CN116314815A - Positive electrode lithium supplementing flame retardant additive and preparation method and application thereof - Google Patents
Positive electrode lithium supplementing flame retardant additive and preparation method and application thereof Download PDFInfo
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- CN116314815A CN116314815A CN202310328017.9A CN202310328017A CN116314815A CN 116314815 A CN116314815 A CN 116314815A CN 202310328017 A CN202310328017 A CN 202310328017A CN 116314815 A CN116314815 A CN 116314815A
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- lithium
- flame retardant
- supplementing
- positive electrode
- retardant additive
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 93
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 93
- 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 78
- 239000003063 flame retardant Substances 0.000 title claims abstract description 78
- 230000001502 supplementing effect Effects 0.000 title claims abstract description 66
- 239000000654 additive Substances 0.000 title claims abstract description 43
- 230000000996 additive effect Effects 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 45
- 239000012298 atmosphere Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 10
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000010452 phosphate Substances 0.000 claims abstract description 7
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical group OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 229920001774 Perfluoroether Polymers 0.000 claims abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 4
- GKTNLYAAZKKMTQ-UHFFFAOYSA-N n-[bis(dimethylamino)phosphinimyl]-n-methylmethanamine Chemical compound CN(C)P(=N)(N(C)C)N(C)C GKTNLYAAZKKMTQ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910000077 silane Inorganic materials 0.000 claims abstract description 4
- 239000002243 precursor Substances 0.000 claims description 24
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- 238000004108 freeze drying Methods 0.000 claims description 14
- 238000001354 calcination Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000007774 positive electrode material Substances 0.000 claims description 11
- 239000011247 coating layer Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 9
- 235000021317 phosphate Nutrition 0.000 claims description 9
- 239000007983 Tris buffer Substances 0.000 claims description 6
- FWDBOZPQNFPOLF-UHFFFAOYSA-N ethenyl(triethoxy)silane Chemical compound CCO[Si](OCC)(OCC)C=C FWDBOZPQNFPOLF-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 6
- WVLBCYQITXONBZ-UHFFFAOYSA-N trimethyl phosphate Chemical compound COP(=O)(OC)OC WVLBCYQITXONBZ-UHFFFAOYSA-N 0.000 claims description 6
- -1 ethoxypentafluoroethyl cyclotriphosphazene Chemical compound 0.000 claims description 5
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical group COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- SPAUYKHQVLTCOL-UHFFFAOYSA-N C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C Chemical compound C1(=CC=CC=C1)OP(OC1=CC=CC=C1)(O)=O.C1(=CC=CC=C1)C SPAUYKHQVLTCOL-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- XTBBZRRBOAVBRA-UHFFFAOYSA-N dimethyl phenyl phosphate Chemical compound COP(=O)(OC)OC1=CC=CC=C1 XTBBZRRBOAVBRA-UHFFFAOYSA-N 0.000 claims description 3
- WOXXJEVNDJOOLV-UHFFFAOYSA-N ethenyl-tris(2-methoxyethoxy)silane Chemical compound COCCO[Si](OCCOC)(OCCOC)C=C WOXXJEVNDJOOLV-UHFFFAOYSA-N 0.000 claims description 3
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 3
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 3
- 150000002823 nitrates Chemical class 0.000 claims description 3
- 150000002978 peroxides Chemical class 0.000 claims description 3
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 3
- DQWPFSLDHJDLRL-UHFFFAOYSA-N triethyl phosphate Chemical compound CCOP(=O)(OCC)OCC DQWPFSLDHJDLRL-UHFFFAOYSA-N 0.000 claims description 3
- XZZNDPSIHUTMOC-UHFFFAOYSA-N triphenyl phosphate Chemical compound C=1C=CC=CC=1OP(OC=1C=CC=CC=1)(=O)OC1=CC=CC=C1 XZZNDPSIHUTMOC-UHFFFAOYSA-N 0.000 claims description 3
- QLCATRCPAOPBOP-UHFFFAOYSA-N tris(1,1,1,3,3,3-hexafluoropropan-2-yl) phosphate Chemical compound FC(F)(F)C(C(F)(F)F)OP(=O)(OC(C(F)(F)F)C(F)(F)F)OC(C(F)(F)F)C(F)(F)F QLCATRCPAOPBOP-UHFFFAOYSA-N 0.000 claims description 3
- VWIHWVBGVWJAPL-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoropropan-2-yl hydrogen carbonate Chemical compound OC(=O)OC(C(F)(F)F)C(F)(F)F VWIHWVBGVWJAPL-UHFFFAOYSA-N 0.000 claims description 2
