC=C(F)C=C1F HBADJIUYIHIBAO-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- PUAQLLVFLMYYJJ-UHFFFAOYSA-N 2-aminopropiophenone Chemical compound CC(N)C(=O)C1=CC=CC=C1 PUAQLLVFLMYYJJ-UHFFFAOYSA-N 0.000 description 1
- 125000004398 2-methyl-2-butyl group Chemical group CC(C)(CC)* 0.000 description 1
- 125000004918 2-methyl-2-pentyl group Chemical group CC(C)(CCC)* 0.000 description 1
- 125000004922 2-methyl-3-pentyl group Chemical group CC(C)C(CC)* 0.000 description 1
- 125000004493 2-methylbut-1-yl group Chemical group CC(C*)CC 0.000 description 1
- 125000004917 3-methyl-2-butyl group Chemical group CC(C(C)*)C 0.000 description 1
- 125000004919 3-methyl-2-pentyl group Chemical group CC(C(C)*)CC 0.000 description 1
- 125000004921 3-methyl-3-pentyl group Chemical group CC(CC)(CC)* 0.000 description 1
- 125000004920 4-methyl-2-pentyl group Chemical group CC(CC(C)*)C 0.000 description 1
- 125000006043 5-hexenyl group Chemical group 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 125000003545 alkoxy group Chemical group 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004305 biphenyl Chemical group 0.000 description 1
- 235000010290 biphenyl Nutrition 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000013066 combination product Substances 0.000 description 1
- 229940127555 combination product Drugs 0.000 description 1
- 125000002433 cyclopentenyl group Chemical group C1(=CCCC1)* 0.000 description 1
- 125000002704 decyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 125000001028 difluoromethyl group Chemical group [H]C(F)(F)* 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004216 fluoromethyl group Chemical group [H]C([H])(F)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000001188 haloalkyl group Chemical group 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000001400 nonyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 125000004368 propenyl group Chemical group C(=CC)* 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4434—Amides thereof the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4449—Esters with hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2404—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic
- C07F9/242—Esteramides the ester moiety containing a substituent or a structure which is considered as characteristic of hydroxyaryl compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/06—Phosphorus compounds without P—C bonds
- C07F9/22—Amides of acids of phosphorus
- C07F9/24—Esteramides
- C07F9/2454—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/2458—Esteramides the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4461—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/44—Amides thereof
- C07F9/4461—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic
- C07F9/4465—Amides thereof the amide moiety containing a substituent or a structure which is considered as characteristic of aliphatic amines
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- 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
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- Materials Engineering (AREA)
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Abstract
The invention discloses a lithium battery electrolyte additive, an electrolyte and a lithium battery. Relates to the technical field of lithium ion batteries. The additive comprises the following structures:wherein R is 1 And R is R 2 Are independently selected from hydrogen atoms, C 1‑8 Alkyl, C 2‑8 Alkenyl, fluoro substituent, fluoro group substituted C 1‑8 Alkyl, sulfonyl, fluorosulfonyl, sulfonic acid, or fluorosulfonyl; wherein R is 3 、R 4 And R is 5 Are independently selected from hydrogen atoms, C 1‑8 Alkyl, halogenSubstitution C 1‑8 At least one of alkyl, hydroxy, nitrile, or phenyl; wherein R is 1 、R 2 、R 3 、R 4 And R is 5 At least one of which is selected from fluoro substituents or fluoro groups substituted C 1‑8 An alkyl group. The lithium battery electrolyte additive can improve the cycle stability and overcharge resistance of the battery.
Description
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a lithium battery electrolyte additive, an electrolyte and a lithium battery.
