CN117219865A - Local high-concentration electrolyte with flame retardant property for lithium ion battery - Google Patents
Local high-concentration electrolyte with flame retardant property for lithium ion battery Download PDFInfo
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- CN117219865A CN117219865A CN202311389350.7A CN202311389350A CN117219865A CN 117219865 A CN117219865 A CN 117219865A CN 202311389350 A CN202311389350 A CN 202311389350A CN 117219865 A CN117219865 A CN 117219865A
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 86
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 14
- 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 13
- 239000003063 flame retardant Substances 0.000 title claims abstract description 13
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 50
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 229910003002 lithium salt Inorganic materials 0.000 claims abstract description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 20
- -1 lithium salt anions Chemical class 0.000 claims abstract description 18
- 159000000002 lithium salts Chemical class 0.000 claims abstract description 18
- 239000000654 additive Substances 0.000 claims abstract description 12
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000013543 active substance Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000011737 fluorine Substances 0.000 claims abstract description 8
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 8
- 150000005215 alkyl ethers Chemical class 0.000 claims abstract description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 47
- 239000011521 glass Substances 0.000 claims description 34
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical compound [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 33
- 239000006245 Carbon black Super-P Substances 0.000 claims description 32
- 239000002033 PVDF binder Substances 0.000 claims description 32
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 32
- 239000011230 binding agent Substances 0.000 claims description 30
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001035 drying Methods 0.000 claims description 22
- 238000005303 weighing Methods 0.000 claims description 20
- 238000007790 scraping Methods 0.000 claims description 14
- 239000004570 mortar (masonry) Substances 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 13
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 12
- 238000009837 dry grinding Methods 0.000 claims description 12
- 239000011888 foil Substances 0.000 claims description 12
- 238000004080 punching Methods 0.000 claims description 12
- 239000006258 conductive agent Substances 0.000 claims description 11
- 239000007983 Tris buffer Substances 0.000 claims description 9
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 claims description 9
- 238000002360 preparation method Methods 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- CYTQBVOFDCPGCX-UHFFFAOYSA-N trimethyl phosphite Chemical compound COP(OC)OC CYTQBVOFDCPGCX-UHFFFAOYSA-N 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000007774 positive electrode material Substances 0.000 claims description 4
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 4
- FQLSDFNKTNBQLC-UHFFFAOYSA-N tris(2,3,4,5,6-pentafluorophenyl)phosphane Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1P(C=1C(=C(F)C(F)=C(F)C=1F)F)C1=C(F)C(F)=C(F)C(F)=C1F FQLSDFNKTNBQLC-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 claims description 3
- IESBVSNCDNHMSL-UHFFFAOYSA-N 2-[bis(2,2,2-trifluoroethoxy)methoxy]-1,1,1-trifluoroethane Chemical compound FC(F)(F)COC(OCC(F)(F)F)OCC(F)(F)F IESBVSNCDNHMSL-UHFFFAOYSA-N 0.000 claims description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 239000006230 acetylene black Substances 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 2
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims description 2
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- 229910021389 graphene Inorganic materials 0.000 claims description 2
- 238000000227 grinding Methods 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
- PDECINHTUQHWJM-UHFFFAOYSA-N lithium;trifluoroborane Chemical compound [Li].FB(F)F PDECINHTUQHWJM-UHFFFAOYSA-N 0.000 claims description 2
- YQCIWBXEVYWRCW-UHFFFAOYSA-N methane;sulfane Chemical compound C.S YQCIWBXEVYWRCW-UHFFFAOYSA-N 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- YFNKIDBQEZZDLK-UHFFFAOYSA-N triglyme Chemical compound COCCOCCOCCOC YFNKIDBQEZZDLK-UHFFFAOYSA-N 0.000 claims description 2
- KFDQGLPGKXUTMZ-UHFFFAOYSA-N [Mn].[Co].[Ni] Chemical compound [Mn].[Co].[Ni] KFDQGLPGKXUTMZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000853 adhesive Substances 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 claims 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 claims 1