- GBPVMEKUJUKTBA-UHFFFAOYSA-N methyl 2,2,2-trifluoroethyl carbonate Chemical compound COC(=O)OCC(F)(F)F GBPVMEKUJUKTBA-UHFFFAOYSA-N 0.000 claims description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 15
- 239000003792 electrolyte Substances 0.000 abstract description 10
- 239000013589 supplement Substances 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 12
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 10
- 239000007789 gas Substances 0.000 description 10
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 229910013553 LiNO Inorganic materials 0.000 description 6
- 238000000498 ball milling Methods 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 238000001694 spray drying Methods 0.000 description 6
- 238000001816 cooling Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000000084 colloidal system Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229960004887 ferric hydroxide Drugs 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 2
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- BWUZCLFBFFQLLM-UHFFFAOYSA-N 1,1,1-trifluoropropan-2-yl hydrogen carbonate Chemical compound FC(F)(F)C(C)OC(O)=O BWUZCLFBFFQLLM-UHFFFAOYSA-N 0.000 description 1
- CBTAIOOTRCAMBD-UHFFFAOYSA-N 2-ethoxy-2,4,4,6,6-pentafluoro-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound CCOP1(F)=NP(F)(F)=NP(F)(F)=N1 CBTAIOOTRCAMBD-UHFFFAOYSA-N 0.000 description 1
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- 229910002566 KAl(SO4)2·12H2O Inorganic materials 0.000 description 1
- 229910018068 Li 2 O Inorganic materials 0.000 description 1
- 229910012851 LiCoO 2 Inorganic materials 0.000 description 1
- 229910010707 LiFePO 4 Inorganic materials 0.000 description 1
- 229910013870 LiPF 6 Inorganic materials 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 239000007773 negative electrode material Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62C—FIRE-FIGHTING
- A62C3/00—Fire prevention, containment or extinguishing specially adapted for particular objects or places
- A62C3/16—Fire prevention, containment or extinguishing specially adapted for particular objects or places in electrical installations, e.g. cableways
-
- 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
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Public Health (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a positive electrode lithium supplementing flame retardant additive, and a preparation method and application thereof, and belongs to the technical field of lithium batteries. The positive electrode lithium supplementing flame retardant additive is prepared by mixing a lithium supplementing material with a flame retardant solution, and sequentially reacting and drying the obtained mixed material in an inert atmosphere; the flame retardant is phosphite, phosphate, fluorocarbonate, fluoroether, silane or phosphazene; the lithium supplementing material is represented by Li x M y N 1‑y O z Wherein, M and N are any two elements of Fe, co, ni, mn, cu, V, mo, ti, al and Si, x=2-6, y=0.5-1, and z=2-4. The positive electrode lithium supplementing flame retardant additive provided by the invention can supplement lithium at the same timeThe flame retardant effect is achieved, and the addition amount of the existing flame retardant in the electrolyte is reduced, so that the low-temperature performance and the lithium ion transmission rate of the electrolyte are not affected.
Description
Technical Field
The invention belongs to the technical field of lithium battery additives, and particularly relates to a positive electrode lithium supplementing flame retardant additive, and a preparation method and application thereof.
Background
With the continuous development of new energy industry, lithium ion batteries are widely concerned, and the improvement of energy density is the key point of future development. In the battery cycle process, lithium ions in the positive electrode material can move to the negative electrode, an SEI film is generated on the surface of the negative electrode, and the SEI film consumes 7-10% of active lithium, which means Li extracted from the positive electrode material + Part of the lithium is irreversibly consumed, and lithium loss causes a decrease in battery capacity, a decrease in coulombic efficiency, and a deterioration in cycle performance. In order to further increase the energy density of lithium ion batteries, the supplementation of active lithium is an effective means to solve this problem. The current positive electrode lithium supplementing agent is mainly applied to power batteries.