Background
The lithium ion battery has the remarkable advantages of high energy density, low self-discharge rate, wide use temperature range, long cycle life, no memory effect and the like, and is widely applied to the fields of 3C digital codes, new energy automobiles, energy storage power stations, aerospace and the like. Among them, the electrolyte plays a role in transporting ions in the lithium ion battery, and is a critical part. In the first charging process of the lithium ion battery, the electrolyte reacts with the negative electrode to form a layer of SEI film, and the SEI film has important influence on main electric properties (such as cycle life, self-discharge, power and the like) of the lithium ion battery. However, as charge and discharge proceeds, the SEI film may be dissolved, decomposed, broken, recombined or thickened, so that the battery performance is gradually attenuated; particularly, when the lithium ion battery is used in a high temperature state, the degradation speed may be greatly increased. In order to meet the requirement of the energy density of the battery, the voltage of the battery is higher and higher at present, and at high voltage, the positive electrode active material is in a lithium deficiency state, has strong oxidizing property, is easy to oxidize and decompose electrolyte in direct contact with the positive electrode active material, and simultaneously generates a large amount of gas; in addition, the positive electrode active material in an excessively lithium deficient state is relatively unstable and is liable to undergo some side reactions.
In the prior art, the safety of the lithium ion battery is mainly improved by adding an overcharge additive or a flame retardant additive into the electrolyte. For example, 2',4' -dimethyl-2, 4-difluorobiphenyl is added as an overcharging additive, for example, a combination product of a phosphazene compound and a silicon atom is added as a flame retardant additive, for example, an additive with a benzene or biphenyl structure is added, so that the overcharging performance and the flame retardant performance of the battery are improved, and the safety of the battery is improved. However, although the above-mentioned prior art can improve the safety of the lithium ion battery, the addition of the overcharge additive or the flame retardant additive can increase the internal resistance and K value of the lithium ion battery, resulting in the degradation of the cycle and the high-low temperature performance of the lithium ion battery, which can definitely cause adverse effects on the electrical performance of the lithium ion battery.
Based on this, there is a need to develop a new additive for lithium battery electrolytes to solve the above problems.
Disclosure of Invention
The first technical problem to be solved by the invention is as follows:
an additive is provided.
The second technical problem to be solved by the invention is as follows:
a method for preparing the additive is provided.
The third technical problem to be solved by the invention is:
the use of said additive.
The invention also provides an electrolyte, which comprises the additive.
The invention also provides a lithium ion battery, which comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
In order to solve the first technical problem, the invention adopts the following technical scheme:
an additive comprising the structure:
wherein R is 1 And R is R 2 Are independently selected from hydrogen atoms, C 1-8 Alkyl, C 2-8 Alkenyl, fluoro substituent, fluoro group substituted C 1-8 Alkyl, sulfonyl, fluorosulfonyl, sulfonic acid, or fluorosulfonyl;
wherein R is 3 、R 4 And R is 5 Are independently selected from hydrogen atoms, C 1-8 Alkyl, halogen substituted C 1-8 At least one of alkyl, hydroxy, nitrile, or phenyl;
wherein R is 1 、R 2 、R 3 、R 4 And R is 5 At least one of which is selected from fluoro substituents or fluoro groups substituted C 1-8 An alkyl group.
According to the embodiments of the present invention, one of the technical solutions has at least one of the following advantages or beneficial effects:
in the structure of the additive, the ortho-para epoxy group is arranged on the benzene ring, and when the epoxy group loses electrons, residual electrons on the epoxy group can resonate on the benzene ring, and when the additive is used for a battery, the influence of the overcharge of the battery on the circulation stability can be relieved to a certain extent. Furthermore, in the structure of the additive, a resonance structure of-N-P=S-is arranged on one epoxy group, and when the other two epoxy groups lose electrons, the benzene ring and the-N-P=S-resonate, so that the additive has dynamic self-adjusting capability, and the stability of the structure of the additive can be maintained. Further, in the structure of the additiveWhen the structure loses electrons, the-C=C-and-C=O-can resonate with benzene rings and the-N-P=S-, the resonance range of electrons is further enlarged, and when the additive is used for a battery, the enlarged resonance range can ensure the stability of an intermediate during the oxidation-reduction reaction of the additive, further maintain the stability of the structure of the additive and further promote the stability of electrolyte.
In the structure of the additive, the structure of-N-P=S-also contains a P group and an S atom, when the additive is used for a battery, the P group can generate flame-retardant phosphorus free radicals in the cycle process of the battery, so that the flame-retardant effect is achieved; the S atoms can poison the active site of the positive electrode material, reduce the strong oxidizing property of the electrolyte material to the positive electrode, and improve the circulation stability of the positive electrode.
