CN114628710A - Electrolyte for carbon fluoride battery and application - Google Patents
Electrolyte for carbon fluoride battery and application Download PDFInfo
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- CN114628710A CN114628710A CN202011460352.7A CN202011460352A CN114628710A CN 114628710 A CN114628710 A CN 114628710A CN 202011460352 A CN202011460352 A CN 202011460352A CN 114628710 A CN114628710 A CN 114628710A
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- ferrocene
- lithium
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 65
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 title abstract description 24
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000011149 active material Substances 0.000 claims abstract description 9
- 239000000654 additive Substances 0.000 claims abstract description 9
- 230000000996 additive effect Effects 0.000 claims abstract description 9
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 20
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 16
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 14
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 claims description 12
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 229910013188 LiBOB Inorganic materials 0.000 claims description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000020 Nitrocellulose Substances 0.000 claims description 5
- 229920001220 nitrocellulos Polymers 0.000 claims description 5
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical group C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 claims description 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 235000010333 potassium nitrate Nutrition 0.000 claims description 3
- 239000004323 potassium nitrate Substances 0.000 claims description 3
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- KHAUBYTYGDOYRU-IRXASZMISA-N trospectomycin Chemical compound CN[C@H]([C@H]1O2)[C@@H](O)[C@@H](NC)[C@H](O)[C@H]1O[C@H]1[C@]2(O)C(=O)C[C@@H](CCCC)O1 KHAUBYTYGDOYRU-IRXASZMISA-N 0.000 claims description 3
- SRELSORUSHAWQG-UHFFFAOYSA-N 2-ethoxy-1-methoxyethanol Chemical compound CCOCC(O)OC SRELSORUSHAWQG-UHFFFAOYSA-N 0.000 claims description 2
- 229910013398 LiN(SO2CF2CF3)2 Inorganic materials 0.000 claims description 2
- 229910001290 LiPF6 Inorganic materials 0.000 claims description 2
- FJWGYAHXMCUOOM-QHOUIDNNSA-N [(2s,3r,4s,5r,6r)-2-[(2r,3r,4s,5r,6s)-4,5-dinitrooxy-2-(nitrooxymethyl)-6-[(2r,3r,4s,5r,6s)-4,5,6-trinitrooxy-2-(nitrooxymethyl)oxan-3-yl]oxyoxan-3-yl]oxy-3,5-dinitrooxy-6-(nitrooxymethyl)oxan-4-yl] nitrate Chemical compound O([C@@H]1O[C@@H]([C@H]([C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O)O[C@H]1[C@@H]([C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@@H](CO[N+]([O-])=O)O1)O[N+]([O-])=O)CO[N+](=O)[O-])[C@@H]1[C@@H](CO[N+]([O-])=O)O[C@@H](O[N+]([O-])=O)[C@H](O[N+]([O-])=O)[C@H]1O[N+]([O-])=O FJWGYAHXMCUOOM-QHOUIDNNSA-N 0.000 claims description 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- MCVFFRWZNYZUIJ-UHFFFAOYSA-M lithium;trifluoromethanesulfonate Chemical compound [Li+].[O-]S(=O)(=O)C(F)(F)F MCVFFRWZNYZUIJ-UHFFFAOYSA-M 0.000 claims description 2
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 125000002723 alicyclic group Chemical group 0.000 claims 1
- 229910002651 NO3 Inorganic materials 0.000 abstract description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 abstract description 7
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 230000003993 interaction Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 32
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- -1 fluorine alkane Chemical class 0.000 description 12
- 230000014759 maintenance of location Effects 0.000 description 12
- 239000002033 PVDF binder Substances 0.000 description 11
- 239000004743 Polypropylene Substances 0.000 description 11
- 239000008151 electrolyte solution Substances 0.000 description 11
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 11
- 239000012046 mixed solvent Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- 229920001155 polypropylene Polymers 0.000 description 11
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 11
- 239000007774 positive electrode material Substances 0.000 description 11
- 238000013112 stability test Methods 0.000 description 11
- 229920006395 saturated elastomer Polymers 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 7
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 239000011241 protective layer Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- LZDKZFUFMNSQCJ-UHFFFAOYSA-N 1,2-diethoxyethane Chemical compound CCOCCOCC LZDKZFUFMNSQCJ-UHFFFAOYSA-N 0.000 description 1
- YBDACTXVEXNYOU-UHFFFAOYSA-N C(F)(F)(F)F.[Li] Chemical compound C(F)(F)(F)F.[Li] YBDACTXVEXNYOU-UHFFFAOYSA-N 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 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
- H01M6/00—Primary cells; Manufacture thereof
- H01M6/14—Cells with non-aqueous electrolyte
- H01M6/16—Cells with non-aqueous electrolyte with organic electrolyte
- H01M6/162—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte
- H01M6/168—Cells with non-aqueous electrolyte with organic electrolyte characterised by the electrolyte by additives
-
- 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
- H01M2300/0088—Composites
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an electrolyte for a carbon fluoride battery, which comprises an active material and an additive; the active material is one or more of ferrocene and derivatives thereof; the additive comprises a metal nitrate; the ferrocene in the electrolyte can increase the energy density, meanwhile, the addition of the nitrate greatly improves the shelf stability of the battery, and the obvious coupling interaction exists between the ferrocene and the nitrate, so that the exertion of the higher energy density of the battery is ensured.
