CN114276385B - Flame-retardant precursor and preparation method and application thereof - Google Patents
Flame-retardant precursor and preparation method and application thereof Download PDFInfo
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- CN114276385B CN114276385B CN202111629895.1A CN202111629895A CN114276385B CN 114276385 B CN114276385 B CN 114276385B CN 202111629895 A CN202111629895 A CN 202111629895A CN 114276385 B CN114276385 B CN 114276385B
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- gel electrolyte
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- 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 108
- 239000003063 flame retardant Substances 0.000 title claims abstract description 107
- 239000002243 precursor Substances 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000011245 gel electrolyte Substances 0.000 claims abstract description 62
- 238000000034 method Methods 0.000 claims abstract description 16
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000003792 electrolyte Substances 0.000 claims description 67
- 239000000243 solution Substances 0.000 claims description 66
- 238000006243 chemical reaction Methods 0.000 claims description 48
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 26
- 239000010439 graphite Substances 0.000 claims description 26
- 229910002804 graphite Inorganic materials 0.000 claims description 26
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 238000004132 cross linking Methods 0.000 claims description 21
- 229910003002 lithium salt Inorganic materials 0.000 claims description 21
- 159000000002 lithium salts Chemical class 0.000 claims description 21
- 239000002904 solvent Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 18
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 18
- 229910052744 lithium Inorganic materials 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 15
- 230000000379 polymerizing effect Effects 0.000 claims description 15
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 14
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical compound OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 claims description 13
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 claims description 13
- 238000002347 injection Methods 0.000 claims description 12
- 239000007924 injection Substances 0.000 claims description 12
- 238000006116 polymerization reaction Methods 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- UWFRVQVNYNPBEF-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)propan-1-one Chemical compound CCC(=O)C1=CC=C(C)C=C1C UWFRVQVNYNPBEF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 8
- 239000011230 binding agent Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010025 steaming Methods 0.000 claims description 7
- PLDLPVSQYMQDBL-UHFFFAOYSA-N 2-[[3-(oxiran-2-ylmethoxy)-2,2-bis(oxiran-2-ylmethoxymethyl)propoxy]methyl]oxirane Chemical compound C1OC1COCC(COCC1OC1)(COCC1OC1)COCC1CO1 PLDLPVSQYMQDBL-UHFFFAOYSA-N 0.000 claims description 6
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 6
- VNIBTHCKBVEHRM-UHFFFAOYSA-N FP(N=P(F)(F)F)(NP)(F)F Chemical compound FP(N=P(F)(F)F)(NP)(F)F VNIBTHCKBVEHRM-UHFFFAOYSA-N 0.000 claims description 6
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical group [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 6
- OUPZKGBUJRBPGC-UHFFFAOYSA-N 1,3,5-tris(oxiran-2-ylmethyl)-1,3,5-triazinane-2,4,6-trione Chemical compound O=C1N(CC2OC2)C(=O)N(CC2OC2)C(=O)N1CC1CO1 OUPZKGBUJRBPGC-UHFFFAOYSA-N 0.000 claims description 5
- LCFVJGUPQDGYKZ-UHFFFAOYSA-N Bisphenol A diglycidyl ether Chemical compound C=1C=C(OCC2OC2)C=CC=1C(C)(C)C(C=C1)=CC=C1OCC1CO1 LCFVJGUPQDGYKZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 5
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 5
- QXJQHYBHAIHNGG-UHFFFAOYSA-N trimethylolethane Chemical compound OCC(C)(CO)CO QXJQHYBHAIHNGG-UHFFFAOYSA-N 0.000 claims description 5
- SHKUUQIDMUMQQK-UHFFFAOYSA-N 2-[4-(oxiran-2-ylmethoxy)butoxymethyl]oxirane Chemical compound C1OC1COCCCCOCC1CO1 SHKUUQIDMUMQQK-UHFFFAOYSA-N 0.000 claims description 4
- UUODQIKUTGWMPT-UHFFFAOYSA-N 2-fluoro-5-(trifluoromethyl)pyridine Chemical compound FC1=CC=C(C(F)(F)F)C=N1 UUODQIKUTGWMPT-UHFFFAOYSA-N 0.000 claims description 4
- MECNWXGGNCJFQJ-UHFFFAOYSA-N 3-piperidin-1-ylpropane-1,2-diol Chemical compound OCC(O)CN1CCCCC1 MECNWXGGNCJFQJ-UHFFFAOYSA-N 0.000 claims description 4
- KUAUJXBLDYVELT-UHFFFAOYSA-N 2-[[2,2-dimethyl-3-(oxiran-2-ylmethoxy)propoxy]methyl]oxirane Chemical compound C1OC1COCC(C)(C)COCC1CO1 KUAUJXBLDYVELT-UHFFFAOYSA-N 0.000 claims description 3
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical group C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 claims description 3
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 2
- 239000012295 chemical reaction liquid Substances 0.000 claims description 2
- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 claims description 2
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 claims description 2
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims 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 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 description 14
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 13
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 229910001416 lithium ion Inorganic materials 0.000 description 12
- 239000007787 solid Substances 0.000 description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 10
- 239000005457 ice water Substances 0.000 description 10
- 230000009286 beneficial effect Effects 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 125000003700 epoxy group Chemical group 0.000 description 5
