CN117013072A - Electrolyte for lithium nickel manganese oxide battery and preparation method and application thereof - Google Patents
Electrolyte for lithium nickel manganese oxide battery and preparation method and application thereof Download PDFInfo
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- CN117013072A CN117013072A CN202310950298.1A CN202310950298A CN117013072A CN 117013072 A CN117013072 A CN 117013072A CN 202310950298 A CN202310950298 A CN 202310950298A CN 117013072 A CN117013072 A CN 117013072A
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- electrolyte
- manganese oxide
- nickel manganese
- lithium nickel
- oxide battery
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 99
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 229930003935 flavonoid Natural products 0.000 claims abstract description 32
- 235000017173 flavonoids Nutrition 0.000 claims abstract description 32
- 150000002215 flavonoids Chemical class 0.000 claims abstract description 31
- 239000013538 functional additive Substances 0.000 claims abstract description 13
- 239000002994 raw material Substances 0.000 claims abstract description 11
- GAMYVSCDDLXAQW-AOIWZFSPSA-N Thermopsosid Natural products O(C)c1c(O)ccc(C=2Oc3c(c(O)cc(O[C@H]4[C@H](O)[C@@H](O)[C@H](O)[C@H](CO)O4)c3)C(=O)C=2)c1 GAMYVSCDDLXAQW-AOIWZFSPSA-N 0.000 claims abstract description 9
- 229930003944 flavone Natural products 0.000 claims abstract description 9
- 235000011949 flavones Nutrition 0.000 claims abstract description 9
- VHBFFQKBGNRLFZ-UHFFFAOYSA-N vitamin p Natural products O1C2=CC=CC=C2C(=O)C=C1C1=CC=CC=C1 VHBFFQKBGNRLFZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZONYXWQDUYMKFB-UHFFFAOYSA-N SJ000286395 Natural products O1C2=CC=CC=C2C(=O)CC1C1=CC=CC=C1 ZONYXWQDUYMKFB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229930003949 flavanone Natural products 0.000 claims abstract description 5
- 235000011981 flavanones Nutrition 0.000 claims abstract description 5
- 150000002212 flavone derivatives Chemical class 0.000 claims abstract description 5
- -1 naphthoflavone Natural products 0.000 claims abstract description 4
- GOMNOOKGLZYEJT-UHFFFAOYSA-N isoflavone Chemical compound C=1OC2=CC=CC=C2C(=O)C=1C1=CC=CC=C1 GOMNOOKGLZYEJT-UHFFFAOYSA-N 0.000 claims abstract description 3
- CJWQYWQDLBZGPD-UHFFFAOYSA-N isoflavone Natural products C1=C(OC)C(OC)=CC(OC)=C1C1=COC2=C(C=CC(C)(C)O3)C3=C(OC)C=C2C1=O CJWQYWQDLBZGPD-UHFFFAOYSA-N 0.000 claims abstract description 3
- 235000008696 isoflavones Nutrition 0.000 claims abstract description 3
- 150000002207 flavanone derivatives Chemical class 0.000 claims abstract 2
- 239000000654 additive Substances 0.000 claims description 53
- 230000000996 additive effect Effects 0.000 claims description 47
- 239000003960 organic solvent Substances 0.000 claims description 23
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 22
- 229910003002 lithium salt Inorganic materials 0.000 claims description 22
- 159000000002 lithium salts Chemical class 0.000 claims description 22
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 16
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 claims description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 5
- 150000005676 cyclic carbonates Chemical class 0.000 claims description 4
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 3
- 229910013870 LiPF 6 Inorganic materials 0.000 claims description 3
- SOPLBEYALUUGBF-UHFFFAOYSA-N O1C(=CC(=O)C2=CC=CC=C12)C1=CC=CC=C1.C1=CC=CC2=CC=CC=C12 Chemical compound O1C(=CC(=O)C2=CC=CC=C12)C1=CC=CC=C1.C1=CC=CC2=CC=CC=C12 SOPLBEYALUUGBF-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
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 229920001567 vinyl ester resin Polymers 0.000 claims 1
- 230000014759 maintenance of location Effects 0.000 abstract description 9
- VFMMPHCGEFXGIP-UHFFFAOYSA-N 7,8-Benzoflavone Chemical compound O1C2=C3C=CC=CC3=CC=C2C(=O)C=C1C1=CC=CC=C1 VFMMPHCGEFXGIP-UHFFFAOYSA-N 0.000 abstract 2
- OUGIDAPQYNCXRA-UHFFFAOYSA-N beta-naphthoflavone Chemical compound O1C2=CC=C3C=CC=CC3=C2C(=O)C=C1C1=CC=CC=C1 OUGIDAPQYNCXRA-UHFFFAOYSA-N 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 24
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 23
- 239000000243 solution Substances 0.000 description 20
- 238000003756 stirring Methods 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 16
- 229910052786 argon Inorganic materials 0.000 description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 239000011356 non-aqueous organic solvent Substances 0.000 description 10