In the power battery, the lithium iron phosphate and the ternary material are used as main materials, and the coulombic efficiency and the circulation process can be improved after the positive electrode lithium supplementing agent is added, but the power battery also needs to improve the multiplying power performance, and the thermal runaway of the battery can be possibly caused when the multiplying power performance is improved. In the high-rate charging process, lithium ions are rapidly released from the positive electrode to move towards the negative electrode, so that more active lithium is instantaneously present on the surface of the negative electrode, and at the moment, SEI film decomposition is easy to occur to cause lithium dendrite, so that more high-active oxygen is released from the surface of the positive electrode material, and thermal runaway of the battery is caused.
The current method for solving the thermal runaway of the battery is to add a flame retardant additive into the electrolyte, but the consumption of the flame retardant additive in the electrolyte is large (at least 5%), so that the cost and viscosity of the electrolyte are increased, and the conductivity and lithium ion transmission rate of the electrolyte are reduced, thereby influencing the cycle performance and the low-temperature performance of the battery.
Disclosure of Invention
The invention provides a positive electrode lithium supplementing flame retardant additive, a preparation method and application thereof.
In order to achieve the aim, the invention provides a positive electrode lithium supplementing flame retardant additive, which is prepared by mixing a lithium supplementing material with a flame retardant solution, and sequentially reacting and drying the obtained mixed material in an inert atmosphere; the flame retardant is phosphite, phosphate, fluorocarbonate, fluoroether, silane or phosphazene; the lithium supplementing material is represented by Li x M y N 1-y O z Wherein, M and N are any two elements of Fe, co, ni, mn, cu, V, mo, ti, al and Si, x=2-6, y=0.5-1, and z=2-4.
Preferably, the positive electrode lithium supplementing flame retardant additive takes a lithium supplementing material as a core and takes a flame retardant as a coating layer; the content of the inner core is 95 to 99.9 percent and the content of the coating layer is 0.1 to 5 percent according to the mass percent.
Preferably, the method comprises the steps of, the flame retardant is trimethyl phosphite, tris (2, 2-trifluoroethyl) phosphite, tris (hexafluoroisopropyl) phosphate, trimethyl phosphate, toluene diphenyl phosphate, triphenyl phosphate, tris (2, 2-trifluoroethyl) phosphate, dimethyl phenyl phosphate, triethyl phosphate, bis (2, 2-trifluoroethyl) carbonate, and methyl trifluoroethyl carbonate, bis hexafluoroisopropyl carbonate, 4-trifluoromethyl ethylene carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane or ethoxypentafluoroethyl cyclotriphosphazene.
Preferably, M is Fe or Ni, and N is Al or Si.
The invention provides a preparation method of the positive electrode lithium supplementing flame retardant additive, which is characterized by comprising the following steps:
1) Mixing a lithium source, an M source and an N source to obtain precursor powder;
2) Calcining the precursor powder in a vacuum environment to obtain a lithium supplementing material;
3) Mixing the lithium supplementing material with a flame retardant solution, reacting the obtained mixture in an inert atmosphere, drying the obtained reactant, and uniformly coating the flame retardant on the surface of the lithium supplementing material to obtain the positive electrode lithium supplementing flame retardant additive.
Preferably, the lithium source in the step 1) is one or more of lithium oxide, hydroxide, peroxide, inorganic salt or organic salt; the M source is one or more of oxide, hydroxide, sulfate, chlorate and nitrate of M; the N source is one or more of N oxides, hydroxides, sulfates, chlorates, nitrates and phosphates.
Preferably, the calcination temperature in the step 2) is 700-1000 ℃, the time is 1-10 h, and the vacuum degree is more than or equal to 1 x 10 -5 Pa。
Preferably, the reaction in step 3) is carried out in an inert atmosphere for a period of time ranging from 0.5 to 3 hours.
Preferably, the drying in step 3) is freeze drying; the temperature during freeze drying is-50 to-10 ℃.
The invention provides application of the positive electrode lithium-supplementing flame-retardant additive in positive electrode lithium, wherein the addition amount of the positive electrode lithium-supplementing flame-retardant additive is 0.1-5 wt% of the positive electrode active material.