In the structure of the additive, R is 1 、R 2 、R 3 、R 4 And R is 5 At least one of which is selected from fluoro substituents or fluoro groups substituted C 1-8 Alkyl, thereby guaranteeing the existence of fluorine element, when the additive is used for the battery, the surface of the battery cathode material forms a stable SEI film before the battery circulates, and the circulation stability and the energy density of the battery are further improved.
According to one embodiment of the invention, the R 3 、R 4 And R is 5 Are independently selected from hydrogen atoms, C 1-6 Alkyl or halogen substituted C 1-6 An alkyl group.
According to one embodiment of the invention, the preparation raw materials of the additive comprise a compound A, a compound B and a compound C;
wherein, the structural formula of the compound A is as follows:
wherein, the structural formula of the compound B is as follows:
wherein, the structural formula of the compound C is as follows:
wherein M is 1 And M 2 Each independently selected from halogen or hydroxy.
In order to solve the second technical problem, the invention adopts the following technical scheme:
a method of preparing the additive comprising the steps of:
mixing the compound A and the compound B in a first solvent, heating, and reacting to obtain an intermediate product;
mixing the intermediate product, the compound C, the palladium catalyst, the fluoride salt and the arylboronic acid in a second solvent, heating and reacting to obtain the additive.
According to one embodiment of the invention, the molar ratio of compound a to compound B is 1-2:1-3.
According to one embodiment of the invention, the molar ratio of compound a to compound B is 1-1.1:1-3.
According to one embodiment of the invention, the molar ratio of compound a to compound B is 1-1.3:1-3.
According to one embodiment of the invention, the molar ratio of compound a to compound B is 1-1.5:1-3.
According to one embodiment of the invention, the molar ratio of compound a to compound B is 1-1.8:1-3.
According to one embodiment of the invention, the compound C is used in an amount of 2 to 5mol.
According to one embodiment of the invention, the amount of compound C is selected from the interval consisting of either or both of the following amounts: 2mol, 3mol, 4mol, 5mol.
According to one embodiment of the invention, the molar ratio of palladium catalyst, fluoride salt and arylboron is between 0.1 and 0.5:1:0.3-0.5.
According to one embodiment of the present invention, the first solvent and the second solvent are each independently selected from at least one of isopropanol, N-butanol, methanol, dimethyl sulfoxide, N-dimethylformamide, and tetrahydrofuran.
According to one embodiment of the present invention, a method for synthesizing compound a comprises the steps of:
a1, mixing an imino-containing compound in an organic solvent in a protective atmosphere, adjusting the temperature to be between 50 ℃ below zero and 100 ℃ below zero, and adding n-butyllithium;
a2, adding N, N-diethyl phosphorus dichloride into the product of the A1, and reacting for 10-12 hours at room temperature;
a3, adding a sulfur-containing compound and halogen acid into the product of A2, reacting for 2-4 hours at room temperature, adjusting the pH value to 9-10, reacting for 5-10 hours at room temperature, and purifying to obtain the compound A.
According to one embodiment of the present invention, a method for synthesizing compound B comprises the steps of:
b1, mixing resorcinol, acetone, acetic acid and chloroplatinic acid in an environment with pH value of 2-4, and reacting for 5-12 hours at 25-40 ℃;
b2 mixing the product of B1 with chloric acid at room temperature, adding CH after reaction 2 Cl, ferrous chloride and excess NaOH, heating in water bath, and refluxing for 12-24 hours.
B3, mixing the product of the B2 with halogen acid, and reacting at 30-40 ℃ to obtain the compound B.
According to one embodiment of the invention, compound C may be synthesized by acrylic acid or acrylate in a conventional manner.
According to one embodiment of the present invention, compound a or compound B may also be synthesized by any other means. The mode and the step of synthesis do not affect the structure of the compound A or the compound B.
In yet another aspect of the invention, an electrolyte is also provided. Comprising an additive as described in embodiment 1 above. The application adopts all the technical schemes of the additive, so that the application has at least all the beneficial effects brought by the technical schemes of the embodiment.