- 150000002500 ions Chemical class 0.000 abstract description 8
- 238000007086 side reaction Methods 0.000 abstract description 7
- 210000001787 dendrite Anatomy 0.000 abstract description 6
- 230000002401 inhibitory effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 230000005518 electrochemistry Effects 0.000 abstract description 2
- 238000001465 metallisation Methods 0.000 abstract description 2
- 238000007614 solvation Methods 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 76
- 238000012360 testing method Methods 0.000 description 18
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 10
- 238000004090 dissolution Methods 0.000 description 9
- 239000012467 final product Substances 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 150000001450 anions Chemical group 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- NCZYUKGXRHBAHE-UHFFFAOYSA-K [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] Chemical compound [Li+].P(=O)([O-])([O-])[O-].[Fe+2].[Li+] NCZYUKGXRHBAHE-UHFFFAOYSA-K 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000011978 dissolution method Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000004770 highest occupied molecular orbital Methods 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 229940017219 methyl propionate Drugs 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000003775 Density Functional Theory Methods 0.000 description 1
- HFCVPDYCRZVZDF-UHFFFAOYSA-N [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O Chemical compound [Li+].[Co+2].[Ni+2].[O-][Mn]([O-])(=O)=O HFCVPDYCRZVZDF-UHFFFAOYSA-N 0.000 description 1
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000004210 ether based solvent Substances 0.000 description 1
- 125000001033 ether group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Secondary Cells (AREA)
Abstract
The invention belongs to the field of lithium metal battery electrochemistry, and in particular relates to a local high-concentration electrolyte with flame retardant property for a lithium ion battery. The fluorine-containing alkyl ether is added into the electrolyte as a diluent, is used for inhibiting the growth problem of lithium dendrites generated in the circulation process of a lithium metal anode in a lithium metal battery, can also generate an SEI film rich in LiF and lithium salt anions, reduces the side reaction of the electrolyte and lithium metal, reduces the viscosity of the electrolyte, improves the solvation structure of the lithium salt in the electrolyte, accelerates the transmission of lithium ions, ensures that the lithium metal deposition is more uniform, improves the ion conductivity and wettability thereof, and effectively improves the coulomb efficiency of the lithium ion battery. The introduction of the additive can form a stable CEI film on the surface of the positive electrode, inhibit the reaction of electrolyte and positive electrode active substances, improve the cycle performance of the battery and prolong the service life of the battery.
Description
Technical Field
The invention belongs to the field of lithium metal battery electrochemistry, and particularly relates to a local high-concentration electrolyte with flame retardant property for a lithium ion battery.
Background
The lithium metal material has a high theoretical energy density (3860 mAh g) -1 ) And ultra-low electrochemical potential (-3.040 v vs. she), and the use of the lithium metal battery as a negative electrode in lithium-sulfur batteries, ternary batteries, lithium-air batteries, etc., has become a hot spot for research of high-energy-density secondary batteries, and the market for use of lithium metal batteries in portable devices in the medical field, traffic field, detection field, etc., has been increasing. However, the problems brought by the lithium metal battery are not small, firstly, dendrite problems are solved, because the deposition and growth of lithium metal ions are not uniform, dendrite crystals are formed in the charge-discharge cycle process of the lithium battery, the lithium battery is easy to pierce through a diaphragm, the battery is short-circuited, and fire disasters are seriously caused; and secondly, the instability of the interface between the electrode and the electrolyte. The lithium metal can be contacted with the electrolyte to react to generate a solid electrolyte interface phase (SEI) film on the surface of the lithium metal, and the SEI film battery is continuously damaged and repaired along with the change of the volume of a lithium cathode in the charge-discharge cycle, so that the electrolyte and the lithium metal are continuously consumed, and the coulomb efficiency and the cycle life of the battery are reduced.