Compared with the prior art, the invention has the advantages and positive effects that:
the positive electrode lithium supplementing flame retardant additive provided by the invention mixes the lithium supplementing material with the flame retardant solution and then dries the mixture, so that the flame retardant forms a compact coating layer on the surface of the lithium supplementing agent to form a core-shell structure taking the lithium supplementing material as a core and the flame retardant as a shell, and the core lithium supplementing material can provide extra lithium ions to compensate for the SEI film and lithium ions consumed in the circulating process; the shell flame retardant can capture high-activity oxygen released by the positive electrode material before the thermal runaway of the battery, so that the thermal runaway of the battery is prevented; and can capture oxygen radical generated by the lithium supplementing agent during formation.
Furthermore, the preparation method provided by the invention adopts a vacuum sintering mode to prepare the lithium supplementing material, the sintering time is short, the obtained lithium supplementing material is loose and does not agglomerate, the particle size of the material is small, additional crushing is not needed, and the byproducts are few. The use of freeze drying can avoid deactivation of the flame retardant additive by high temperature drying. Meanwhile, the method provided by the invention is simple in process and suitable for industrial production.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but 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 be within the scope of the invention.
The invention provides a positive electrode lithium supplementing flame retardant additive, which is prepared by mixing a lithium supplementing material and a flame retardant solution, and sequentially reacting and drying the obtained mixed material in an inert atmosphere; the flame retardant is phosphite, phosphate, fluorocarbonate, fluoroether, silane or phosphazene; the lithium supplementing material is represented by Li x M y N 1- y O z Wherein, M and N are any two elements of Fe, co, ni, mn, cu, V, mo, ti, al and Si, x=2-6, y=0.5-1, and z=2-4.
In the invention, the positive electrode lithium supplementing flame retardant additive takes a lithium supplementing material as a core and takes a flame retardant as a coating layer. The content of the inner core is preferably 95-99.9% by mass, and the content of the coating layer is preferably 0.1-5% by mass. In the invention, the dosage of the coating layer is controlled to be 0.1-5%, so that the flame retardant effect can be ensured and the capacity of the lithium supplementing material is not influenced.
In the present invention, the flame retardant is preferably trimethyl phosphite, tris (2, 2-trifluoroethyl) phosphite, tris (hexafluoroisopropyl) phosphate, trimethyl phosphate, toluene diphenyl phosphate, triphenyl phosphate, tris (2, 2-trifluoroethyl) phosphate, dimethyl phenyl phosphate, triethyl phosphate, or a mixture thereof bis (2, 2-trifluoroethyl) carbonate, methyltrifluoroethyl carbonate, bishexafluoroisopropyl carbonate, 4-trifluoromethyl ethylene carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane or ethoxypentafluoroethylcyclotriphosphazene, more preferred are ethoxypentafluoroethylcyclotriphosphazene, trimethyl phosphite, trimethyl phosphate, and vinyltriethoxysilane.
In the present invention, M is preferably Fe or Ni, and N is preferably Al or Si.
The positive electrode lithium supplementing flame retardant provided by the invention is characterized in that the surface of the lithium supplementing agent is coated with the flame retardant, and the core lithium supplementing agent can provide extra lithium ions to compensate the SEI film and lithium ions consumed in the circulating process; the coating layer outer shell flame retardant can capture high-activity oxygen released by the positive electrode material before the thermal runaway of the battery, so that the thermal runaway of the battery is prevented; meanwhile, oxygen radical free radicals generated by the lithium supplementing agent during formation can be captured, so that formation gas is reduced, high-temperature storage gas production is reduced, and the electrochemical performance and the safety performance of the battery are improved. The lithium is supplemented, and meanwhile, the flame retardant effect is achieved, so that the problems that lithium dendrites possibly caused by the increase of the lithium content at the negative electrode end in the circulation process of the lithium ion battery using the positive electrode lithium supplementing agent at present are solved, SEI films are decomposed due to the lithium dendrites, and thermal runaway caused by high active oxygen is generated in the positive electrode material are solved; meanwhile, the fire retardant is used as a coating layer, so that water and CO in the air can be isolated 2 The air stability of the material is improved, and the increase of the base number in the processes of material storage, transportation, tabletting and the like is inhibited. The flame retardant is added into the positive electrode lithium supplementing material, so that the flame retardant additive is not added into the electrolyte, the safety of the battery is ensured, and the low-temperature performance and the lithium ion transmission rate of the electrolyte are not influenced.