In yet another aspect of the present invention, there is provided a lithium ion battery comprising a positive electrode, a negative electrode, a separator, and the electrolyte. The application adopts all the technical schemes of the electrolyte, so that the electrolyte has at least all the beneficial effects brought by the technical schemes of the embodiment.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
In the description of the present invention, the description of first, second, etc. is for the purpose of distinguishing between technical features only and should not be construed as indicating or implying a relative importance or implicitly indicating the number of technical features indicated or implicitly indicating the precedence of the technical features indicated.
The words "preferably," "more preferably," and the like in the present invention refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.
When a range of values is disclosed herein, the range is considered to be continuous and includes both the minimum and maximum values for the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to include any and all subranges subsumed therein.
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
Unless otherwise indicated or contradicted, terms or phrases used herein have the following meanings:
in an embodiment, the term "alkyl" refers to a saturated hydrocarbon containing primary (positive) carbon atoms, or secondary carbon atoms, or tertiary carbon atoms, or quaternary carbon atoms, or a combination thereof. Phrases containing this term, e.g., "C 1-8 Alkyl "refers to an alkyl group containing 1 to 8 carbon atoms. Suitable examples include, but are not limited to: methyl (Me, -CH) 3 ) Ethyl (Et, -CH) 2 CH 3 ) 1-propyl (n-Pr, n-propyl, -CH 2 CH 2 CH), 2-propyl (i-Pr, i-propyl, -CH (CH) 3 ) 2 ) 1-butyl (n-Bu, n-butyl, -CH) 2 CH 2 CH 2 CH 3 ) 2-methyl-1-propyl (i-Bu, i-butyl, -CH) 2 CH(CH 3 ) 2 ) 2-butyl (s-Bu, s-butyl, -CH (CH) 3 )CH 2 CH 3 ) 2-methyl-2-propyl (t-Bu, t-butyl, -C (CH) 3 ) 3), 1-pentyl (n-pentyl, -CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-pentyl (-CH (CH) 3 )CH 2 CH 2 CH 3 ) 3-amyl radical%-CH(CH 2 CH 3 ) 2 ) 2-methyl-2-butyl (-C (CH) 3 ) 2 CH 2 CH 3 ) 3-methyl-2-butyl (-CH (CH) 3 )CH(CH 3 ) 2 ) 3-methyl-1-butyl (-CH) 2 CH 2 CH(CH 3 ) 2 ) 2-methyl-1-butyl (-CH) 2 CH(CH 3 )CH 2 CH 3 ) 1-hexyl (-CH) 2 CH 2 CH 2 CH 2 CH 2 CH 3 ) 2-hexyl (-CH (CH) 3 )CH 2 CH 2 CH 2 CH 3 ) 3-hexyl (-CH (CH) 2 CH 3 )(CH 2 CH 2 CH 3 ) 2-methyl-2-pentyl (-C (CH) 3 ) 2 CH 2 CH 2 CH 3 ) 3-methyl-2-pentyl (-CH (CH) 3 )CH(CH 3 )CH 2 CH 3 ) 4-methyl-2-pentyl (-CH (CH) 3 )CH 2 CH(CH 3 ) 2 ) 3-methyl-3-pentyl (-C (CH) 3 )(CH 2 CH 3 ) 2 ) 2-methyl-3-pentyl (-CH (CH) 2 CH 3 )CH(CH 3 ) 2 ) 2, 3-dimethyl-2-butyl (-C (CH) 3 ) 2 CH(CH 3 ) 2 ) 3, 3-dimethyl-2-butyl (-CH (CH) 3 )C(CH 3 ) 3 and octyl (- (CH) 2 ) 7 CH 3 )。
In the examples, "C 1～10 Alkyl "refers to an alkyl group having 1 to 10 carbon atoms and is meant to include both branched and straight chain saturated aliphatic hydrocarbon groups having the indicated number of carbon atoms. For example, C 1 ～ 10 As in "C 1 ～ 10 Alkyl "is defined to include groups having 1, 2,3, 4, 5, 6, 7, 8, 9, or 10 carbon atoms in a straight or branched chain structure. For example, "C 1 ～ 10 The alkyl group "specifically includes methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl and the like.