In liquid electrolytes, carbonate and ether groups are the most widely used electrolyte solvents, and it is generally believed that carbonate solvents can undergo more serious side reactions with lithium metal, whereas ether-based electrolytes exhibit good compatibility with lithium metal due to the good cathode stability inherent in ethers. In the research of Wang and colleagues, carbonate-based and ether-based electrolytes are prepared respectively, and by analyzing reduction stability, SEI film characterization and DFT calculation of the carbonate-based and ether-based electrolytes, the ether-based electrolytes have better cycle stability not due to the inherent good reduction stability of ether, but due to the fact that lithium salt and ether-based electrolyte complex show higher LUMO energy level than carbonate complex, the decomposition of anions in the ether-based electrolytes is more prominent, and a more stable anion-derived SEI film is formed.
In conventional Low Concentration Electrolytes (LCEs), most of solvent molecules and lithium salt anions are in a free state, do not participate in constituting an SEI film component, cause pulverization of the surface of a lithium anode, but rather increase side reactions between an electrolyte and lithium metal, resulting in continuous consumption of metallic lithium. Thus, the preparation of High Concentration Electrolytes (HCEs) in which all solvent molecules are coordinately complexed with lithium ions and lithium salt anions are complexed with cations to form CIPs (contact ion pairs, single anions are complexed with single cations) and AGGs (aggregates, single anions are complexed with multiple cations) has been initiated to overcome these disadvantages. The formation of ion-solvent complexes reduces the reduction stability of the electrolyte to the metal anode, since the lowest unoccupied molecular orbital Level (LUMO) of the pure solvent decreases after complexing with the alkali metal ions. The lithium salt anions are reduced preferentially to generate an SEI film derived from anions, and the SEI film rich in inorganic components is beneficial to the stability of the lithium anode. The Highest Occupied Molecular Orbital (HOMO) energy level of the complexing of the solvent molecules with lithium ions is lower than that of the solvent, thereby inhibiting the oxidation of the electrolyte and the corrosion of the cathode. However, the high-concentration electrolyte has a high viscosity, and lithium ions are transported to be hindered, which results in a decrease in ion conductivity and wettability, and an increase in cost.
Disclosure of Invention
Aiming at the problem of lithium dendrite growth of the current liquid electrolyte, the SEI film rich in inorganic components is generated by a method for preparing the fluorine-containing local high-concentration electrolyte, the phenomenon of lithium dendrite generated by nonuniform deposition of a lithium metal cathode in a circulating process and the phenomenon of reduced circulating performance caused by dead lithium generated by the reaction of the lithium metal and the electrolyte are inhibited, and the use cost is reduced.
According to the lithium metal battery electrolyte, the fluorine-containing alkyl ether is used as the diluent, the solvation structure of lithium salt is improved to promote lithium ion transmission and uniform lithium metal deposition, in addition, the viscosity of the electrolyte can be reduced by adding the diluent, the wettability of the electrolyte to a battery anode and cathode material and a diaphragm is increased, the coulomb efficiency of the lithium metal battery is effectively improved, and the cycle life of the lithium metal battery is prolonged.
The invention adopts the following technical scheme:
the method comprises the steps of dissolving lithium salt in a mixed solvent of an ether-based solvent and a diluent in a certain proportion by a dissolution method, preparing local high-concentration electrolyte with different concentrations by controlling the addition amount of the lithium salt and the proportion of the solvent, further introducing an anode film-forming additive on the basis, and simultaneously constructing a solid electrolyte interface layer on the surfaces of an anode and a cathode to inhibit side reactions between an electrode and the electrolyte.