- 238000002329 infrared spectrum Methods 0.000 description 5
- 239000011244 liquid electrolyte Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical group [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 3
- 229940125898 compound 5 Drugs 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000007600 charging Methods 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 229940125782 compound 2 Drugs 0.000 description 2
- 229940126214 compound 3 Drugs 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OKVJWADVFPXWQD-UHFFFAOYSA-N difluoroborinic acid Chemical compound OB(F)F OKVJWADVFPXWQD-UHFFFAOYSA-N 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical group CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 238000007086 side reaction Methods 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- RBKMZOVCGJIRNQ-UHFFFAOYSA-N B([O-])(F)F.C(C(=O)O)(=O)O.[Li+] Chemical compound B([O-])(F)F.C(C(=O)O)(=O)O.[Li+] RBKMZOVCGJIRNQ-UHFFFAOYSA-N 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-N Metaphosphoric acid Chemical compound OP(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229940125904 compound 1 Drugs 0.000 description 1
- 238000010280 constant potential charging Methods 0.000 description 1
- 238000010277 constant-current charging Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- GRPIQKZLNSCFTB-UHFFFAOYSA-N n-[bis(dimethylamino)-fluoroimino-$l^{5}-phosphanyl]-n-methylmethanamine Chemical compound CN(C)P(=NF)(N(C)C)N(C)C GRPIQKZLNSCFTB-UHFFFAOYSA-N 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003014 phosphoric acid esters Chemical class 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
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
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- Secondary Cells (AREA)
Abstract
The invention relates to a flame-retardant precursor, a preparation method and application thereof, and a solid-state battery further formed by a gel electrolyte containing the flame-retardant precursor is excellent in cycle performance, does not generate fire or explode in 150 ℃ heating and needling tests, and is good in flame-retardant effect and high in safety under the condition of small consumption of the flame-retardant precursor. The gel electrolyte in the solid-state battery has good contact with the interface between the anode and the cathode, excellent electrochemical performance and safety performance, relatively simple process and low manufacturing cost, and is suitable for mass production.
Description
Technical Field
The invention relates to the technical field of solid-state batteries, in particular to a flame-retardant precursor, a preparation method and application thereof.
Background
Currently, lithium ion batteries increasingly pursue high energy density and long-acting cycle stability, and lithium ion batteries assembled by utilizing traditional liquid electrolyte are easy to cause thermal runaway under the conditions of overcharge, overdischarge, extrusion, impact or short circuit and the like so as to cause safety problems such as fire and even explosion, and the safety has become a key obstacle for restricting the development of the lithium ion batteries. The development of an electrolyte with good flame retardant effect is one of effective ways for solving the safety problem of the lithium ion battery, and the solid electrolyte has the characteristics of flame retardance or incombustibility, but the solid electrolyte has low ionic conductivity, large interface impedance and poor electrical performance of the lithium ion battery; the ionic conductivity of the gel electrolyte is close to that of the liquid electrolyte, the interface contact effect is good, but the polymer skeleton of the gel electrolyte generally does not have a flame retardant effect, and the lithium ion battery assembled by using the gel electrolyte still has the problems of fire, continuous combustion, explosion and the like.
CN103633368A discloses a flame retardant additive for electrolyte and flame retardant lithium ion battery electrolyte, and the electrolyte using the flame retardant additive disclosed by the invention has low viscosity, low toxicity, wider electrochemical window and temperature range, and high-efficiency flame retardant effect; the lithium battery adopting the electrolyte has good electrochemical performance, greatly improves safety and has wider application market.
CN105977533a discloses a flame-retardant electrolyte of a secondary lithium sulfur battery and a preparation method thereof, the disclosed electrolyte comprises lithium salt, an organic solvent and a flame retardant, the concentration of the lithium salt in the electrolyte is 0.5-5 mol/L, the flame retardant is a fluorinated phosphazene flame retardant, and the mass percentage content of the flame retardant electrolyte is 0.1-20% of the total weight of the flame retardant electrolyte. Adding lithium salt into an organic solvent, stirring uniformly to prepare electrolyte, then adding a flame retardant into the electrolyte, and continuously stirring until the mixture is uniformly mixed, thus obtaining the flame-retardant electrolyte of the secondary lithium-sulfur battery. The flammability of the electrolyte added with the fluoro phosphazene additive is greatly reduced, and the influence on the conductivity is small; the electrochemical performance of the secondary lithium sulfur battery assembled by the electrolyte containing the fluorinated phosphazene flame retardant is obviously improved, and the aim of combining the flame retardant effect and the electrochemical performance can be fulfilled.