- 238000005303 weighing Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- 229910002804 graphite Inorganic materials 0.000 description 8
- 239000010439 graphite Substances 0.000 description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 101100537779 Homo sapiens TPM2 gene Proteins 0.000 description 6
- 102100036471 Tropomyosin beta chain Human genes 0.000 description 6
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 5
- 229910002099 LiNi0.5Mn1.5O4 Inorganic materials 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 229910001416 lithium ion Inorganic materials 0.000 description 5
- 239000002000 Electrolyte additive Substances 0.000 description 4
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 230000001351 cycling effect Effects 0.000 description 4
- 229910052744 lithium Inorganic materials 0.000 description 4
- 229910001428 transition metal ion Inorganic materials 0.000 description 4
- BTGRAWJCKBQKAO-UHFFFAOYSA-N adiponitrile Chemical compound N#CCCCCC#N BTGRAWJCKBQKAO-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000002208 flavanones Chemical class 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 235000013824 polyphenols Nutrition 0.000 description 3
- 238000007086 side reaction Methods 0.000 description 3
- 229910013716 LiNi Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000001787 dendrite Anatomy 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- RTRZOHKLISMNRD-UHFFFAOYSA-N isoflavanone Chemical compound C1OC2=CC=CC=C2C(=O)C1C1=CC=CC=C1 RTRZOHKLISMNRD-UHFFFAOYSA-N 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 239000007774 positive electrode material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000007784 solid electrolyte Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- FBADCSUQBLLAHW-SOFGYWHQSA-N (e)-4-trimethylsilyloxypent-3-en-2-one Chemical compound CC(=O)\C=C(/C)O[Si](C)(C)C FBADCSUQBLLAHW-SOFGYWHQSA-N 0.000 description 1
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 description 1
- ZLHVIYHWWQYJID-UHFFFAOYSA-N 4'-hydroxyflavanone Chemical compound C1=CC(O)=CC=C1C1OC2=CC=CC=C2C(=O)C1 ZLHVIYHWWQYJID-UHFFFAOYSA-N 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- NEILRVQRJBVMSK-UHFFFAOYSA-N B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C Chemical compound B(O)(O)O.C[SiH](C)C.C[SiH](C)C.C[SiH](C)C NEILRVQRJBVMSK-UHFFFAOYSA-N 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 230000022131 cell cycle Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- HVQAJTFOCKOKIN-UHFFFAOYSA-N flavonol Natural products O1C2=CC=CC=C2C(=O)C(O)=C1C1=CC=CC=C1 HVQAJTFOCKOKIN-UHFFFAOYSA-N 0.000 description 1
- 150000007946 flavonol Chemical class 0.000 description 1
- 235000011957 flavonols Nutrition 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 231100000171 higher toxicity Toxicity 0.000 description 1
- 238000004770 highest occupied molecular orbital Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-N hydroperoxyl Chemical compound O[O] OUUQCZGPVNCOIJ-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- BDKWOJYFHXPPPT-UHFFFAOYSA-N lithium dioxido(dioxo)manganese nickel(2+) Chemical compound [Mn](=O)(=O)([O-])[O-].[Ni+2].[Li+] BDKWOJYFHXPPPT-UHFFFAOYSA-N 0.000 description 1
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 238000006864 oxidative decomposition reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- ZRZFJYHYRSRUQV-UHFFFAOYSA-N phosphoric acid trimethylsilane Chemical compound C[SiH](C)C.C[SiH](C)C.C[SiH](C)C.OP(O)(O)=O ZRZFJYHYRSRUQV-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- IAHFWCOBPZCAEA-UHFFFAOYSA-N succinonitrile Chemical compound N#CCCC#N IAHFWCOBPZCAEA-UHFFFAOYSA-N 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
-
- 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)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Secondary Cells (AREA)
Abstract
The invention discloses an electrolyte for a lithium nickel manganese oxide battery, a preparation method and application thereof, wherein the preparation raw materials of the electrolyte comprise flavonoid functional additives; the flavonoid functional additive comprises at least one of flavone, flavanone, isoflavone, naphthoflavone, alpha-naphthoflavone and beta-naphthoflavone; the flavonoid functional additive accounts for 0.5-2.5% of the electrolyte by mass. The electrolyte for the lithium nickel manganese oxide battery can effectively improve the capacity retention rate of the battery, reduce interface impedance and prolong the cycle life of the battery.