The preparation method of the lithium ion battery with the local high-concentration electrolyte with flame retardant property comprises the following steps:
(1) Preparation of a positive electrode material: the positive electrode material comprises an active substance, a conductive agent, a binder and a solvent, the positive electrode powder material is put into a baking oven in advance and dried at 60 ℃ for 0.5h, the active substance, the conductive agent and the binder are weighed according to a certain mass ratio for standby, the binder is added into a dried glass bottle, NMP is added into the binder, and the mixture is put onto a magnetic stirrer for stirring; then the weighed active substance and the conductive agent are added into a mortar, and the mortar is ground into fine powder by adopting a dry grinding mode (the grinding time is 40-50 min). Adding the ground active substance and the conductive agent into the stirred binder, continuously stirring for about 12 hours, scraping the mixture into a solution with certain viscosity (which ensures that the solution does not flow at will after coating), drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
Wherein the active material is one of ternary positive electrodes of lithium iron phosphate, carbon sulfur, lithium cobaltate, lithium titanate and lithium nickel cobalt manganate;
the conductive agent is one of acetylene black, super-P, graphene and carbon nano tube;
the binder is one of polyvinylidene fluoride, styrene-butadiene rubber, carboxymethyl cellulose and polyacrylonitrile;
the mass ratio of the active substance, the conductive agent and the binder is 8:1:1.
(2) Preparation of electrolyte: preparing local high-concentration electrolyte by adopting a dissolution method, weighing a certain amount of lithium salt, adding the lithium salt into a dried glass bottle, adding an ether solvent, then adding a fluorine-containing alkyl ether diluent according to a certain proportion, preparing local high-concentration electrolyte with different concentrations and different proportions, adding an anode film-forming additive according to a certain mass ratio, and operating all the steps in a glove box.
Wherein the ether solvent is one of tetrahydrofuran, tetraethylene glycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether;
the diluent is one or more of 3, 3-trifluoro methyl propionate, tri (trifluoro ethoxy) methane, fluoromethyl-1, 3-hexafluoroisopropyl ether;
the volume ratio of the solvent to the diluent is 2:1-1:4.
The lithium salt is one or more of lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate, lithium perchlorate and lithium trifluoroborate;
the concentration of the lithium salt in the ether solvent is 1M-4M.
The positive film-forming additive used is one or more of tris (2, 2-trifluoroethyl) phosphite (TFEP), trimethyl phosphite (TMP) or tris (pentafluorophenyl) phosphine (TPFPP).
The film forming additive accounts for 0.5 to 5 weight percent of the mass of the electrolyte.
(3) Preparation of button cell:
preparing a battery shell, a positive electrode plate, a lithium metal plate, an elastic sheet and a gasket in advance; the positive electrode shell, the positive electrode plate, the diaphragm, the electrolyte, the lithium negative electrode, the gasket, the elastic sheet and the negative electrode shell are stacked from bottom to top, the positive electrode plate and the negative electrode plate are put in the middle position without contacting with the periphery of the battery shell, and after the equipment is finished, the positive electrode plate and the negative electrode plate are put on a battery tabletting machine, and 40Kg cm of the battery is applied -3 Is encapsulated by the pressure of the pressure sensor.
The beneficial effects are that:
the invention utilizes the high stability of the ether-containing solvent to reduce the side reaction between the electrolyte and the electrode, improves the compatibility between the electrode and the electrolyte, prepares the local high-concentration electrolyte by adding the diluent, reduces the viscosity of the high-concentration electrolyte, simultaneously generates the anionic-derived SEI film, and has the film structure rich in inorganic components, thereby successfully inhibiting the short circuit problem caused by the growth of lithium dendrites formed by uneven deposition of the lithium metal anode and improving the cycling stability of the lithium anode; and the positive electrode film forming additive is introduced to further inhibit side reaction between the electrolyte and the positive electrode, so that the integrity of the positive electrode material is effectively protected, and the cycle life of the lithium battery is prolonged.