In the prior art, in order to improve the flame retardant effect of the liquid electrolyte, the liquid electrolyte can be added with small molecular flame retardants such as phosphate esters, phosphazenes, fluorides, ionic liquids and the like, but the small molecular flame retardants have higher use amount and strong volatility, are easy to decompose on the surface of the electrode to generate byproducts, and are not beneficial to maintaining stable electrochemical performance of the lithium ion battery.
In view of the above, it is important to develop a flame retardant that is beneficial to maintaining stable electrochemical performance of lithium ion batteries.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a flame-retardant precursor, a preparation method and application thereof, and a solid-state battery further formed by the gel electrolyte containing the flame-retardant precursor is excellent in cycle performance, does not fire or explode in 150 ℃ heating and needling tests, and has good flame-retardant effect and high safety under the condition of less consumption of the flame-retardant precursor.
To achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a flame retardant precursor, where the structure of the flame retardant precursor is shown in formula i:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 And R is 6 At least two (e.g., 3, 4, 5, 6, etc.)) are
The others are each independently selected from F or
The flame-retardant precursor has a ring-shaped phosphazene flame-retardant structure, and consists of phosphorus and nitrogen elements, and when the flame-retardant precursor is decomposed by heating, strong dehydrating agents such as metaphosphoric acid or polymetaphosphoric acid can be generated, so that the surface of a matrix substance matched with the flame-retardant precursor is carbonized to form a flame-retardant protective layer; secondly, non-combustible gas such as nitrogen, ammonia or nitrogen oxides is generated, the concentration of the combustible gas on the surface of the substrate material matched with the non-combustible gas is diluted, the surface temperature is reduced, and combustion is inhibited. The composite flame retardant effect of the condensed phase and the gas phase is simultaneously exerted, and the excellent flame retardant effect can be exerted under the condition of low consumption; in addition, the introduction of F element further improves the flame-retardant effect of the flame-retardant precursor, and in addition, the F element is beneficial to ion transmission in the battery, is beneficial to activation of the battery, has no effect on other halogens, and has obvious disadvantages.
Preferably, the flame retardant precursor comprises any one of compounds 1 to 5 or a combination of at least two thereof
In a second aspect, the present invention provides a method for preparing the flame retardant precursor according to the first aspect, the method comprising the steps of:
(1) Mixing glycidol, an acid-binding agent and a solvent, and standing at-5-5deg.C (e.g., -4deg.C, -3deg.C, -2deg.C, -1deg.C, 0deg.C, 1deg.C, 2deg.C, 3deg.C, 4deg.C, etc.), to obtain a first solution;
(2) Mixing hexafluoro-triphosphazene with a solvent to obtain a second solution;
(3) Adding the second solution into the first solution under the conditions of-5-5 ℃ (such as-4 ℃, -3 ℃, -2 ℃, -1 ℃, 0 ℃,1 ℃,2 ℃, 3 ℃,4 ℃ and the like) and stirring, performing a first reaction, heating, performing a second reaction, and performing aftertreatment to obtain the flame-retardant precursor.
Preferably, in step (1), the molar ratio of glycidol to acid-binding agent is 1 (1.01-1.05), wherein 1.01-1.05 may be 1.02, 1.03, 1.04, 1.05, etc.,
the acid binding agent comprises triethylamine and is prepared from the following components,
in the step (2), the molar ratio of the hexafluoro-tripolyphosphazene to the glycidol is 1: (2-6), wherein 2-6 may be 2.5, 3, 3.5, 4, 4.5, 5, 5.5, etc.,
in step (3), the time of the first reaction is 3 to 5 hours, for example, 3.5 hours, 4 hours, 4.5 hours, 5 hours, etc.,
the temperature of the second reaction is 20-30deg.C, such as 22deg.C, 24deg.C, 26deg.C, 28deg.C, etc.,
the second reaction time is 24-48h, such as 30h, 35h, 40h, 45h, etc.,
the post-treatment comprises filtration, rotary steaming and drying.
The invention prepares different compounds from the standpoint of raw materials mainly by adjusting the mole ratio of glycidol to acid-binding agent and the mole ratio of hexafluoro-tripolyphosphazene to glycidol.
In a third aspect, the invention provides a gel electrolyte, wherein the gel electrolyte is prepared from the flame retardant precursor, the crosslinking monomer, the catalyst and the electrolyte.
According to the invention, epoxy groups are firstly introduced into the cyclophosphazene flame-retardant structure to obtain a flame-retardant precursor, and then the flame-retardant precursor is fixed on a polymer framework by using a crosslinking monomer, so that compared with the liquid electrolyte added with a micromolecular flame retardant, the side reaction between the flame-retardant structure and electrodes can be effectively relieved, and in addition, more introduced epoxy groups have an ether-oxygen bond structure, so that the lithium ions can be transmitted in a gel electrolyte, and the characteristics can ensure that the solid-state battery has long-acting cyclic stability and better capacity exertion.