Description
Technical Field
The invention relates to the technical field of battery materials, in particular to electrolyte for a lithium nickel manganese oxide battery, and a preparation method and application thereof.
Background
Nowadays, lithium Ion Batteries (LIBs) have become an integral part of people's life. With the popularity of electric vehicles and the pursuit of power and performance, the development of high energy density LIBs has been promoted. The prior art can improve the energy density of the battery by increasing the specific capacity or the working voltage of the positive electrode material. By LiNi 0.5 Mn 1.5 O 4 Lithium ion batteries with (LNMO) spinel as the positive electrode material have a voltage of 4.7V (vs. Li/Li) + ) High operating voltage of 650wh kg -1 Is generally considered to be one of the most commercially viable lithium batteries. While pursuing high voltage, the cycle performance of the battery is not negligible, and the cycle stability of the battery is drastically deteriorated with a great potential safety hazard. When the voltage is higher than 4.4V, the traditional carbonate-based electrolyte can be subjected to oxidative decomposition, and serious side reaction occurs between the electrode and the electrolyte, so that electrolysis is causedLiquid and active Li + Ion is continuously consumed, and lithium dendrite on the cathode grows, so that the capacity of the LNMO battery is quickly attenuated, and the cycle life and the safety of the battery are not facilitated. In addition, liPF in commercial carbonate-based electrolytes 6 The salt is easy to hydrolyze to generate HF, corrode the surface of the positive electrode, cause the dissolution of transition metal ions, and are unfavorable for the cycle performance of the battery. In order to solve the above-mentioned problems of carbonate-based electrolytes, a great deal of work has been done in recent years by researchers, including increasing lithium salt concentration, adding electrolyte additives, and developing new electrolyte systems, such as sulfone-based electrolytes and solid electrolytes. Among them, some multifunctional electrolyte additives are receiving increasing attention because they can induce an effective interfacial film (CEI/SEI) to prevent further electrolyte decomposition, protect the electrode body from HF corrosion, and can achieve the desired effect in small doses. The negative electrode film forming additive with excellent FEC (vinylene carbonate) property has good low-temperature performance, and the formed SEI film is thin, has toughness and self-repairing property, and is the most effective in improving the high-voltage cycling stability of the battery, but has poor high-temperature performance, and can be decomposed into HF and VC, and the HF damages the CEI film to cause dissolution of positive electrode metal ions, so that the self-discharge of the battery core is aggravated. SN (succinonitrile) can suppress the adverse effect of FEC decomposition at high temperature to some extent, but its melting point (55 ℃) is high, and it is solid at normal temperature and needs to be melted before use. The electrolyte containing high ADN (adiponitrile) can cause lithium to be salted out at low temperature, the high-temperature effect and the high-voltage effect of HTCN (hexatri-nitrile) are better than those of ADN or SN, but the nitrile additive is more expensive and has higher toxicity. Tris (trimethylsilane) phosphate (TMSP) and tris (trimethylsilane) borate TMSB are effective high pressure resistant film forming additives, and have small film forming impedance, SEI film layers derived from TMSP are more stable than TMSB, TMSB film forming impedance is smaller, but TMSP and TMSB are relatively sensitive to water vapor, so that sealing and air contact prevention are strictly ensured during storage, boric acid generated by hydrolysis of TMSB becomes precipitated and separated out as foreign matters when the TMSB is insoluble, TMSP is also possibly hydrolyzed, but phosphoric acid is not separated out in a solid form, and deterioration is possibly more difficult to find. In addition, 4- (trimethylsiloxy) -3-penten-2-one (TMSPO) was introduced as a bisThe functional electrolyte additive not only can form an excellent passivation film on the surface of the LNMO, but also can eliminate HF, so that the cycling stability of the LNMO/Li and LNMO/graphite batteries is improved, but the TMSPO has no obvious effect on the negative electrode side.