Local high-concentration electrolyte (LHCEs) is prepared by adding a diluent into the high-concentration electrolyte, so that the solubility of lithium salt in the diluent is extremely low, the local concentration is higher than LCEs after the diluent is added, a large amount of AGGs can be formed, the rapid diffusion of lithium ions in lithium salt/solvent clusters is promoted, the defects of HCEs are overcome, and the advantages of the HCEs are maintained. The fluorine-containing alkyl ether is selected as a diluent, and the fluorine element is introduced to further provide a flame retardant effect for the electrolyte.
Besides constructing a solid electrolyte interface layer on the surface of a battery cathode, a positive electrode film forming additive is added to construct a CEI layer on the battery cathode, so that side reactions between electrolyte and positive electrode active substances are inhibited.
Description of the drawings:
FIG. 1 is an electrolyte LSV test prepared in example 1.
FIG. 2 is an electrolyte LSV test prepared in comparative example 3.
Fig. 3 is wettability test data of the electrolytes prepared in example 1 and comparative example 1, wherein fig. 3.A is a graph showing contact angles of the local high concentration electrolytes of example 1 and fig. 3.b is a graph showing contact angles of the high concentration electrolytes of comparative example 1.
Fig. 4 is lithium-symmetric battery cycle test data of the electrolyte prepared in example 1.
Fig. 5 is cycle test data of lithium-symmetric cells of the electrolyte prepared in comparative example 3.
Fig. 6 is a graph showing the specific discharge capacity of an electrolyte-assembled lithium-iron-phosphate lithium battery prepared in example 1.
Fig. 7 is a discharge specific capacity chart of an electrolyte-assembled lithium-iron-phosphate lithium battery prepared in comparative example 2.
FIG. 8 shows the flame retardant property test of the electrolyte prepared in comparative example 1 (a) and example 1 (b).
Fig. 9 is a schematic structural view of an assembled battery of the present invention.
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 a person skilled in the art without any inventive effort, are intended to be within the scope of the present invention, based on the examples of the present invention.
Example 1
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then 0.8g of lithium iron phosphate and 0.1g of super-P are added to a mortar and ground by dry grinding for 1h until it is in the form of a fine powder (no distinct particles after coating). Adding the ground lithium iron phosphate and Super-P into a stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity (the solution does not flow at will after scraping), coating the solution onto an aluminum foil (the thickness of the aluminum foil is 0.017+/-0.001 mm, the whole thickness after scraping is 0.032+/-0.001 mm), drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 1:1 to prepare the 4M local high-concentration electrolyte. After weighing, tris (2, 2-trifluoroethyl) phosphite was added in an amount of 1wt% based on the prepared 4M local high concentration electrolyte, and magnetically stirred for 12 hours to obtain the final electrolyte.
In order to verify the electrochemical performance of the electrolyte, an ion conductivity test is performed by using a conductivity tester; stainless steel is used as a working electrode, lithium metal is used as a comparison electrode to prepare an SS// Li battery, and an electrolyte electrochemical window is tested through LSV;
lithium metal (lithium metal sheets with the diameter of 16mm and the thickness of 0.2 mm) is adopted as electrodes on two sides to prepare a Li// Li battery, and the polarization performance of the battery is tested;
the lithium iron phosphate anode and the lithium metal cathode are adopted to prepare a battery (according to the anode shell, the anode plate, the diaphragm and electrolyte (based on the battery shell with the diameter of 20mm, 50 microliters of electrolyte is dripped above the diaphragm), the lithium cathode (the lithium metal wafer with the diameter of 16mm and the thickness of 0.2 mm), a gasket, an elastic sheet and a cathode shell are stacked in sequence from bottom to top, and are put on a battery tablet press, and 40Kg cm of electrolyte is applied -3 Is packaged) and the charge and discharge performance is tested.
Example 2
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 1:1 to prepare the 4M local high-concentration electrolyte. After further weighing, tris (2, 2-trifluoroethyl) phosphite was added in an amount of 2wt% based on the 4M local high concentration electrolyte, and magnetically stirred for 12 hours to obtain the final product.