Preferably, the crosslinking monomer comprises a glycidyl ether including any one or a combination of at least two of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol a diglycidyl ether, triglycidyl isocyanurate, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether, or pentaerythritol tetraglycidyl ether, wherein typical but non-limiting combinations include: a combination of ethylene glycol diglycidyl ether and 1, 4-butanediol diglycidyl ether, a combination of neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether and bisphenol A diglycidyl ether, a combination of bisphenol A diglycidyl ether, triglycidyl isocyanurate, trimethylolethane triglycidyl ether and trimethylolpropane triglycidyl ether, a combination of resorcinol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether and pentaerythritol tetraglycidyl ether, and the like,
the catalyst comprises a lithium fluoride salt.
The catalyst selected by the invention comprises lithium fluoride salt, is different from the traditional catalyst, can not generate excessive side reaction products because of remaining in a gel electrolyte system after the polymerization of the flame retardant precursor and the crosslinking monomer is initiated, and has little influence on the electrochemical performance of the solid-state battery.
The lithium fluoride salts include any one or a combination of at least two of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium oxalyldifluoroborate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide, or lithium bistrifluorosulfonylimide, wherein typical but non-limiting combinations include: a combination of lithium hexafluorophosphate and lithium hexafluoroarsenate, a combination of lithium oxalato difluoroborate, lithium trifluoromethylsulfonate and lithium bistrifluoromethylsulfonimide, a combination of lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium oxalato difluoroborate, lithium trifluoromethylsulfonate, lithium bistrifluoromethylsulfonimide and lithium bistrifluorosulfonylimide, and the like,
the electrolyte comprises a lithium salt and a solvent,
the lithium salt comprises lithium hexafluorophosphate,
the solvent in the electrolyte comprises any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate or ethylmethyl carbonate, wherein typical but non-limiting combinations include: the combination of ethylene carbonate, propylene carbonate and dimethyl carbonate, the combination of ethylene carbonate and diethyl carbonate, the combination of diethyl carbonate and dimethyl carbonate, the combination of ethylene carbonate, diethyl carbonate and dimethyl carbonate, and the like, and further preferably the combination of ethylene carbonate, diethyl carbonate and dimethyl carbonate.
Preferably, the concentration of the lithium salt substance in the electrolyte is 0.5 to 2mol/L, for example 0.6mol/L, 0.8mol/L, 1mol/L, 1.2mol/L, 1.4mol/L, 1.6mol/L, 1.8mol/L, etc.,
the crosslinking monomer comprises 1% -40%, such as 5%, 10%, 15%, 20%, 25%, 30%, 35%, etc. of the amount of the flame retardant precursor,
the catalyst comprises 0.1% -2.0% of the total mass of the flame retardant precursor and the crosslinking monomer, such as 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.2%, 1.4%, 1.6%, 1.8%, etc.,
the total mass of the flame-retardant precursor and the crosslinking monomer accounts for 1% -20% of the mass of the electrolyte, for example, 2%, 4%, 6%, 8%, 10%, 2%, 14%, 16%, 18% and the like.
In a fourth aspect, the present invention provides a method for preparing the gel electrolyte according to the third aspect, the method comprising the steps of:
and mixing the flame-retardant precursor, the crosslinking monomer, the catalyst and the electrolyte in the formula amount to form a reaction solution, and polymerizing the reaction solution to obtain the gel electrolyte.
Preferably, the polymerization temperature is 20-70 ℃, such as 30 ℃, 40 ℃, 50 ℃, 60 ℃ and the like,
the polymerization time is 1 to 24 hours, for example, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours, etc.
In a fifth aspect, the present invention provides a solid-state battery comprising a positive electrode, a negative electrode and the gel electrolyte according to the third aspect.
Preferably, the positive electrode includes any one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium iron manganese phosphate, lithium nickel manganate or lithium nickel cobalt manganate,
the negative electrode comprises any one of graphite, lithium titanate, silicon carbon negative electrode or metal lithium.
Illustratively, the method of preparing the solid-state battery comprises the steps of:
and mixing the flame-retardant precursor, the crosslinking monomer, the catalyst and the electrolyte according to the formula amount to form a reaction solution, injecting the reaction solution between the positive electrode and the negative electrode, and polymerizing to form the gel electrolyte to obtain the solid-state battery.
The gel electrolyte in the solid-state battery is formed by directly initiating reaction between the anode and the cathode in situ by using the flame-retardant precursor and the crosslinking monomer, has good interface contact, excellent electrochemical performance and safety performance, relatively simple process and low manufacturing cost, and is suitable for mass production.
Preferably, the injection coefficient of the reaction liquid between the positive electrode and the negative electrode is 0.5 to 5g/Ah, for example, 1g/Ah, 1.5g/Ah, 2g/Ah, 2.5g/Ah, 3g/Ah, 3.5g/Ah, 4g/Ah, 4.5g/Ah, etc.