In the examples, "C 1～4 Alkyl "means an alkyl group having 1 to 4 carbon atoms, and includes, for example, methyl, ethyl, propyl, and iso-propylPropyl, n-butyl, isobutyl, tert-butyl, etc.
In the examples, "C 1 ～ 10 Alkoxy "means an alkyl group as defined above attached through an oxygen atom, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, and the like. Similarly, "C 1 ～ 10 Haloalkyl "refers to halogen substituted alkyl as defined above.
In the examples, "alkenyl" is meant to include a radical having at least one unsaturated site, i.e., carbon-carbon sp 2 A hydrocarbon of a normal carbon atom, a secondary carbon atom, a tertiary carbon atom or a cyclic carbon atom of the double bond. Phrases containing this term, e.g., "C 2-8 Alkenyl "refers to alkenyl groups containing 2 to 8 carbon atoms. Suitable examples include, but are not limited to: vinyl (-ch=ch) 2 ) Propenyl (-CH) 2 CH＝CH 2 ) Cyclopentenyl (-C) 5 H 7 ) And 5-hexenyl (-CH) 2 CH 2 CH 2 CH 2 CH＝CH 2 )。
In embodiments, halogen "or" halo "refers to F, cl, br or I.
In embodiments, "halo substituted" means that an optional amount of H at any optional position on the corresponding group is substituted with halo, e.g., fluoromethyl, including monofluoromethyl, difluoromethyl, trifluoromethyl.
In the examples, the reagents, methods and apparatus employed in the present invention, unless otherwise indicated, are all those conventional in the art.
Example 1
An additive comprising the structure:
wherein R is 1 Is ethyl;
wherein R is 2 Is a hydrogen atom;
wherein R is 3 Is methyl;
wherein R is 4 Is fluorineA base;
wherein R is 5 Is fluoroethyl.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-50 ℃, and adding 0.3mol of n-butyllithium;
a2, adding 2mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 10 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 10, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 2
An additive comprising the structure:
wherein R is 1 Is a hydrogen atom;
wherein R is 2 Is ethyl;
wherein R is 3 Is methyl;
wherein R is 4 Is fluoroethyl;
wherein R is 5 Is fluoro.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-50 ℃, and adding 0.3mol of n-butyllithium;
a2, adding 2mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 10 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 10, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 3
An additive comprising the structure:
wherein R is 1 Is a hydrogen atom;
wherein R is 2 Is a hydrogen atom;
wherein R is 3 Is methyl;
wherein R is 4 Is fluoro;
wherein R is 5 Is fluoroethyl.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-100 ℃, and adding 0.3mol of n-butyllithium;
a2, adding 2mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 12 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 10, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 4
An additive comprising the structure:
wherein R is 1 Is butyl;
wherein R is 2 Is ethyl;
wherein R is 3 Is methyl;
wherein R is 4 Is fluoro;
wherein R is 5 Is fluoroethyl.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-50 ℃, and adding 0.25mol of n-butyllithium;
a2 1.5mol of N, N-diethyl phosphorus dichloride is added into the product of A1, and the mixture is reacted for 12 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 8, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 5
An additive comprising the structure:
wherein R is 1 Is ethyl;
wherein R is 2 Is a hydrogen atom;
wherein R is 3 Is fluoro;
wherein R is 4 Is a hydrogen atom;
wherein R is 5 Is fluoroethyl.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-50 ℃, and adding 0.3mol of n-butyllithium;
a2, adding 2mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 12 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 10, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in the environment with pH of 4, mixing 1.8mol of resorcinol, 2mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.4mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 2mol of HClO 3 Reacting at 30 DEG CCompound B is obtained.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 6
An additive comprising the structure:
wherein R is 1 Is ethyl;
wherein R is 2 Is a hydrogen atom;
wherein R is 3 Is methyl;
wherein R is 4 Is fluoro;
wherein R is 5 Is methyl.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-50 ℃, and adding 0.3mol of n-butyllithium;
a2, adding 2mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 10 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 10, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 7
An additive comprising the structure:
wherein R is 1 Is ethyl;
wherein R is 2 Is a hydrogen atom;
wherein R is 3 Is methyl;
wherein R is 4 Is fluoro;
wherein R is 5 Is phenyl.