Accordingly, it is urgent to develop an electrolyte for improving the cycle performance of the high voltage LNMO battery.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems existing in the prior art. Therefore, the electrolyte for the lithium nickel manganese oxide battery can effectively improve the capacity retention rate of the battery, reduce interface impedance and prolong the cycle life of the battery.
In a second aspect of the invention, a method for preparing an electrolyte for a lithium nickel manganese oxide battery is provided.
In a third aspect of the invention, a lithium nickel manganese oxide battery is provided.
According to a first aspect of the invention, an electrolyte for a lithium nickel manganese oxide battery is provided, wherein the preparation raw materials of the electrolyte comprise flavonoid functional additives;
the flavonoid functional additive comprises at least one of flavone, flavanone, isoflavone, naphthalene flavone, alpha-naphthalene flavone and beta-naphthalene flavone;
the flavonoid functional additive accounts for 0.5-2.5% of the electrolyte by mass.
According to some embodiments of the invention, at least the following benefits are provided:
the Flavonoid (FLA) functional additive with the weight percentage can be oxidized and reduced preferentially, the capacity retention rate of the battery is obviously improved, and a stable interface film is formed at the positive electrode of the lithium nickel manganese oxide battery in the charging and discharging process. The FLA additive forms a compact and stable CEI layer at the positive electrode and has strong interaction with HF in the system, so that corrosion of HF on active materials in the lithium nickel manganese oxide battery and side reaction with electrolyte are inhibited under high voltage, dissolution of transition metal ions in the lithium nickel manganese oxide battery is further inhibited, and the structural stability of the lithium nickel manganese oxide battery material is facilitated.
According to some embodiments of the invention, the structural formula of the flavone is shown as I:
according to some embodiments of the invention, the flavanone has the structural formula shown in II:
according to some embodiments of the invention, the structural formula of the isoflavanone is shown in iii:
according to some embodiments of the invention, the structural formula of the isoflavanone is shown as iv:
according to some embodiments of the invention, the α -naphthaleneflavone has the structural formula shown in v:
according to some embodiments of the invention, the beta-naphthalene flavonoid has a structural formula shown in VI:
according to some embodiments of the present invention, the preparation raw materials of the electrolyte further include the following components in percentage by mass:
80-85% of an organic solvent;
0.5 to 2.5 percent of flavonoid functional additive.
According to some embodiments of the present invention, the preparation raw materials of the electrolyte further include the following components in percentage by mass:
10-15% of lithium salt;
80-85% of organic solvent;
0.5-5% of negative film forming additive.
According to some preferred embodiments of the invention, the lithium salt comprises 12% by mass of the electrolyte.
According to some preferred embodiments of the invention, the organic solvent comprises 81-83.5% of the electrolyte by mass.
According to some preferred embodiments of the invention, the lithium salt comprises 12% by mass of the electrolyte.
According to some preferred embodiments of the invention, the negative film-forming additive comprises 4% by mass of the electrolyte.
According to some preferred embodiments of the invention, the lithium salt comprises 12% by mass of the electrolyte.
According to some embodiments of the invention, the organic solvent comprises: and a carbonate-based organic solvent including cyclic carbonates and linear carbonates.
According to some embodiments of the invention, the cyclic carbonate comprises at least one of Ethylene Carbonate (EC) and Propylene Carbonate (PC); the linear carbonate includes at least one of diethyl carbonate (DEC), dimethyl carbonate (DMC), and ethylmethyl carbonate (EMC).