Compared with the prior art, the invention has the following beneficial effects:
(1) The solid-state battery further formed by the gel electrolyte containing the flame-retardant precursor has the discharge capacity retention rate of more than 90.7% after 800 times of circulation, excellent circulation performance, no fire or explosion in 150 ℃ heating and needling tests, good flame-retardant effect and high safety under the condition of less consumption of the flame-retardant precursor.
(2) The gel electrolyte in the solid-state battery is formed by directly initiating reaction between the anode and the cathode in situ by using the flame-retardant precursor and the crosslinking monomer, has good interface contact, excellent electrochemical performance and safety performance, relatively simple process and low manufacturing cost, and is suitable for mass production.
Drawings
FIG. 1 is an infrared spectrum of a flame retardant precursor according to preparation example 5.
FIG. 2 is an infrared spectrum of the gel electrolyte described in example 7.
FIG. 3 shows the microstructure of the positive electrode surface of example 1 before the polymerization reaction of the reaction solution.
FIG. 4 shows the microstructure of the positive electrode surface of example 1 after the polymerization reaction of the reaction solution.
Detailed Description
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Preparation example 1
The flame-retardant precursor is a compound 1, and has the following structural formula:
the preparation method of the flame-retardant precursor comprises the following steps:
(1) Uniformly dissolving 0.100mol of glycidol and 0.102mol of triethylamine in 50mL of toluene solvent, transferring to ice water bath, and obtaining a first solution after the temperature is stable;
(2) Uniformly dissolving 0.05mol of hexafluoro-tripolyphosphazene in 30mL of toluene solvent to obtain a second solution;
(3) Slowly dripping the second solution into the first solution under the condition of maintaining ice water bath and intense stirring, reacting for 3 hours, transferring to the room temperature condition for reacting for 24 hours, and sequentially filtering, rotary steaming and drying to obtain the flame-retardant precursor compound 1.
Preparation example 2
The flame-retardant precursor is a compound 2, and has the following structural formula:
the preparation method of the flame-retardant precursor comprises the following steps:
(1) Uniformly dissolving 0.100mol of glycidol and 0.102mol of triethylamine in 50mL of toluene solvent, transferring to ice water bath, and obtaining a first solution after the temperature is stable;
(2) Uniformly dissolving 0.033mol of hexafluoro-tripolyphosphazene in 30mL of toluene solvent to obtain a second solution;
(3) Slowly dripping the second solution into the first solution under the condition of maintaining ice water bath and intense stirring, reacting for 3 hours, transferring to the room temperature condition for reacting for 24 hours, and sequentially filtering, rotary steaming and drying to obtain the flame-retardant precursor compound 2.
Preparation example 3
The flame-retardant precursor is a compound 3, and has the following structural formula:
the preparation method of the flame-retardant precursor comprises the following steps:
(1) Uniformly dissolving 0.100mol of glycidol and 0.103mol of triethylamine in 50mL of toluene solvent, transferring to ice water bath, and obtaining a first solution after the temperature is stable;
(2) Uniformly dissolving 0.025mol of hexafluoro-triphosphazene in 30mL of toluene solvent to obtain a second solution;
(3) Slowly dripping the second solution into the first solution under the condition of maintaining ice water bath and intense stirring, reacting for 3 hours, transferring to the room temperature condition for reacting for 24 hours, and sequentially filtering, rotary steaming and drying to obtain the flame-retardant precursor compound 3.
Preparation example 4
The flame-retardant precursor is a compound 4, and has the following structural formula:
the preparation method of the flame-retardant precursor comprises the following steps:
(1) Uniformly dissolving 0.100mol of glycidol and 0.104mol of triethylamine in 50mL of toluene solvent, transferring to ice water bath, and obtaining a first solution after the temperature is stable;
(2) Uniformly dissolving 0.020mol of hexafluoro-triphosphazene in 30mL of toluene solvent to obtain a second solution;
(3) Slowly dripping the second solution into the first solution under the condition of maintaining ice water bath and intense stirring, reacting for 3 hours, transferring to the room temperature condition for reacting for 24 hours, and sequentially filtering, rotary steaming and drying to obtain the flame-retardant precursor compound 4.
Preparation example 5
The flame-retardant precursor is a compound 5, the infrared spectrum of the structure of the flame-retardant precursor is shown in the attached figure 1, and the structural formula is as follows:
the preparation method of the flame-retardant precursor comprises the following steps:
(1) Uniformly dissolving 0.105mol of glycidol and 0.107mol of triethylamine in 50mL of toluene solvent, transferring to ice water bath, and obtaining a first solution after the temperature is stable;
(2) Uniformly dissolving 0.017mol of hexafluoro-triphosphazene in 30mL of toluene solvent to obtain a second solution;
(3) Slowly dripping the second solution into the first solution under the condition of maintaining ice water bath and intense stirring, reacting for 3 hours, transferring to the room temperature condition for reacting for 24 hours, and sequentially filtering, rotary steaming and drying to obtain the flame-retardant precursor compound 5.