Description
Technical Field
The invention belongs to the field of lithium/carbon fluoride batteries, and particularly relates to electrolyte for a lithium carbon fluoride battery and application of the electrolyte.
Background
The primary battery has long service life, higher energy density and working voltage, and has wide application prospect even though the lithium ion battery secondary battery technology is widely applied today, and particularly the lithium/carbon fluoride battery with higher energy density is more concerned.
The lithium/carbon fluoride battery has the advantages of high energy density, good shelf stability and the like, and a key technical direction is how to further improve the energy density and give full play to the advantages. Energy density is generally increased by adding electrochemically active species, but shelf stability is lost because the active species react with the electrode material.
Disclosure of Invention
In view of the above problems, the present invention provides an electrolyte for a lithium/fluorocarbon battery that combines higher energy density and shelf stability. The electrolyte can provide active material capacity, and meanwhile, a protective layer is formed on the surface of the negative electrode, so that the shelf stability of the battery is improved.
The technical scheme of the invention is as follows:
in one aspect, the invention provides an electrolyte for a fluorinated carbon battery, comprising an active material, an additive, a solvent, and an electrolyte salt;
the active material is one or more of ferrocene and derivatives thereof; the concentration is 0.01-20 mol/L, preferably 0.1-10 mol/L;
the structures of ferrocene and ferrocene derivatives are shown below;
two of them (C)5H5) X on the cyclopentadiene ring is respectively H, (OCH)2CH2)nOCH31 to 5 of (n ═ 0 to 10), the number of X on each cyclopentadiene ring being 1 to 5; wherein the ferrocene and its derivatives are preferably ferrocene or 1, 1-diethylene glycol monomethyl ether ferrocene;
the additive comprises metal nitrate, wherein the metal nitrate comprises one or more than two of lithium nitrate, silver nitrate, potassium nitrate, sodium nitrate, rubidium nitrate, cesium nitrate, ferric nitrate and nitrocellulose, and preferably one or two of lithium nitrate and nitrocellulose; the content of the additive is 0.01-20%, preferably 0.1-5%;
the solvent comprises one or more than two of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolane, dioxane, tetrahydrofuran and compounds corresponding to the following structural formula:
wherein R1, R2, R3, R4, R5, R6, R7, R8 and R9 can be linear chain or branched chain C1 to C50 aliphatic groups, linear chain or branched chain C3 to C50 aliphatic cyclic groups, linear chain or branched chain fluorine alkane, aromatic hydrocarbon or C7 to C50 substituted aromatic hydrocarbon groups respectively;
the electrolyte salt is one or more of the following lithium salts: LiN (SO)3CF3)2、LiN(SO3CF2CF3)2、LiSO3CF3、LiBr、LiI、LiPF6And LiBOB. Among them, preferred is LiN (SO)3CF3)2、LiSO3CF3LiBOB; the concentration is 0.01-20 mol/L; preferably 0.1 to 10 mol/l.
In another aspect, the invention provides the use of an electrolyte as described above in a lithium/carbon fluoride battery.
Advantageous effects
1. The electrolyte for the lithium/carbon fluoride battery has higher energy density and shelf stability, can provide active substance capacity, and meanwhile, nitrate reacts with metal lithium to generate an insoluble solid electrolyte membrane which can only diffuse lithium ions, so that a protective layer is formed on the surface of a negative electrode, ferrocene or derivatives thereof are prevented from diffusing to the negative electrode to react with the metal lithium, and the shelf stability of the battery is improved.
2. The ferrocene in the electrolyte can increase the energy density, meanwhile, the addition of the nitrate also greatly improves the shelf stability of the battery, and the obvious coupling interaction exists between the ferrocene and the nitrate, thereby ensuring the exertion of higher energy density of the battery.