The invention provides a preparation method of the positive electrode lithium supplementing flame retardant additive, which is characterized by comprising the following steps:
1) Mixing a lithium source, an M source and an N source to obtain precursor powder;
2) Calcining the precursor powder in a vacuum environment to obtain a lithium supplementing material;
3) Mixing the lithium supplementing material with a flame retardant solution, reacting the obtained mixture in an inert atmosphere, drying the obtained reactant, and uniformly coating the flame retardant on the surface of the lithium supplementing material to obtain the positive electrode lithium supplementing flame retardant additive.
The invention mixes lithium source, M source and N source to obtain precursor powder. In the present invention, the mixing is preferably performed by grinding or dissolving the lithium source, the M source, and the N source in a solvent and then spray-drying. In the present invention, the solvent is preferably deionized water, ethanol or a mixed solution of water and ethanol. In the present invention, the spray-drying temperature is preferably 150 to 250 ℃.
In the present invention, the lithium source is preferably one or more of lithium oxide, hydroxide, peroxide, inorganic salt or organic salt; more preferably Li 2 O、LiOH、Li 2 CO 3 、LiNO 3 、Li 2 C 2 O 4 、CH 3 One or more of COOLi; most preferably LiOH, li 2 CO 3 Or LiNO 3 . In the invention, the M source is preferably one or more of oxide, hydroxide, sulfate, chlorate and nitrate of M; more preferably Fe 2 O 3 、Fe 3 O 4 、FeC 2 O 4 、Fe(NO 3 ) 3 ·9H 2 O、FeCl 3 、Fe 2 (SO 4 ) 3 、NiO、Ni(NO 3 ) 2 、Ni 2 SO 4 Or NiCl 3 The method comprises the steps of carrying out a first treatment on the surface of the Most preferably Fe (NO) 3 ) 3 ·9H 2 O or Ni (NO) 3 ) 2 . In the invention, the N source is preferably one or more of oxides, hydroxides, sulfates, chlorates, nitrates and phosphates of N; more preferably Al 2 O 3 、AlCl 3 、Al 2 (SO 4 ) 3 、KAl(SO 4 ) 2 ·12H 2 O、CuCl 2 、CuSO 4 ·5H 2 O、Cu(NO 3 ) 2 、MnO 2 SiOx, silicate or silicone; most preferably Al 2 (SO 4 ) 3 、CuSO 4 ·5H 2 O、MnO 2 Or a silicone.
After the precursor powder is obtained, the precursor powder is calcined in a vacuum environment to obtain the lithium supplementing material. In the invention, calcination is carried out under vacuum condition, so that the generated by-product gas can be rapidly discharged from the interior of the material, thereby obtaining loose and uncracked materialLithium supplementing material of the block. And the calcination is carried out under the vacuum condition, so that byproducts can be timely discharged, the high-speed forward reaction is promoted, and the calcination time is shortened. In the invention, the temperature of the vacuum calcination is 700-1000 ℃, the time is 1-10 h, and the vacuum degree is more than or equal to 1 x 10 -5 Pa。
After the lithium supplementing material is obtained, the lithium supplementing material is mixed with the flame retardant solution, the obtained mixed material reacts in inert atmosphere, the obtained reactant is dried, and the flame retardant is uniformly coated on the surface of the lithium supplementing material, so that the anode lithium supplementing flame retardant additive is obtained. In the present invention, the reaction is preferably carried out in an inert atmosphere for a period of time of 0.5 to 3 hours. In the present invention, the inert atmosphere is preferably nitrogen. In the present invention, the drying is preferably freeze-drying; the temperature during freeze drying is-50 to-10 ℃. In the present invention, freeze drying can avoid deactivation of the flame retardant additive by high temperature drying.