Example 1
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 30 parts by mass of the flame-retardant precursor, 1 part by mass of ethylene glycol diglycidyl ether and 0.31 part by mass of lithium hexafluorophosphate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 0.5g/Ah, and polymerizing at 50 ℃ for 8 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 2
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 20 parts by mass of the flame-retardant precursor in preparation example 2, 1 part by mass of ethylene glycol diglycidyl ether and 0.21 part by mass of lithium tetrafluoroborate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 0.7g/Ah, and polymerizing at 50 ℃ for 8 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 3
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 15 parts by mass of the flame-retardant precursor in preparation example 3, 1 part by mass of ethylene glycol diglycidyl ether and 0.16 part by mass of lithium trifluoromethylsulfonate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of the substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 0.8g/Ah, and polymerizing at 45 ℃ for 10 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 4
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 12 parts by mass of the flame-retardant precursor, 1 part by mass of ethylene glycol diglycidyl ether and 0.13 part by mass of lithium bis (fluorosulfonyl) imide in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of the substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.0g/Ah, and polymerizing at 45 ℃ for 10 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 5
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of the flame-retardant precursor in preparation example 5, 1 part by mass of ethylene glycol diglycidyl ether and 0.11 part by mass of lithium oxalate difluoroborate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.2g/Ah, and polymerizing at 45 ℃ for 10 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 6
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of the flame-retardant precursor in preparation example 5, 1 part by mass of 1, 4-butanediol diglycidyl ether and 0.11 part by mass of lithium hexafluorophosphate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.0g/Ah, and polymerizing at 50 ℃ for 8 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 7
A solid-state battery, which consists of a lithium nickel cobalt manganese 811 positive electrode, a graphite negative electrode and a gel electrolyte, wherein the infrared spectrum of the gel electrolyte is shown in fig. 2.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of the flame-retardant precursor in preparation example 5, 0.8 part by mass of triglycidyl isocyanurate and 0.108 part by mass of lithium hexafluorophosphate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.2g/Ah, and polymerizing at 50 ℃ for 8 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 8
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of the flame-retardant precursor in preparation example 5, 0.6 part by mass of trimethylolethane triglycidyl ether and 0.106 part by mass of lithium hexafluorophosphate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.2g/Ah, and polymerizing at 45 ℃ for 10 hours to obtain the gel electrolyte and the solid-state battery thereof.
Example 9
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of the flame-retardant precursor in preparation example 5, 0.4 part by mass of pentaerythritol tetraglycidyl ether and 0.104 part by mass of lithium hexafluorophosphate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.5g/Ah, and polymerizing at 45 ℃ for 10 hours to obtain the gel electrolyte and the solid-state battery thereof.
Comparative example 1
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of pentaerythritol tetraglycidyl ether and 0.1 part by mass of lithium hexafluorophosphate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) The reaction solution was injected between the positive electrode of lithium nickel cobalt manganese 811 and the negative electrode of graphite in an amount of 1.5g/Ah, and polymerization was carried out at 45℃for 10 hours, to obtain a gel electrolyte and a solid-state battery thereof.
Comparative example 2
A solid state battery comprised of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) Uniformly dissolving 10 parts by mass of pentaerythritol tetraglycidyl ether, 5 parts by mass of hexafluoro-tripolyphosphazene and 0.1 part by mass of lithium tetrafluoroborate in 100 parts by mass of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) The reaction solution was injected between the positive electrode of lithium nickel cobalt manganese 811 and the negative electrode of graphite in an amount of 1.5g/Ah, and polymerization was carried out at 45℃for 10 hours, to obtain a gel electrolyte and a solid-state battery thereof.
Comparative example 3
This comparative example provides a solid state battery consisting of a lithium nickel cobalt manganate 811 positive electrode, a graphite negative electrode, and a gel electrolyte.
The preparation method of the solid-state battery comprises the following steps:
(1) 10 parts by weight of the flame-retardant precursor described in preparation example 5, 1 part of ethylene glycol diglycidyl ether and 0.11 part of SnCl 4 Uniformly dissolving in 100 parts of electrolyte to obtain a reaction solution, wherein the solvent in the electrolyte is equal volume of ethylene carbonate, methyl ethyl carbonate and dimethyl carbonate, the lithium salt is lithium hexafluorophosphate, and the mass concentration of substances in the electrolyte is 1.05mol/L;
(2) And (3) injecting the reaction solution between the positive electrode of the lithium nickel cobalt manganese 811 and the negative electrode of the graphite according to the injection coefficient of 1.0g/Ah, and polymerizing at 45 ℃ for 10 hours to obtain the gel electrolyte and the solid-state battery thereof.