Battery assembly and performance testing were the same as in example 1.
Example 3
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of PVDF as a binder, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 1:1 to prepare the 4M local high-concentration electrolyte. After weighing, trimethyl phosphite is added according to 1wt% of the 4M local high-concentration electrolyte, and the mixture is magnetically stirred for 12 hours to obtain a final product.
Battery assembly and performance testing were the same as in example 1.
Example 4
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 1:2 to prepare the 4M local high-concentration electrolyte. After further weighing, tris (2, 2-trifluoroethyl) phosphite was added in an amount of 1wt% based on the 4M local high concentration electrolyte, and magnetically stirred for 12 hours to obtain the final product.
Battery assembly and performance testing were the same as in example 1.
Example 5
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 2:1 to prepare the 4M local high-concentration electrolyte. After further weighing, tris (2, 2-trifluoroethyl) phosphite was added in an amount of 1wt% based on the 4M local high concentration electrolyte, and magnetically stirred for 12 hours to obtain the final product.
Battery assembly and performance testing were the same as in example 1.
Example 6
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then 3, 3-trifluoro methyl propionate diluent is added according to the volume ratio of 1:1, so that the 4M local high-concentration electrolyte is prepared. After further weighing, tris (2, 2-trifluoroethyl) phosphite was added in an amount of 1wt% based on the 4M local high concentration electrolyte, and magnetically stirred for 12 hours to obtain the final product.
Battery assembly and performance testing were the same as in example 1.
Example 7
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
5.74g of lithium bis (trifluoromethanesulfonyl) imide is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 1:1 to prepare the 4M local high-concentration electrolyte. After further weighing, tris (2, 2-trifluoroethyl) phosphite was added in an amount of 1wt% based on the 4M local high concentration electrolyte, and magnetically stirred for 12 hours to obtain the final product.
Battery assembly and performance testing were the same as in example 1.
Comparative example 1
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate was weighed in a glove box and added to a dry glass bottle, which was first dissolved with 3ml of ethylene glycol dimethyl ether and transferred to a 5ml volumetric flask for constant volume. After further weighing, tris (2, 2-trifluoroethyl) phosphite was added at 1% by weight of the prepared solution and magnetically stirred for 12 hours to give the final product.
Battery assembly and performance testing were the same as in example 1.
Comparative example 2
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
3.02g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, and then fluoromethyl-1, 3-hexafluoroisopropyl ether diluent is added according to the volume ratio of 1:1 to prepare the 4M local high-concentration electrolyte.
Battery assembly and performance testing were the same as in example 1.
Comparative example 3
Putting lithium iron phosphate, super-P and PVDF into an oven in advance, drying at 60 ℃ for 0.5h, weighing for standby according to the mass ratio of 8:1:1, adding 2.0g of NMP into a glass bottle filled with 0.1g of binder PVDF, and putting the glass bottle on a magnetic stirrer for stirring; then, 0.8g of lithium iron phosphate and 0.1g of super-P were charged into a mortar, and ground by dry grinding for 1 hour until they became a fine powder. Adding the ground lithium iron phosphate and Super-P into the stirred binder PVDF solution, continuing stirring for about 12 hours, scraping the solution into a solution with certain viscosity, coating the solution on an aluminum foil, drying the solution in a vacuum oven at 60 ℃ for 24 hours, and punching the solution by a tablet press after the solvent volatilizes to obtain the prepared positive plate.
0.755g of lithium hexafluorophosphate is weighed in a glove box and added into a dry glass bottle, 3ml of ethylene glycol dimethyl ether is used for dissolution, the solution is transferred into a 5ml volumetric flask for constant volume, 1M low-concentration electrolyte is prepared, and magnetic stirring is carried out for 12 hours, so that a final product is obtained.
Battery assembly and performance testing were the same as in example 1.