The preparation of the additive comprises the following steps:
s1, mixing 5mol of compound A with 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-50 ℃, and adding 0.3mol of n-butyllithium;
a2, adding 2mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 12 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 10, the mixture is reacted for 10 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Example 8
An additive comprising the structure:
wherein R is 1 Is butyl;
wherein R is 2 Is butyl;
wherein R is 3 Is methyl;
wherein R is 4 Is fluoro;
wherein R is 5 Is fluoroethyl.
The preparation of the additive comprises the following steps:
s1, mixing 3.5mol of compound A and 5mol of compound B in 200mL of tetrahydrofuran, heating to 90 ℃, and reacting to obtain an intermediate product;
s2 mixing the intermediate product obtained in S1, 2mol of compound C, 0.2mol of ditriphenylphosphine palladium dichloride, 0.8mol of C 12 H 28 PBF 4 And 0.3mol of PhB (OH) 2 The above additive was obtained by reacting 200mL of N, N-dimethylformamide and heating at 100℃for 12 hours.
Wherein, the preparation method of the compound A comprises the following steps:
a1, mixing an imino-containing compound in 200mL of tetrahydrofuran in a protective atmosphere, adjusting the temperature to-80 ℃, and adding 0.5mol of n-butyllithium;
a2, adding 3mol of N, N-diethyl phosphorus dichloride into the product of A1, and reacting for 12 hours at room temperature;
a3 to the product of A2 was added 2g of sulfur powder and HBrO 3 The mixture is reacted for 2 hours at room temperature, the pH is adjusted to 11, the mixture is reacted for 12 hours at room temperature, and the mixture is purified to obtain the compound A.
Wherein, the synthesis method of the compound B comprises the following steps:
b1 in an environment with pH of 4, mixing 3mol of resorcinol, 1.5mol of acetone, 0.8mol of acetic acid and 0.15mol of chloroplatinic acid, and reacting at 40 ℃ for 12 hours;
b2 mixing the product of B1 with 0.3mol of chloric acid at room temperature, adding 0.3mol of CH after reaction 2 Cl, 0.6mol of trifluoroacetic acid, 5mol of ferrous chloride and excess NaOH are heated in a water bath and refluxed for 24 hours.
B3 mixing the product of B2 with 1.5mol of HClO 3 The reaction was carried out at 30℃to give compound B.
An electrolyte comprises the additive and lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Comparative example
The comparative example is different from example 1 in that the electrolyte of the comparative example does not include an additive.
An electrolyte comprising lithium hexafluorophosphate.
A lithium ion battery comprises a positive electrode, a negative electrode, a diaphragm and the electrolyte.
Performance test:
the batteries of examples 1 to 8 and comparative examples were subjected to an overcharge resistance test and a cycle performance test.
The overcharge resistance test method comprises the following steps:
the batteries of examples 1 to 8 and comparative example were taken, subjected to one complete discharge, then charged at a constant current of 1C, and stopped after charging 1.5 times the terminal voltage (4.2V) or charging time for 1 hour, and the battery state was recorded by observing for 1 hour, as shown in Table 1.
TABLE 1
| Overcharge resistance test | |
| Example 1 | No abnormal condition |
| Example 2 | No abnormal condition |
| Example 3 | No abnormal condition |
| Example 4 | No abnormal condition |
| Example 5 | No abnormal condition |
| Example 6 | No abnormal condition |
| Example 7 | No abnormal condition |
| Example 8 | No abnormal condition |
| Comparative example | Firing on fire |
The cycle performance test method comprises the following steps: the batteries of examples 1 to 8 and comparative example were charged to 4.2V at a constant current of 1C at a constant temperature of 25℃and then charged at a constant voltage to a cutoff current of 0.05C, and then discharged to 3.0V at a constant current of 1C, which was recorded as a charge-discharge cycle. Then 500 cycles were performed according to the above conditions. The capacity retention (%) = (discharge capacity of 500 th cycle/first discharge capacity) ×100% after 500 cycles of the lithium ion battery. The test results are shown in Table 2.
