CN117080556A - Novel solid electrolyte for lithium battery and preparation method and application thereof - Google Patents
Novel solid electrolyte for lithium battery and preparation method and application thereof Download PDFInfo
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- CN117080556A CN117080556A CN202311095717.4A CN202311095717A CN117080556A CN 117080556 A CN117080556 A CN 117080556A CN 202311095717 A CN202311095717 A CN 202311095717A CN 117080556 A CN117080556 A CN 117080556A
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- solid electrolyte
- lithium battery
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- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 61
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title abstract description 16
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 239000003792 electrolyte Substances 0.000 claims abstract description 31
- 239000003999 initiator Substances 0.000 claims abstract description 22
- 239000000654 additive Substances 0.000 claims abstract description 18
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 17
- 230000000996 additive effect Effects 0.000 claims abstract description 15
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 10
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 12
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 claims description 10
- 229910012258 LiPO Inorganic materials 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 claims description 7
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 claims description 4
- -1 lithium hexafluorophosphate Chemical compound 0.000 claims description 4
- FSSPGSAQUIYDCN-UHFFFAOYSA-N 1,3-Propane sultone Chemical compound O=S1(=O)CCCO1 FSSPGSAQUIYDCN-UHFFFAOYSA-N 0.000 claims description 2
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 claims description 2
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 claims description 2
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 claims description 2
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003236 benzoyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C(*)=O 0.000 claims description 2
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000001257 hydrogen Substances 0.000 claims description 2
- 229910052739 hydrogen Inorganic materials 0.000 claims description 2
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 2
- FRMOHNDAXZZWQI-UHFFFAOYSA-N lithium manganese(2+) nickel(2+) oxygen(2-) Chemical compound [O-2].[Mn+2].[Ni+2].[Li+] FRMOHNDAXZZWQI-UHFFFAOYSA-N 0.000 claims description 2
- MHCFAGZWMAWTNR-UHFFFAOYSA-M lithium perchlorate Chemical compound [Li+].[O-]Cl(=O)(=O)=O MHCFAGZWMAWTNR-UHFFFAOYSA-M 0.000 claims description 2
- 229910001486 lithium perchlorate Inorganic materials 0.000 claims description 2
- 229910001496 lithium tetrafluoroborate Inorganic materials 0.000 claims description 2
- VDVLPSWVDYJFRW-UHFFFAOYSA-N lithium;bis(fluorosulfonyl)azanide Chemical compound [Li+].FS(=O)(=O)[N-]S(F)(=O)=O VDVLPSWVDYJFRW-UHFFFAOYSA-N 0.000 claims description 2
- IGILRSKEFZLPKG-UHFFFAOYSA-M lithium;difluorophosphinate Chemical compound [Li+].[O-]P(F)(F)=O IGILRSKEFZLPKG-UHFFFAOYSA-M 0.000 claims description 2
- 125000005010 perfluoroalkyl group Chemical group 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims 1
- 125000005371 silicon functional group Chemical group 0.000 abstract description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000011244 liquid electrolyte Substances 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 6
- 101150058243 Lipf gene Proteins 0.000 description 6
- 239000012046 mixed solvent Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000001035 drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000010406 cathode material Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical group [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- SYRDSFGUUQPYOB-UHFFFAOYSA-N [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-].FC(=O)C(F)=O SYRDSFGUUQPYOB-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- 150000001642 boronic acid derivatives Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
Classifications
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- 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
-
- 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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
-
- 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
Abstract
The application discloses a novel solid electrolyte for a lithium battery, and a preparation method and application thereof, wherein the electrolyte comprises an organic solvent, lithium salt, a basic additive, an initiator and a curing agent: the electrolyte curing agent mainly comprises unsaturated double bonds and silicon functional groups. They not only help to create a conductive and strong interfacial layer on the positive/negative electrodes, but also help to increase stability and safety of the lithium battery, improve battery capacity, and change battery shape. The application provides a preparation method of the electrolyte. The lithium battery containing the electrolyte provided by the application adopts the lithium iron phosphate or nickel-rich ternary positive electrode, and has excellent cycle performance.