The invention provides application of the positive electrode lithium supplementing flame retardant additive in the positive electrode lithium supplementing of a lithium ion battery, wherein the addition amount of the positive electrode lithium supplementing flame retardant additive is 0.1-5 wt% of the positive electrode active material. In the present invention, the positive electrode active material is preferably LiCoO 2 、LiFePO 4 And at least one of NCM, more preferably NCM811. In the present invention, the lithium ion battery preferably further includes a current collector, a negative electrode, a separator, and an electrolyte. The negative electrode active material is preferably at least one of natural graphite, artificial graphite, soft carbon, hard carbon, lithium titanate, silicon carbon, and silicon oxygen; more preferably a silicon oxygen negative electrode.
The technical solutions provided by the present invention are described in detail below in conjunction with examples for further illustrating the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
According to formula Li 5 FeO 4 Weighing LiNO according to the corresponding element mole ratio 3 、Fe(NO 3 ) 3 ·9H 2 O. Fe (NO) 3 ) 3 ·9H 2 The O solution is gradually dripped into boiling deionized water, and is stirred during dripping,and after the dripping is finished, reacting for 3 hours at 90 ℃ to obtain ferric hydroxide colloid. Drop-adding LiNO into ferric hydroxide colloid 3 And (3) obtaining a precursor solution after the solution, and carrying out spray drying (the temperature is 150 ℃) on the precursor solution to obtain precursor powder.
Heating the precursor powder to 950 ℃ at a speed of 15 ℃/min under vacuum condition, preserving heat for 1 hour, and cooling to room temperature at a speed of 15 ℃/min to obtain Li 5 FeO 4 . Li is mixed with 5 FeO 4 Adding the mixture and trimethyl phosphate into a reaction kettle containing inert atmosphere according to the mass ratio of 98:2, mixing for 0.5h, and freeze-drying the reaction product at-50 ℃ for 1h after the reaction is finished to obtain the anode lithium-supplementing flame-retardant additive.
Example 2
The positive electrode lithium-supplementing agent was Li as in example 1 5 FeO 4 . Li is mixed with 5 FeO 4 Adding the mixture and ethoxy pentafluoro cyclotriphosphazene into a reaction kettle containing inert atmosphere according to the mass ratio of 99:1 for reaction for 1h, and freeze-drying the reaction product at-30 ℃ for 2h after the reaction is finished to obtain the anode lithium supplementing flame retardant additive.
Example 3
According to formula Li 2 NiO 2 And weighing LiOH and NiO according to the corresponding molar ratio of each element, placing the weighed samples into a ball milling tank, and ball milling at 500rpm for 5 hours to obtain precursor powder.
Heating the obtained precursor powder to 800 ℃ at a speed of 20 ℃/min under vacuum condition, preserving heat for 8 hours, and cooling to room temperature at a speed of 20 ℃/min to obtain Li 2 NiO 2 . Li is mixed with 2 NiO 2 Adding the mixture and vinyl triethoxysilane into a reaction kettle containing inert atmosphere according to the mass ratio of 95:5 for reaction for 3 hours, and freeze-drying the reaction product at-20 ℃ for 5 hours after the reaction is finished to obtain the anode lithium supplementing flame retardant additive.
Example 4
According to formula Li 4 SiO 4 Weighing LiOH H according to the corresponding molar ratio of each element 2 O、SiO 2 And placing the weighed sample into a ball milling tank, and ball milling at 500rpm for 5 hours to obtain precursor powder.
Subjecting the precursor powder to vacuum conditions to obtainHeating to 900 ℃ at a speed of 15 ℃/min, preserving heat for 6 hours, and cooling to room temperature at a speed of 15 ℃/min to obtain Li 4 SiO 4 Li is taken as 4 SiO 4 Adding the mixture and trimethyl phosphite into a reaction kettle containing inert atmosphere according to the mass ratio of 97:3 for reaction for 3 hours, and freeze-drying the reaction product at-40 ℃ for 1.5 hours after the reaction is finished to obtain the anode lithium-supplementing flame-retardant additive.