Table 1 ionic conductivity at room temperature
Table 2 LSV test of different examples
As can be seen from a comparison of fig. 6 with fig. 7: comparative example 2, without the addition of positive film forming additives, had poor battery cycle performance; as can be seen from table 1: in the ion conductivity test, too little diluent has limited effect of reducing the viscosity of the electrolyte, so the ion conductivity is low; the molecular volume of the diluent is large, the ion conductivity is reduced due to excessive content of the diluent.
Claims (10)
1. The local high-concentration electrolyte with flame retardant property is characterized by comprising lithium salt, an ether solvent for dissolving the lithium salt, a fluorine-containing alkyl ether diluent and a positive electrode film forming additive.
2. The local high-concentration electrolyte with flame retardant property according to claim 1, wherein the lithium salt is one or more of lithium hexafluorophosphate, lithium bis (trifluoromethanesulfonyl) imide, lithium tetrafluoroborate, lithium perchlorate and lithium trifluoroborate; the concentration of the lithium salt in the ether solvent is 1M-4M.
3. The local high-concentration electrolyte with flame retardant property according to claim 1, wherein the ether solvent in which the lithium salt is dissolved is one of tetrahydrofuran, tetraethyleneglycol dimethyl ether, triethylene glycol dimethyl ether, ethylene glycol dimethyl ether, and diethylene glycol dimethyl ether.
4. The localized high concentration electrolyte having flame retardant properties of claim 1 wherein the fluoroalkyl ether diluent is one or more of methyl 3, 3-trifluoropropionate, tris (trifluoroethoxy) methane, fluoromethyl-1, 3-hexafluoroisopropyl ether; the volume ratio of the solvent to the diluent is 2:1-1:4.
5. The local high-concentration electrolyte with flame retardant property according to claim 1, wherein the positive electrode film forming additive is one or more of tris (2, 2-trifluoroethyl) phosphite (TFEP), trimethyl phosphite (TMP) or tris (pentafluorophenyl) phosphine (TPFPP); the film forming additive accounts for 0.5 to 5 weight percent of the mass of the electrolyte.
6. The preparation method of the lithium ion battery is characterized by comprising the following steps:
(1) Preparation of a positive electrode material:
adding the binder into a dry glass bottle, adding NMP, and placing on a magnetic stirrer for stirring; then adding the active substance and the conductive agent into a mortar, and grinding the active substance and the conductive agent into fine powder by adopting a dry grinding mode; adding the ground active substances and the conductive agents into the stirred adhesive, continuously stirring for 12 hours, scraping the materials on an aluminum foil, drying the materials in a vacuum oven at 60 ℃ for 24 hours, and punching the materials by a tablet press after the solvent volatilizes to obtain a positive plate;
(2) Preparation of a local high-concentration electrolyte with flame retardant property:
weighing lithium salt, adding the lithium salt into a dried glass bottle, adding a solvent, adding a fluorine-containing alkyl ether diluent according to a proportion, and finally adding an anode film-forming additive;
(3) Preparation of button cell:
stacking the positive electrode shell, the positive electrode plate, the diaphragm, the electrolyte, the lithium negative electrode, the gasket, the elastic sheet and the negative electrode shell from bottom to top, putting the battery sheet press after the equipment is finished, and applying 40Kg cm -3 And (5) packaging the mixture under the pressure to obtain the lithium ion button cell.
7. The method of claim 6, wherein the active material in step (1) is one of lithium iron phosphate, carbon sulfur, lithium cobaltate, lithium titanate, nickel cobalt manganese ternary positive electrode.
8. The method of claim 6, wherein the conductive agent in step (1) is one of acetylene black, super-P, graphene, and carbon nanotubes.
9. The method of claim 6, wherein the binder in step (1) is one of polyvinylidene fluoride, styrene-butadiene rubber, carboxymethyl cellulose, and polyacrylonitrile.
10. The method of claim 6, wherein the mass ratio of the active material, the conductive agent, and the binder in the step (1) is 8:1:1.
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