Description
Technical Field
The application belongs to the technical field of lithium ion battery electrolyte materials, and particularly relates to a novel solid electrolyte for a lithium battery, and a preparation method and application thereof.
Background
In recent years, as the demand for electronic devices, electric vehicles, and large-capacity energy storage systems has increased, research into lithium-based batteries with high power/energy density and good safety has been advanced. The current lithium ion batteries cannot meet the increasing application requirements, particularly the application requirements related to the rapid development of electric automobiles.
Conventional liquid electrolytes must meet the following conditions: (1) The chemical stability is good at higher potential and temperature, and the decomposition is not easy; (2) has higher ionic conductivity; (3) The lithium battery based on the liquid electrolyte is inert to cathode materials and can not be corroded, so that the selection of the cathode materials and anode materials is limited to a certain extent, meanwhile, the quantity of lithium ions participating in circulation in the charge and discharge process of the lithium battery based on the liquid electrolyte is continuously reduced, the capacity of the battery is reduced, the service life of the battery is shortened, and safety problems such as fire and explosion of the battery caused by liquid leakage are easily generated in the use process.
The basic strategies currently employed are to reduce negative effects, typically by adding various additives to the liquid electrolyte: (1) By using additives such as unsaturated compounds, borates, fluorides, etc., a denser, more efficient SEI/CEI layer is formed; (2) The flame retardant properties of the liquid are increased by using phosphorus-based additives. However, these methods cannot fundamentally solve the hidden trouble problem, and in order to improve the stability and safety of the lithium battery, designing a new electrolyte type to avoid the above drawbacks has become a main solution.
Disclosure of Invention
The technical problems to be solved are as follows:
aiming at the defects of the prior art, the application solves the technical problems that the quantity of lithium ions participating in circulation is continuously reduced in the charging and discharging process of the lithium battery based on the liquid electrolyte at present, the battery capacity is reduced, the service life is shortened, the battery is easy to fire and explode due to leakage in the use process, and the like, and provides the novel solid electrolyte for the lithium battery, the preparation method and the application thereof, and the stability and the safety of the lithium battery are improved.
The technical scheme is as follows:
in order to achieve the above purpose, the present application is realized by the following technical scheme:
a novel solid electrolyte of a lithium battery consists of an organic solvent, lithium salt, a basic additive, an initiator and a curing agent; the concentration of lithium salt in the novel solid electrolyte of the lithium battery is 0.5mol/L-2mol/L, the mass fraction of the basic additive in the novel solid electrolyte of the lithium battery is 0.1% -4%, the mass fraction of the initiator in the novel solid electrolyte of the lithium battery is 0.05% -0.15%, the mass fraction of the curing agent in the novel solid electrolyte of the lithium battery is 1% -9%, and the mass fraction of the organic solvent is 85% -99%.
Further, the curing agent has the following structural formula:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Is hydrogen, a fluorine-containing group, a hydroxyl group, a fatty chain, a phenyl group or other unsaturated structure containing double/triple bonds.
Further, the organic solvent is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and propylene carbonate.
Further, the lithium salt is one or more of lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate and lithium perfluoroalkyl sulfonate.
Further, the basic additive is fluorinated ethylene carbonate FEC, 1, 3-propane sultone PS, vinylene carbonate VC, lithium difluorooxalate borate LiODFB, lithium difluorophosphate LiPO 2 F 2 One or more of them.
Further, the initiator is one or more of azodiisobutyronitrile AIBN, azodiisoheptonitrile ADVN and benzoyl.
The application of the novel solid electrolyte in the lithium iron phosphate, the lithium nickel manganese oxide and the nickel-rich ternary positive electrode battery is that the battery added with the curing agent is placed in a 60 ℃ oven for 5 hours to cure the electrolyte.