TABLE 2
| 1C Capacity Ah | Capacity retention after 500 cycles% | |
| Example 1 | 23.26 | 99.02 |
| Example 2 | 22.53 | 98.46 |
| Example 3 | 22.75 | 98.25 |
| Example 4 | 22.55 | 98.26 |
| Example 5 | 23.04 | 98.33 |
| Example 6 | 23.11 | 98.74 |
| Example 7 | 22.45 | 97.94 |
| Example 8 | 22.21 | 97.85 |
| Comparative example | 20.12 | 70.55 |
The foregoing is merely exemplary embodiments of the present invention and are not intended to limit the scope of the present invention, and all equivalent modifications made by the present invention or direct or indirect application in the relevant art are intended to be included in the scope of the present invention.
Claims (10)
1. An additive, characterized in that: the structure comprises the following steps:
wherein R is 1 And R is R 2 Are independently selected from hydrogen atoms, C 1-8 Alkyl, C 2-8 Alkenyl, fluoro substituent, fluoro group substituted C 1-8 Alkyl, sulfonyl, fluorosulfonyl, sulfonic acid, or fluorosulfonyl;
wherein R is 3 、R 4 And R is 5 Are independently selected from hydrogen atoms, C 1-8 Alkyl, halogen substituted C 1-8 At least one of alkyl, hydroxy, nitrile, or phenyl;
wherein R is 1 、R 2 、R 3 、R 4 And R is 5 At least one of which is selected from fluoro substituents or fluoro groups substituted C 1-8 An alkyl group.
2. An additive according to claim 1, wherein: the R is 3 、R 4 And R is 5 Are independently selected from hydrogen atoms, C 1-6 Alkyl or halogen substituted C 1-6 An alkyl group.
3. An additive according to claim 1, wherein: the preparation raw materials of the additive comprise a compound A, a compound B and a compound C;
wherein, the structural formula of the compound A is as follows:
wherein, the structural formula of the compound B is as follows:
wherein, the structural formula of the compound C is as follows:
wherein M is 1 And M 2 Each independently selected from halogen or hydroxy.
4. A process for preparing the additive of any one of claims 1 to 3, characterized in that: the method comprises the following steps:
mixing the compound A and the compound B in a first solvent, heating, and reacting to obtain an intermediate product;
mixing the intermediate product, the compound C, the palladium catalyst, the fluoride salt and the arylboronic acid in a second solvent, heating and reacting to obtain the additive.
5. The method according to claim 4, wherein: the molar ratio of the compound A to the compound B is 1-2:1-3.
6. The method according to claim 4, wherein: the amount of compound C used is 2-5mol.
7. The method according to claim 4, wherein: the molar ratio of palladium catalyst, fluoride salt and aryl boron is 0.1-0.5:1:0.3-0.5.
8. The method according to claim 4, wherein: the first solvent and the second solvent are independently selected from at least one of isopropanol, N-butanol, methanol, dimethyl sulfoxide, N-dimethylformamide and tetrahydrofuran, respectively.
9. An electrolyte, characterized in that: comprising an additive according to any one of claims 1 to 3.
10. A lithium ion battery, characterized in that: comprising a positive electrode, a negative electrode, a separator, and the electrolyte as claimed in claim 9.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018099091A1 (en) * | 2016-11-30 | 2018-06-07 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN112271330A (en) * | 2020-10-21 | 2021-01-26 | 广州天赐高新材料股份有限公司 | Electrolyte additive, electrolyte and energy storage device |
| CN114142090A (en) * | 2021-11-20 | 2022-03-04 | 九江天赐高新材料有限公司 | Electrolyte additive composition, electrolyte and lithium secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2018099091A1 (en) * | 2016-11-30 | 2018-06-07 | 宁德时代新能源科技股份有限公司 | Electrolyte solution and secondary battery |
| CN112271330A (en) * | 2020-10-21 | 2021-01-26 | 广州天赐高新材料股份有限公司 | Electrolyte additive, electrolyte and energy storage device |
| CN114142090A (en) * | 2021-11-20 | 2022-03-04 | 九江天赐高新材料有限公司 | Electrolyte additive composition, electrolyte and lithium secondary battery |
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