Example 5
According to formula Li 5 Fe 0.95 Al 0.05 O 4 Weighing LiNO according to the corresponding element mole ratio 3 、Fe(NO 3 ) 3 ·9H 2 O、Al(NO 3 ) 3 . Fe (NO) 3 ) 3 ·9H 2 And gradually dropwise adding the O solution into boiling deionized water, stirring in the dropwise adding process, and reacting at 90 ℃ for 3 hours after the dropwise adding is finished to obtain ferric hydroxide colloid. Dropwise adding Al (NO) into ferric hydroxide colloid 3 ) 3 And LiNO 3 And (3) obtaining a precursor solution after the solution, and carrying out spray drying (the temperature is 150 ℃) on the precursor solution to obtain precursor powder.
Heating the precursor powder to 950 ℃ at a speed of 15 ℃/min under vacuum condition, preserving heat for 1 hour, and cooling to room temperature at a speed of 15 ℃/min to obtain Li 5 Fe 0.95 Al 0.05 O 4 . Li is mixed with 5 Fe 0.95 Al 0.05 O 4 Adding the mixture and trimethyl phosphate into a reaction kettle containing inert atmosphere according to the mass ratio of 98:2, mixing for 0.5h, and freeze-drying the reaction product at-50 ℃ for 1h after the reaction is finished to obtain the anode lithium-supplementing flame-retardant additive.
Example 6
According to formula Li 2 Ni 0.98 Si 0.02 O 2 And weighing LiOH, niO, siO corresponding to the molar ratio of each element, placing the weighed sample into a ball milling tank, and ball milling at 500rpm for 5 hours to obtain precursor powder.
Heating the obtained precursor powder to 800 ℃ at a speed of 20 ℃/min under vacuum condition, preserving heat for 8 hours, and cooling to room temperature at a speed of 20 ℃/min to obtain Li 2 Ni 0.98 Si 0.02 O 2 . Li is mixed with 2 Ni 0.98 Si 0.02 O 2 Adding the mixture and vinyl triethoxysilane into a reaction kettle containing inert atmosphere according to the mass ratio of 95:5 for reaction for 3 hours, and freeze-drying the reaction product at-20 ℃ for 5 hours after the reaction is finished to obtain the anode lithium supplementing flame retardant additive.
Comparative example 1
The difference from example 1 is that the lithium-compensating material is obtained by sintering a precursor under nitrogen atmosphere, and the other operation modes are exactly the same as in example 1.
Comparative example 2
The difference from example 1 is that the lithium supplement material prepared is not coated with a flame retardant additive.
Comparative example 3
The difference from example 1 is that the drying mode in the preparation of the lithium-compensating flame retardant is spray drying, the spray drying temperature being 200 ℃.
Performance testing
The products of the above examples and comparative examples were added to a pouch cell for electrochemical performance testing, gas production and needling experiments, wherein the positive electrode was commercial NCM811, the negative electrode was commercial silicon carbon negative electrode composite graphite, and the electrolyte was 1mol/L LiPF 6 And EC: EMC with a mass ratio of 7:3, the battery capacity was 2.0Ah, the formation cutoff voltage was 4.4V, the circulating voltage range was 2.8V to 4.2V, the formation gas yield was tested respectively, the capacity retention rate and the gas expansion rate after 100 cycles of 1C, and the test results are shown in Table 1.
Table 1 test results
Note that: the gas yield test method of the formation in the table is that the gas volume of the gas bag chamber after the formation of the soft package battery is tested by a drainage method, and the gas expansion rate test method is that the thickness change of the highest point before and after the circulation of the soft package battery is measured.
As can be seen from Table 1, the positive electrode lithium supplement agent coated with the flame retardant exerts better safety performance while the lithium supplement amount is not influenced, and the calcination is performed in a vacuum mode, so that the battery cycle performance is improved compared with that of calcination under inert gas, because the particle size of the lithium supplement agent prepared by the method is smaller, the residual alkali amount is low, the lithium supplement agent can be mixed with the positive electrode material uniformly, lithium ions can be fully extracted, and the capacity is exerted.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The positive electrode lithium supplementing flame retardant additive is characterized by being prepared by mixing a lithium supplementing material with a flame retardant solution, and sequentially reacting and drying the obtained mixed material in an inert atmosphere; the flame retardant is phosphite, phosphate, fluorocarbonate, fluoroether, silane or phosphazene; the lithium supplementing material is represented by Li x M y N 1-y O z Wherein, M and N are any two elements of Fe, co, ni, mn, cu, V, mo, ti, al and Si, x=2-6, y=0.5-1, and z=2-4.