Performance testing
The solid-state batteries described in examples 1 to 9 and comparative examples 1 to 3 were subjected to the following tests:
(1) Cycle performance test (25 ℃):
1) Stopping discharging at a constant current of 1C and a final voltage, and standing for 30min;
2) Converting the constant-current charging at 1C to constant-voltage charging until the charging current is reduced to 0.05C, stopping charging, and standing for 30min;
3) Stopping discharging at a constant current of 1C and a final voltage, standing for 30min, and recording the discharge capacity;
4) Continuously cycling for 800 times according to 2) to 3), wherein the ratio of 800 times of discharge capacity to the first discharge capacity is taken as the discharge capacity retention rate.
(2) Heating test at 150 ℃): the solid-state battery was put into a temperature box, the temperature box was raised from the test ambient temperature to 150 ℃ + -2 ℃ at a temperature rise rate of 5 ℃/min, and after maintaining this temperature for 30min, heating was stopped, and the solid-state battery was observed for 1h.
(3) Needling test: the steel needle with the diameter of 5mm (the conical angle of the needle point is 45 degrees, the surface of the needle is smooth and clean, no rust, no oxide layer and no greasy dirt) penetrates from the direction perpendicular to the polar plate of the solid-state battery at the speed of (25+/-5) mm/s, the penetrating position is the geometric center of the penetrated surface, the steel needle stays in the solid-state battery, and the solid-state battery is observed for 1h.
(4) Appearance morphology: and testing by using a scanning electron microscope.
The test results are summarized in table 1.
TABLE 1
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The analysis of the data in table 1 shows that the solid-state battery further formed by the gel electrolyte containing the flame-retardant precursor provided by the invention has the discharge capacity retention rate of more than 90.7% after 800 cycles, excellent cycle performance, no fire or explosion in 150 ℃ heating and needling tests, good flame-retardant effect and high safety under the condition of less flame-retardant precursor consumption.
Analysis of comparative example 1 and examples 1 to 9 revealed that the solid-state battery prepared with the gel electrolyte of comparative example 1 had excellent cycle performance, but failed the 150 ℃ heating test without containing the flame retardant component, and also developed ignition and explosion in the needling test.
As can be seen from analysis of comparative example 2 and examples 1 to 9, the gel electrolyte of comparative example 2 is added with the small molecular flame retardant hexafluoro-triphosphazene, and the solid-state battery can pass the needling test, but the conditions of ignition and explosion occur in the heating test at 150 ℃, which indicates that the small molecular flame retardant is easy to separate out from the gel electrolyte under the condition of heating, and the safety performance of the solid-state battery can not be effectively ensured; in addition, the solid-state battery of comparative example 2 was relatively poor in long-term cycle performance in comparison with the manner in which the flame retardant structure was fixed to the polymer backbone employed in examples 1 to 9, and also demonstrated that the small-molecule flame retardant was inferior in maintaining the stability of the electrochemical performance of the solid-state battery as in examples 1 to 9.
Analysis of comparative example 3 and example 6 shows that comparative example 3 has inferior performance to example 6, and that the use of lithium fluoride salt as a catalyst is more advantageous for improving the performance of the solid-state battery than the conventional catalyst.
Analysis examples 1-9 show that, under the same crosslinking degree, the prepared solid-state battery has better cycle performance along with the increase of the number of epoxy groups on the flame-retardant precursor, mainly because more epoxy groups are beneficial to the transmission and migration of lithium ions and the ionic conductivity is higher; however, increasing the degree of crosslinking of the gel electrolyte has an impeding effect on the transport and migration of lithium ions, which reduces the ionic conductivity and causes a loss in the cycling performance of the solid-state battery.
Taking preparation example 5 as an example, FIG. 1 is an infrared spectrum diagram of a flame-retardant precursor thereof, wherein the wavelength in the spectrum diagram of the flame-retardant precursor is 2950cm -1 The peak of (C) is methylene structure, 2916cm -1 The peak of (C-H) is 1193cm -1 The peak is of P=N structure, 1019cm -1 The peak of (C) is P-O-C structure, 850cm -1 The peaks of (2) are epoxy groups, and these peaks appearIt was confirmed that the structure of compound 5 could be obtained by the method of production example 5 of the present invention.
The solid-state battery prepared in example 7 was disassembled, and the gel electrolyte therein was subjected to infrared spectroscopic test, the result of which is shown in FIG. 2, at a wavelength of 1720cm -1 And 1293cm -1 The peak of C=O structure and the peak of C-N structure in the crosslinking agent appear respectively, and at the same time, the wavelength is 1052cm -1 Structural peaks of C-O-C of fatty chains appear, which proves that the flame-retardant precursor and the cross-linking agent have polymerization reaction.
Taking example 1 as an example, fig. 3 shows the microscopic morphology of the positive electrode surface before the polymerization reaction of the reaction solution, and fig. 4 shows the microscopic morphology of the positive electrode surface after the polymerization reaction of the reaction solution, and the result proves that the interface contact between the gel electrolyte and the electrode is good.