Detailed Description
Example 1
Preparing electrolyte solution by mixing 0.025mol LiN (SO) as conductive salt3CF3)2And 0.136g of ferrocene and 0.12g of lithium nitrate are added into a mixed solvent of 5ml of dimethyl carbonate, 12.5ml of ethylene glycol dimethyl ether and 7.5ml of dioxolane, stirred, dissolved and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
The energy density of the battery using the electrolyte in this example was much higher than that of comparative example 1, while the shelf stability was not much different from that of comparative example 1 and was higher than that of comparative example 2. The increased energy density is mainly brought by the ferrocene, meanwhile, the addition of the nitrate also greatly improves the shelf stability of the battery, and the ferrocene and the nitrate have obvious coupling interaction, so that the higher energy density of the battery is ensured to be exerted.
Comparative example 1
Preparing an electrolyte solution: 0.025mol of LiN (SO) as a conductive salt2CF3)2Adding into mixed solvent of dimethyl carbonate 5ml, ethylene glycol dimethyl ether 12.5ml and dioxolane 7.5ml, stirring for dissolving, and sealing for use.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein, the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 microns, the diaphragm is a 25 micron polypropylene diaphragm,finally forming a flexible package battery with the area of 80mm X10 mm, saturating and injecting the electrolyte, standing for 12 hours, removing the redundant electrolyte, and sealing for testing.
The energy density test flow of the battery comprises the following steps: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Comparative example 2
Preparing an electrolyte solution: 0.025mol of LiN (SO) as a conductive salt2CF3)2And 0.136g of ferrocene are added into a mixed solvent of 5ml of dimethyl carbonate, 12.5ml of ethylene glycol dimethyl ether and 7.5ml of dioxolane, stirred and dissolved, and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Comparative example 3
Preparing electrolyte solution by mixing 0.025mol LiN (SO) as conductive salt3CF3)2And 0.12g of lithium nitrate were added to a mixed solvent of 5ml of dimethyl carbonate, 12.5ml of ethylene glycol dimethyl ether and 7.5ml of dioxolane,stirring to dissolve, and sealing for later use.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 2
Preparing an electrolyte solution: 0.05mol of LiN (SO) as a conductive salt2CF3)20.4g of ferrocene monomethyl ether and 0.2g of lithium nitrate are added into a mixed solvent of 5ml of diethyl carbonate, 12.5ml of ethylene glycol diethyl ether and 7.5ml of dioxolane, stirred and dissolved, and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 3
Preparing an electrolyte solution: 0.04mol of LiN (SO) as a conductive salt2CF2CF3)20.3g of ferrocenyl dimethyl ether and 0.2g of potassium nitrate are added into a mixed solvent of 5ml of diethyl carbonate, 10ml of tetraethylene glycol dimethyl ether and 7.5ml of dioxolane, stirred, dissolved and sealed for standby.
The positive electrode material used for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 4
Preparing an electrolyte solution: 0.07mol of conductive salt LiSO3CF3And 0.5g of ferrocene and 0.3g of nitrocellulose are added into a mixed solvent of 5ml of dimethyl carbonate, 10ml of tetraethylene glycol dimethyl ether and 7.5ml of dioxolane, stirred, dissolved and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 5
Preparing an electrolyte solution: 0.04mol of LiN (SO) as a conductive salt2CF2CF3)20.3g of ferrocene dimethyl ether and 0.3g of cesium nitrate are added into a mixed solvent of 12.5ml of diethyl carbonate and 12.5ml of dioxane, stirred, dissolved and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 6
Preparing an electrolyte solution: 0.04mol LiBOB of conductive salt, 0.3g ferrocene diethyl ether and 0.2g lithium nitrate are added into a mixed solvent of 10ml dimethyl carbonate, 10ml ethylene glycol dimethyl ether and 7.5ml dioxolane, stirred and dissolved, and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein fluorineCarbon conversion: PVDF: the mass ratio of the conductive carbon black is 8: 1: 1) the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode and stands for 12 hours, and the opening is sealed to be tested after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 7
Preparing an electrolyte solution: 0.05mol of LiN (SO) as a conductive salt2CF3)20.7g of ferrocene and 0.2g of sodium nitrate are added into a mixed solvent of 10ml of diethyl carbonate, 10ml of tetraglyme and 7.5ml of dioxolane, stirred, dissolved and sealed for standby application.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Example 8
Preparing an electrolyte solution: 0.04mol of conductive salt LiN(SO2CF2CF3)20.6g of ferrocene dimethyl ether and 0.2g of rubidium nitrate are added into a mixed solvent of 5ml of diethyl carbonate, 10ml of tetraethylene glycol dimethyl ether and 7.5ml of dioxolane, stirred, dissolved and sealed for standby.