Compared with the existing electrolyte technology applied to the high-voltage nickel lithium manganate battery, the battery cycle performance is effectively improved after the FLA-containing functional additive is used. This is because in carbonate solvents EC and DMC, FLA-like additives have lower LUMO energy, indicating that FLA is more prone to acquire electrons during initial discharge and is reduced at higher potential; the HOMO energy of FLA-like additives is higher than EC and DMC, indicating that they tend to lose one valence electron and be oxidized at lower potentials than EC and DMC. Thus, FLA-based additives have higher electrochemical activity than EC and DMC, and their preferential redox may form a double-sided solid electrolyte interface film, avoiding further redox decomposition of other electrolyte components. Furthermore, the binding energy of FLA-based additives to HF is lower than that of EC and DMC to HF, and FLA-based additives are more prone to react with HF than EC and DMC according to the principle that the lower the energy is, the more stable; the bond length between HF and FLA additive is shorter than that formed by EC, DMC and HF, so that the formed structure is more stable, the interaction is stronger, and the addition of FLA additive can improve HF corrosion of LNMO electrode and dissolution of transition metal ions.
According to some preferred embodiments of the invention, the organic solvent comprises: ethylene carbonate, dimethyl carbonate and ethylmethyl carbonate.
According to some preferred embodiments of the invention, the weight ratio of the ethylene carbonate, the dimethyl carbonate and the ethylmethyl carbonate is 3:3:4.
According to some embodiments of the invention, the lithium salt comprises lithium hexafluorophosphate (LiPF 6 )。
According to some embodiments of the invention, the negative electrode film-forming additive comprises at least one of fluoroethylene carbonate (FEC), vinylene Carbonate (VC), ethylene carbonate (VEC), 1, 3-Propane Sultone (PS), and acrylonitrile.
According to some embodiments of the invention, the negative electrode film-forming additive comprises fluoroethylene carbonate.
SEI film formed by fluoroethylene carbonate (FEC) has toughness and self-repairing property, and can improve the high-voltage cycling stability of the battery to a certain extent. However, the FLA additive can be decomposed into HF and VC at high temperature, and the HF damages the CEI film to dissolve out metal ions of the positive electrode, so that the self-discharge of the battery core is aggravated, and the high-temperature performance is poor.
According to a second aspect of the present invention, there is provided a method for preparing an electrolyte for a lithium nickel manganese oxide battery, the method comprising mixing preparation raw materials of the electrolyte for the lithium nickel manganese oxide battery.
According to some embodiments of the invention, the method of preparation comprises mixing the lithium salt and the organic solvent before adding the negative film forming additive and the multifunctional additive.
Preferably, the preparation method comprises the following steps:
the preparation method comprises the steps of mixing the lithium salt and the organic solvent at room temperature in a glove box, and then adding a negative electrode film forming additive and a multifunctional additive.
According to some embodiments of the invention, the glove box is in an inert atmosphere.
Preferably, the inert atmosphere comprises at least one of argon and helium.
More preferably, the inert atmosphere is argon.
According to some embodiments of the invention, the environmental indicators in the glove box include H 2 O≤1ppm，O 2 ≤1ppm
According to a third aspect of the invention, a lithium nickel manganese oxide battery is provided, wherein the preparation raw materials of the lithium nickel manganese oxide battery comprise electrolyte for the lithium nickel manganese oxide battery.
According to some embodiments of the invention, the negative electrode of the lithium nickel manganese oxide battery comprises graphite.
The FLA additive generates a stable interface film SEI layer with high ionic conductivity on the graphite cathode, thereby reducing the active Li consumed by the destruction and repair of the SEI film + Thereby increasing reversible insertion and extraction of Li + The content reduces interface impedance and prolongs the cycle life of the battery.
According to some embodiments of the invention, the lithium nickel manganese oxide battery has a charge cut-off voltage of 3.3-4.9V.