The applicant states that the detailed method of the present invention is illustrated by the above examples, but the present invention is not limited to the detailed method described above, i.e. it does not mean that the present invention must be practiced in dependence upon the detailed method described above. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.
Claims (8)
1. The gel electrolyte is characterized in that the preparation raw materials of the gel electrolyte comprise a flame-retardant precursor, a crosslinking monomer, a catalyst and electrolyte, wherein the flame-retardant precursor has the following structure:
；
the crosslinking monomer is selected from glycidyl ether, and the glycidyl ether is selected from any one or a combination of at least two of ethylene glycol diglycidyl ether, 1, 4-butanediol diglycidyl ether, neopentyl glycol diglycidyl ether, resorcinol diglycidyl ether, bisphenol A diglycidyl ether, triglycidyl isocyanurate, trimethylolethane triglycidyl ether, trimethylolpropane triglycidyl ether or pentaerythritol tetraglycidyl ether;
the catalyst is selected from lithium fluoride salts;
the lithium fluoride salt is selected from any one or a combination of at least two of lithium hexafluorophosphate, lithium hexafluoroarsenate, lithium tetrafluoroborate, lithium oxalyldifluoroborate, lithium trifluoromethanesulfonate, lithium bistrifluoromethylsulfonimide and lithium bistrifluorosulfonylimide;
the electrolyte comprises lithium salt and solvent;
in the electrolyte, the mass concentration of the lithium salt is 1.05-2 mol/L;
the gel electrolyte is prepared by a method comprising the following steps:
and mixing the flame-retardant precursor, the crosslinking monomer, the catalyst and the electrolyte in the formula amount to form a reaction solution, and polymerizing the reaction solution to obtain the gel electrolyte.
2. The gel electrolyte of claim 1, wherein the method of preparing the flame retardant precursor comprises the steps of:
(1) Mixing glycidol, an acid binding agent and a solvent, and standing at the temperature of-5-5 ℃ to obtain a first solution;
(2) Mixing hexafluoro-triphosphazene with a solvent to obtain a second solution;
(3) And adding the second solution into the first solution at the temperature of between 5 ℃ below zero and 5 ℃ under stirring, carrying out a first reaction, heating, carrying out a second reaction, and carrying out aftertreatment to obtain the flame-retardant precursor.
3. The gel electrolyte according to claim 2, wherein in the step (1), the molar ratio of the glycidol to the acid-binding agent is 1 (1.01-1.05),
the acid binding agent comprises triethylamine and is prepared from the following components,
in the step (2), the molar ratio of the hexafluoro-tripolyphosphazene to the glycidol is 1: (2-6),
in the step (3), the time of the first reaction is 3-5h,
the temperature of the second reaction is 20-30 ℃,
the second reaction time is 24-48h,
the post-treatment comprises filtration, rotary steaming and drying.
4. The gel electrolyte according to claim 1, wherein the lithium salt in the electrolyte is selected from the group consisting of lithium hexafluorophosphate,
the solvent in the electrolyte is selected from any one or a combination of at least two of ethylene carbonate, propylene carbonate, dimethyl carbonate, diethyl carbonate and ethylmethyl carbonate.
5. The gel electrolyte of claim 1, wherein the crosslinking monomer comprises 1% -40% of the flame retardant precursor weight,
the catalyst accounts for 0.1 to 2.0 percent of the total mass consumption of the flame-retardant precursor and the crosslinking monomer,
the total mass of the flame-retardant precursor and the crosslinking monomer accounts for 1-20% of the mass of the electrolyte.
6. A method of preparing the gel electrolyte of any one of claims 1 to 5, comprising the steps of:
and mixing the flame-retardant precursor, the crosslinking monomer, the catalyst and the electrolyte in the formula amount to form a reaction solution, and polymerizing the reaction solution to obtain the gel electrolyte.
7. The process according to claim 6, wherein the polymerization temperature is 20 to 70 ℃,
the polymerization time is 1-24 and h.
8. A solid-state battery, characterized in that the solid-state battery comprises a positive electrode, a negative electrode and the gel electrolyte according to any one of claims 1 to 5,
the positive electrode comprises any one of lithium cobaltate, lithium manganate, lithium iron phosphate, lithium manganese iron phosphate, lithium nickel manganate or lithium nickel cobalt manganate,
the negative electrode comprises any one of graphite, lithium titanate, silicon carbon negative electrode or metal lithium;
the preparation method of the solid-state battery comprises the following steps:
mixing a formula amount of flame-retardant precursor, a crosslinking monomer, a catalyst and an electrolyte to form a reaction solution, injecting the reaction solution between a positive electrode and a negative electrode, polymerizing to form the gel electrolyte, obtaining the solid-state battery,
the injection coefficient of the reaction liquid between the anode and the cathode is 0.5-5 g/Ah.
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