The application also discloses a preparation method of the novel solid electrolyte of the lithium battery, which comprises the following steps:
the first step: in a glove box protected by argon, adding lithium salt and a basic additive into an organic solvent to form a contrast electrolyte;
and a second step of: and in a glove box protected by argon, adding an initiator and a curing agent into the contrast electrolyte, and shaking to uniformly mix the initiator and the curing agent, so as to obtain the novel solid electrolyte of the lithium battery.
The beneficial effects are that:
the application provides a novel solid electrolyte for a lithium battery, and a preparation method and application thereof, and compared with the prior art, the novel solid electrolyte has the following beneficial effects:
1. the solid electrolyte can ensure the stable circulation of the battery and can not cause electrolyte overflow and leakage so as to prevent safety accidents, and can ensure that the lithium iron phosphate anode can stably circulate for 400 circles under a voltage window of 2.5-3.65V, and the capacity is not attenuated;
2. the curing agent disclosed by the application contains unsaturated double bonds and silicon functional groups, is favorable for helping the solidification of liquid electrolyte to prevent leakage, improves the safety of a lithium battery, and can also generate a conductive and firm SEI layer on a negative electrode. The structure can be used as a basic unit to develop more efficient curing agents;
3. the preparation method of the novel solid electrolyte of the lithium battery is simple;
4. the capacity retention rates of the novel solid electrolyte for the lithium battery reach 102.23% and 98.85% respectively in the lithium iron phosphate and high-nickel ternary lithium battery, and the capacity retention rate of the conventional liquid electrolyte for 400 circles is only 85.81% and 90.99%.
Drawings
FIG. 1 is a diagram showing the behavior of the solid electrolyte (B) and the liquid electrolyte of comparative example 1 (A) according to the present application;
FIG. 2 is a graph showing the charge and discharge at room temperature of a lithium iron phosphate battery prepared with the solid electrolyte according to example 2 of the present application;
FIG. 3 is a graph showing the comparison of the cycle performance test of lithium iron phosphate prepared from the electrolyte in example 2 and comparative example 2 of the present application at room temperature;
fig. 4 is a graph showing the comparison of the cycle performance test at room temperature of the high nickel ternary positive electrode full cell prepared by the electrolyte in example 3 of the present application and comparative example 3.
Detailed Description
The present application will be described in further detail with reference to examples.
The following describes in detail the embodiments of the present application, which are implemented on the premise of the technical solution of the present application, and give detailed embodiments and specific operation procedures, but the scope of protection of the present application is not limited to the following examples.
Example 1:
the preparation method of the novel solid electrolyte of the lithium battery comprises the following steps:
the first step: liPF at a concentration of 1.0M was placed in an argon-shielded glove box 6 Adding lithium salt into mixed solvent (EC: EMC: DMC=1:1:1) of organic solvent carbonate, stirring well, and adding 2wt% of base additive LiPO 2 F 2 Fully and uniformly mixing to form contrast electrolyte;
and a second step of: adding 0.1wt% of initiator AIBN and 3wt% of curing agent into the contrast electrolyte in a glove box protected by argon, and shaking to uniformly mix the initiator AIBN and the curing agent to obtain novel solid electrolyte of the lithium battery; in the electrolyte, the concentration of lithium salt is 1.0M, the curing agent has the following structure (formula 1), and the novel solid electrolyte of the lithium battery is applied to a lithium iron phosphate/graphite battery.
Example 2:
the embodiment provides a preparation method of a novel solid electrolyte of a lithium battery, which comprises the following steps:
the first step: liPF at a concentration of 1.2M was placed in an argon-shielded glove box 6 Adding lithium salt into mixed solvent (EC: EMC: DMC=1:1:1) of organic solvent carbonate, stirring well, and adding 2wt% of base additive LiPO 2 F 2 Fully and uniformly mixed with the mixture,
forming a contrast electrolyte;
and a second step of: adding 0.1wt% of initiator AIBN and 3wt% of curing agent into the contrast electrolyte in a glove box protected by argon, and shaking to uniformly mix the initiator AIBN and the curing agent to obtain novel solid electrolyte of the lithium battery; in the electrolyte, the concentration of lithium salt is 1.2M, the curing agent has the following structure (formula 2), and the novel solid electrolyte of the lithium battery is applied to a lithium iron phosphate/graphite battery.