Preferably, the charge cut-off voltage of the lithium nickel manganese oxide battery can reach 4.4V.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Drawings
The foregoing and/or additional aspects and advantages of the invention will become apparent and may be better understood from the following description of embodiments taken in conjunction with the accompanying drawings in which:
FIG. 1 is a graph showing the capacity retention ratio of the present invention at room temperature 1C cycle for 500 weeks in comparison with the comparative example;
FIG. 2 is a graph showing the capacity retention of the inventive example versus the comparative example at a high temperature of 55℃and a high rate of 1C cycle of 500 weeks.
Detailed Description
The conception and the technical effects produced by the present invention will be clearly and completely described in conjunction with the embodiments below to fully understand the objects, features and effects of the present invention. It is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments, and that other embodiments obtained by those skilled in the art without inventive effort are within the scope of the present invention based on the embodiments of the present invention.
Example 1
The embodiment provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Example 2
The embodiment provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Example 3
The embodiment provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Example 4
The embodiment provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Example 5
The embodiment provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Example 6
This example provides an electrolyte for a lithium nickel manganese oxide battery, which differs from example 1 in that flavanone is used as a FLA additive.
Example 7
This example provides an electrolyte for a lithium nickel manganese oxide battery, which differs from example 1 in that naphthalene flavone is used as a FLA additive.
Example 8
This example provides an electrolyte for a lithium nickel manganese oxide battery, which differs from example 1 in that alpha-naphthaleneflavone is used as a FLA additive.
Example 9
This example provides an electrolyte for a lithium nickel manganese oxide battery, which differs from example 1 in that beta-naphthaleneflavone is used as a FLA additive.
Comparative example 1
The comparative example provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
LiPF 6 12％；
EC/DMC/EMC(3/3/4) 82％；
FEC 4％；
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Comparative example 2
The comparative example provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Comparative example 3
The comparative example provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the embodiment also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Comparative example 4
The comparative example provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the comparative example also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Comparative example 5
The comparative example provides an electrolyte for a lithium nickel manganese oxide battery, which comprises the following components in percentage by mass:
wherein the mass ratio of the organic solvent to EC, DMC, EMC is 3:3:4.
the comparative example also provides a preparation method of the electrolyte for the lithium nickel manganese oxide battery, which comprises the following steps:
s1, in a glove box filled with high-purity argon, controlling the water content in the glove box to be less than 1ppm, and respectively weighing the components in percentage by mass;
s2, dissolving electrolyte lithium salt in a nonaqueous organic solvent, and stirring to form a uniform solution;
s3, adding the negative electrode film-forming additive and the multifunctional additive into the uniform solution obtained in the step 2 one by one, and uniformly stirring to obtain the electrolyte.
Test case
First battery cycle performance test
The flavonoid additive-containing high-voltage lithium ion battery electrolyte is applied to a high-voltage system, and a high-voltage lithium ion battery anode uses lithium nickel manganese oxide LiNi 0.5 Mn 1.5 O 4 The negative electrode uses artificial graphite, and the electrolyte containing the additive is used as electrolyte to prepare a soft package battery so as to evaluate the normal temperature (25 ℃) cycle performance and the high temperature (55 ℃) cycle performance of the high-voltage electrolyte. And (3) performing charge-discharge cycle at 1C rate in a voltage range of 3.3-4.9V in normal temperature and high temperature cycle performance test, and recording battery capacity retention rate for 500 weeks in cycle as comparison.
The mass percentages listed in the following tables are the mass percentages of the components in the electrolyte.