The positive electrode material for testing the electrolyte performance was carbon fluoride (F/C ═ 1) and the areal density was 10mg/cm2(wherein the mass ratio of the carbon fluoride to the PVDF to the conductive carbon black is 8: 1: 1), the negative electrode material is metal lithium, the thickness is 150 micrometers, the diaphragm is a 25-micrometer polypropylene diaphragm, the flexible package battery with the area of 80mm X10 mm is finally formed, electrolyte is injected in a saturated mode, standing is carried out for 12 hours, and the opening is sealed for testing after the redundant electrolyte is removed.
The energy density test flow of the battery is as follows: after standing at room temperature for 12 hours or more, the cell was discharged at a current of 0.5A to a voltage of 1.5V, and the cell capacity and energy were recorded to calculate the energy density.
The shelf stability test flow of the battery is as follows: after being left for one month in an environment of 55 ℃, the battery is discharged to the voltage cut-off of 1.5V at the current of 0.5A, the battery capacity is recorded, and the residual capacity retention rate is calculated by comparing with the normal-temperature battery capacity.
Tables 1,
| Energy Density/Wh/kg | Capacity retention rate | |
| Example 1 | 1200 | 95.5％ |
| Comparative example 1 | 850 | 95％ |
| Comparative example 2 | 1100 | 85％ |
| Comparative example 3 | 855 | 95.2％ |
| Example 2 | 1250 | 95％ |
| Example 3 | 1100 | 95％ |
| Example 4 | 1150 | 95.6％ |
| Example 5 | 1260 | 95.5％ |
| Example 6 | 1240 | 95％ |
| Example 7 | 1050 | 96％ |
| Example 8 | 1080 | 95.4％ |
Claims (9)
1. An electrolyte for a fluorinated carbon battery, characterized in that the electrolyte comprises an active material and an additive;
the active material is one or more of ferrocene and derivatives thereof;
the structures of ferrocene and ferrocene derivatives are shown below;
wherein, the number of X on each cyclopentadiene ring is 1-5; two (C)5H5) X on the cyclopentadiene ring is independently selected from H, (OCH)2CH2)nOCH31 to 5 of (n-0 to 10);
the additive includes a metal nitrate.
2. The electrolyte of claim 1, wherein the ferrocene and its derivatives are ferrocene or 1, 1-diethylene glycol monomethyl ether ferrocene.
3. The electrolyte of claim 1, wherein the metal nitrate comprises one or more of lithium nitrate, silver nitrate, potassium nitrate, sodium nitrate, rubidium nitrate, cesium nitrate, ferric nitrate, and nitrocellulose.
4. The electrolyte of claim 3, wherein the metal nitrate is one or both of lithium nitrate and nitrocellulose.
5. The electrolyte of claim 1, wherein the concentration of the active material in the electrolyte is 0.01 to 20 moles/liter; the additive content is 0.01 wt% -20 wt%.
6. The electrolyte of claim 5, wherein the concentration of the active material in the electrolyte is 0.1 to 10 moles/liter; the content of the additive is 0.1-5 wt%.
7. The electrolyte of claim 1, further comprising a solvent, an electrolyte salt;
the solvent comprises one or more than two of ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, dioxolane, dioxane, tetrahydrofuran and compounds corresponding to the following structural formula:
wherein, R1, R2, R3, R4, R5, R6, R7, R8, R9 are each independently selected from linear or branched C1 to C50 aliphatic, linear or branched C3 to C50 alicyclic, linear or branched fluoroalkane, aromatic hydrocarbon, or C7 to C50 substituted aromatic hydrocarbon group;
the electrolyte salt is one or more of the following lithium salts: LiN (SO)2CF3)2、LiN(SO2CF2CF3)2、LiN(SO2CF2CF2CF3)2、LiSO3CF3、LiBr、LiI、LiPF6、LiBOB；
The concentration of the electrolyte salt is 0.01-20 mol/L.
8. The electrolyte of claim 7, wherein the electrolyte salt is LiN (SO)3CF3)2、LiSO3CF3One or more of LiBOB and LiBOB; the concentration of the electrolyte salt is 0.1-10 mol/L.
9. Use of the electrolyte of claim 1 in a lithium/fluorocarbon battery.
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