2. The positive electrode lithium-supplementing flame-retardant additive according to claim 1, wherein the positive electrode lithium-supplementing flame-retardant additive takes a lithium-supplementing material as a core and takes a flame retardant as a coating layer; the content of the inner core is 95 to 99.9 percent and the content of the coating layer is 0.1 to 5 percent according to the mass percent.
3. The positive electrode lithium-supplementing flame-retardant additive according to claim 1, wherein, the flame retardant is trimethyl phosphite, tris (2, 2-trifluoroethyl) phosphite, tris (hexafluoroisopropyl) phosphate, trimethyl phosphate, toluene diphenyl phosphate, triphenyl phosphate, tris (2, 2-trifluoroethyl) phosphate, dimethyl phenyl phosphate, triethyl phosphate, bis (2, 2-trifluoroethyl) carbonate, and methyl trifluoroethyl carbonate, bis hexafluoroisopropyl carbonate, 4-trifluoromethyl ethylene carbonate, 1, 2-tetrafluoroethyl-2, 3-tetrafluoropropyl ether, vinyltriethoxysilane, vinyltris (2-methoxyethoxy) silane or ethoxypentafluoroethyl cyclotriphosphazene.
4. The positive electrode lithium-compensating flame retardant additive of claim 1, wherein M is Fe or Ni and N is Al or Si.
5. The method for preparing the positive electrode lithium-supplementing flame-retardant additive according to any one of claims 1 to 4, which is characterized by comprising the following steps:
1) Mixing a lithium source, an M source and an N source to obtain precursor powder;
2) Calcining the precursor powder in a vacuum environment to obtain a lithium supplementing material;
3) Mixing the lithium supplementing material with a flame retardant solution, reacting the obtained mixture in an inert atmosphere, drying the obtained reactant, and uniformly coating the flame retardant on the surface of the lithium supplementing material to obtain the positive electrode lithium supplementing flame retardant additive.
6. The preparation method according to claim 5, wherein the lithium source in step 1) is one or more of lithium oxide, hydroxide, peroxide, inorganic salt or organic salt; the M source is one or more of oxide, hydroxide, sulfate, chlorate and nitrate of M; the N source is one or more of N oxides, hydroxides, sulfates, chlorates, nitrates and phosphates.
7. The preparation method according to claim 5, wherein the calcination temperature in step 2) is 700-1000 ℃ for 1-10 hours, and the vacuum degree is not less than 1 x 10 -5 Pa。
8. The process according to claim 5, wherein the reaction is carried out in an inert atmosphere in step 3) for a period of 0.5 to 3 hours.
9. The method of claim 5, wherein the drying in step 3) is freeze drying; the temperature during freeze drying is-50 to-10 ℃.
10. The use of the positive electrode lithium-supplementing flame retardant additive according to any one of claims 1 to 4 in positive electrode lithium supplementing, wherein the addition amount of the positive electrode lithium-supplementing flame retardant additive is 0.1 to 5wt% of the positive electrode active material.
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| CN117059804A (en) * | 2023-10-13 | 2023-11-14 | 瑞浦兰钧能源股份有限公司 | Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery |
| CN117457910A (en) * | 2023-12-22 | 2024-01-26 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece and sodium ion battery |
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| CN117059804A (en) * | 2023-10-13 | 2023-11-14 | 瑞浦兰钧能源股份有限公司 | Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery |
| CN117059804B (en) * | 2023-10-13 | 2024-03-19 | 瑞浦兰钧能源股份有限公司 | Chemical pre-lithium agent, lithium ion battery and preparation method of lithium ion battery |
| CN117457910A (en) * | 2023-12-22 | 2024-01-26 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece and sodium ion battery |
| CN117457910B (en) * | 2023-12-22 | 2024-04-02 | 天鹏锂能技术(淮安)有限公司 | Positive pole piece and sodium ion battery |
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