Example 3:
the preparation method of the novel solid electrolyte of the lithium battery comprises the following steps:
the first step: liPF at a concentration of 1.2M was placed in an argon-shielded glove box 6 Adding lithium salt into mixed solvent (EC: EMC: DMC=1:1:1) of organic solvent carbonate, stirring well, and adding 2wt% of base additive LiPO 2 F 2 Fully and uniformly mixed with the mixture,
forming a contrast electrolyte;
and a second step of: adding 0.1wt% of initiator AIBN and 3wt% of curing agent into the contrast electrolyte in a glove box protected by argon, and shaking to uniformly mix the initiator AIBN and the curing agent to obtain novel solid electrolyte of the lithium battery; in the electrolyte, the concentration of lithium salt is 1.2M, the curing agent has the following structure (formula 2), and the novel solid electrolyte of the lithium battery is applied to a high-nickel ternary/graphite battery.
Comparative example 1
The preparation method of the lithium battery electrolyte without the initiator and the curing agent comprises the following specific steps:
in an argon-protected glove box, liPF was measured in the glove box 6 Lithium salt (mass concentration of 1.0M) was then added to the carbonate mixed solvent (EC: EMC: dmc=1:1:1), stirred well and then 2wt% of base additive LiPO was added 2 F 2 Shaking thoroughly, mixing well, initiator-free and curingThe application of the lithium battery electrolyte in the lithium iron phosphate/graphite battery is provided.
Comparative example 2
The preparation method of the novel solid electrolyte of the lithium battery without the curing agent comprises the following steps:
the first step: liPF was placed in an argon-protected glove box 6 Adding lithium salt (the mass concentration of the substance is 1.2M) into the mixed solvent (EC: EMC: DMC=1:1:1) of the organic solvent carbonate, uniformly stirring, and adding 2wt% of base additive LiPO 2 F 2 Fully shaking, uniformly mixing to form contrast electrolyte;
and a second step of: in a glove box protected by argon, adding 0.1wt% of initiator AIBN into the contrast electrolyte, shaking to uniformly mix the initiator AIBN, and applying the novel solid electrolyte of the lithium battery without curing agent in the lithium iron phosphate/graphite battery.
Comparative example 3
The preparation method of the lithium battery electrolyte without the initiator and the curing agent comprises the following specific steps:
LiPF was placed in an argon-protected glove box 6 Adding lithium salt (the mass concentration of the substance is 1.2M) into the mixed solvent (EC: EMC: DMC=1:1:1) of the organic solvent carbonate, uniformly stirring, and adding 2wt% of base additive LiPO 2 F 2 Fully shaking and uniformly mixing; the lithium battery electrolyte without initiator and curing agent is applied to the high-nickel ternary/graphite battery.
The solid electrolyte prepared in example 1-example 3 and the liquid electrolyte prepared in comparative example 1-comparative example 3 were used to assemble corresponding lithium batteries, respectively, and the following steps were performed:
(1) 8 parts of lithium iron phosphate positive electrode/high nickel ternary positive electrode and 1 part of acetylene black are added into N-methylpyrrolidone (NMP)
Mixing at a constant speed of 2000rpm for 1h at room temperature; 1 part of polyvinylidene fluoride binder was then added
(PVDF) stirred overnight at 2000r/min to give a prepared slurry;
(2) Uniformly coating the slurry on an aluminum foil in a drying room by using a coating machine, slicing the aluminum foil into a shape with the length of 20cm and the width of 10cm by using a slicing machine after the aluminum foil is dried, drying the aluminum foil at 80 ℃ for 12 hours, tabletting the aluminum foil by using a tabletting machine to obtain an electric core with the specified surface density, cutting the electric core into square pole pieces by using a template, and putting the square pole pieces into a glove box for standby; the preparation method of the graphite cathode is the same as that of the graphite cathode, and the current collector is copper foil;
(3) The prepared positive electrode, metallic lithium negative electrode/graphite negative electrode, separator and the electrolytes of examples 1 to 3 and comparative examples 1 to 3 were assembled into a battery in a drying room.