TABLE 1 impact of different novel composite additive Components on cell cycle performance results
The experimental data according to table 1 are shown in fig. 1 and 2. Flavone (FLA) medicine as a novel multifunctional electrolyte additive applied to high-pressure LiNi 0.5 Mn 1.5 O 4 The graphite battery can remarkably improve the cycle capacity retention rate at normal temperature and high temperature, and improves the cycle performance. LiNi at 1C and 25 DEG C 0.5 Mn 1.5 O 4 The capacity retention rate of the graphite battery is improved from 50.20% to 81.2%, and LiNi is carried out under the conditions of 1C and 55 DEG C 0.5 Mn 1.5 O 4 The capacity retention rate of the graphite battery is improved from 35.7% to 78.10%. The improvement of the cycle performance is mainly due to the fact that the FLA additive can generate oxidation-reduction reaction in preference to the solvent, and the Li-rich electrode is generated 2 CO 3 The CEI film and the SEI film not only have better interface stability, but also ensure higher ion conductivity, thereby reducing interface impedance. The CEI film is thin and dense, can inhibit the dissolution of transition metal ions, improves the stability of the bulk structure, and in addition, FLA is more prone to react with HF, thereby relieving the side reaction generated by high pressure and high temperature of HF to LiNi 0.5 Mn 1.5 O 4 Corrosion of graphite cell active material. Meanwhile, the stable SEI film on the surface of the negative electrode is beneficial to Li + Intercalation and deintercalation, avoiding the occurrence of lithium dendrites, and these factors together improve LiNi 0.5 Mn 1.5 O 4 Cycling performance of graphite cells. The flavonol in comparative example 4 has hydroxyl group connected with carbon-carbon double bond, and the structure is called enol structure, is extremely unstable and is easy to isomerize, corresponding aldehyde or ketone is generated through transfer of hydrogen atoms and electron rearrangement, in the process, the product contains moisture and reacts with lithium salt to generate acid, and the cycle performance of the battery is extremely unfavorable, so that the performance is reduced; the benzene ring of 4-hydroxy flavanone in comparative example 5 contains phenolic hydroxyl group, the lone electron pair of the hydroxyl group and the benzene ring generate p-pi conjugation, the electron cloud density of the phenolic hydroxyl oxygen is reduced, the phenolic anion is more stable, and H is easier to ionize + The electrolyte is acidic, the acidity of the electrolyte is increased to a certain extent, and the corrosion of acidic substances to the anode material can be caused by improper use or storage of the full battery, so that the cycle performance of the battery is reduced.
While the embodiments of the present invention have been described in detail, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art. Furthermore, embodiments of the invention and features of the embodiments may be combined with each other without conflict.
Claims (10)
1. An electrolyte for a lithium nickel manganese oxide battery is characterized in that the preparation raw materials of the electrolyte comprise flavonoid functional additives;
the flavonoid functional additive comprises at least one of flavone, flavanone, isoflavone, naphthalene flavone, alpha-naphthalene flavone and beta-naphthalene flavone;
the flavonoid functional additive accounts for 0.5-2.5% of the electrolyte by mass.
2. The electrolyte for a lithium nickel manganese oxide battery according to claim 1, wherein the preparation raw materials of the electrolyte further comprise the following components in percentage by mass:
80-85% of an organic solvent;
0.5 to 2.5 percent of flavonoid functional additive.
3. The electrolyte for a lithium nickel manganese oxide battery according to claim 1, wherein the preparation raw materials of the electrolyte further comprise the following components in percentage by mass:
10-15% of lithium salt;
80-85% of organic solvent;
0.5-5% of negative film forming additive.
4. The electrolyte for a lithium nickel manganese oxide battery according to claim 3, wherein the organic solvent comprises: and a carbonate-based organic solvent including cyclic carbonates and linear carbonates.
5. The electrolyte for a lithium nickel manganese oxide battery according to claim 4, wherein the cyclic carbonate includes at least one of vinyl ester and propylene carbonate; the linear carbonate includes at least one of diethyl carbonate, dimethyl carbonate and methylethyl carbonate.
6. The electrolyte for a lithium nickel manganese oxide battery according to claim 3, wherein the lithium salt includes lithium hexafluorophosphate (LiPF 6 )。
7. The electrolyte for a lithium nickel manganese oxide battery according to claim 3, wherein the negative electrode film-forming additive comprises fluoroethylene carbonate.
8. A method for producing an electrolyte for a lithium nickel manganese oxide battery according to any one of claims 1 to 7, characterized in that the method comprises mixing raw materials for producing an electrolyte for a lithium nickel manganese oxide battery.
9. The preparation method according to claim 8, wherein the preparation method comprises mixing the lithium salt and the organic solvent and then adding a negative electrode film-forming additive and a multifunctional additive.
10. A lithium nickel manganese oxide battery, characterized in that the preparation raw materials of the lithium nickel manganese oxide battery comprise the electrolyte for the lithium nickel manganese oxide battery according to any one of claims 1 to 8.
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