The prepared battery is subjected to constant current charge and discharge test at room temperature on a blue battery tester, the cut-off voltage is 2.5-3.65V of lithium iron phosphate, the high nickel anode is 2.75-4.4V, and the test temperature is 25 ℃. As can be seen from fig. 1, the method of the present application can be used to successfully prepare a lithium battery solid electrolyte, and fig. 2 and 3 show that the lithium iron phosphate positive electrode has better cycle stability in the presence of a curing agent, and also has excellent effects (fig. 4) on a high nickel positive electrode full battery system, and specific data are shown in table 1.
Table 1 lithium battery test data based on experimental and comparative electrolytes
The above embodiments are only for illustrating the technical concept and features of the present application, and are intended to enable those skilled in the art to understand the present application and to implement the same, but are not intended to limit the scope of the present application, and all equivalent changes or modifications made according to the spirit of the present application should be included in the scope of the present application.
Claims (8)
1. A novel solid electrolyte for a lithium battery is characterized in that: the novel solid electrolyte of the lithium battery consists of an organic solvent, lithium salt, a basic additive, an initiator and a curing agent; the concentration of lithium salt in the novel solid electrolyte of the lithium battery is 0.5mol/L-2mol/L, the mass fraction of the basic additive in the novel solid electrolyte of the lithium battery is 0.1% -4%, the mass fraction of the initiator in the novel solid electrolyte of the lithium battery is 0.05% -0.15%, the mass fraction of the curing agent in the novel solid electrolyte of the lithium battery is 1% -9%, and the mass fraction of the organic solvent is 85% -99%.
2. The novel solid electrolyte for lithium battery according to claim 1, wherein the curing agent has the following structural formula:
wherein R is 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 、R 8 Is hydrogen, a fluorine-containing group, a hydroxyl group, a fatty chain, a phenyl group or other unsaturated structure containing double/triple bonds.
3. The novel solid electrolyte for a lithium battery according to claim 1, wherein: the organic solvent is one or more of ethylene carbonate, dimethyl carbonate, diethyl carbonate, methyl ethyl carbonate and propylene carbonate.
4. The novel solid electrolyte for a lithium battery according to claim 1, wherein: the lithium salt is one or more of lithium bis (fluorosulfonyl) imide, lithium perchlorate, lithium hexafluorophosphate, lithium tetrafluoroborate and lithium perfluoroalkyl sulfonate.
5. The novel solid electrolyte for a lithium battery according to claim 1, wherein: the basic additive is fluorinated ethylene carbonate FEC, 1, 3-propane sultone PS, vinylene carbonate VC, lithium difluorooxalato borate LiODFB and lithium difluorophosphate LiPO 2 F 2 One or more of them.
6. The novel solid electrolyte of the lithium battery according to claim 1, wherein the initiator is one or more of azodiisobutyronitrile AIBN, azodiisoheptonitrile ADVN and benzoyl.
7. Use of the novel solid electrolyte for lithium batteries according to any one of claims 1 to 6 in lithium iron phosphate, lithium nickel manganese oxide and nickel-rich ternary positive electrode batteries, characterized in that: the batteries added with the curing agent are all placed in an oven at 60 ℃ for 5 hours to cure the electrolyte.
8. A method for preparing the novel solid electrolyte for a lithium battery according to any one of claims 1 to 6, comprising the steps of:
the first step: in a glove box protected by argon, adding lithium salt and a basic additive into an organic solvent to form a contrast electrolyte;
and a second step of: in a glove box protected by argon, adding an initiator and a curing agent into the contrast electrolyte, shaking to uniformly mix the initiator and the curing agent,
obtaining the novel solid electrolyte of the lithium battery.
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