CN114094180A - Ether electrolyte containing silver nitrate additive for lithium metal battery - Google Patents
Ether electrolyte containing silver nitrate additive for lithium metal battery Download PDFInfo
- Publication number
- CN114094180A CN114094180A CN202111387355.7A CN202111387355A CN114094180A CN 114094180 A CN114094180 A CN 114094180A CN 202111387355 A CN202111387355 A CN 202111387355A CN 114094180 A CN114094180 A CN 114094180A
- Authority
- CN
- China
- Prior art keywords
- silver nitrate
- electrolyte
- additive
- lithium metal
- lithium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 title claims abstract description 154
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 239000003792 electrolyte Substances 0.000 title claims abstract description 91
- 229910001961 silver nitrate Inorganic materials 0.000 title claims abstract description 80
- 229910052744 lithium Inorganic materials 0.000 title claims abstract description 64
- 239000000654 additive Substances 0.000 title claims abstract description 36
- 230000000996 additive effect Effects 0.000 title claims abstract description 36
- 102000004190 Enzymes Human genes 0.000 claims abstract description 8
- 108090000790 Enzymes Proteins 0.000 claims abstract description 8
- 239000000843 powder Substances 0.000 claims description 26
- 229910052782 aluminium Inorganic materials 0.000 claims description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 22
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims description 11
- 238000007789 sealing Methods 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 claims description 8
- 238000011049 filling Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000010946 fine silver Substances 0.000 claims description 6
- 239000004570 mortar (masonry) Substances 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- SBUOHGKIOVRDKY-UHFFFAOYSA-N 4-methyl-1,3-dioxolane Chemical group CC1COCO1 SBUOHGKIOVRDKY-UHFFFAOYSA-N 0.000 claims description 4
- 229910003002 lithium salt Inorganic materials 0.000 claims description 4
- 159000000002 lithium salts Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- HNCXPJFPCAYUGJ-UHFFFAOYSA-N dilithium bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].[Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F.FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F HNCXPJFPCAYUGJ-UHFFFAOYSA-N 0.000 claims 1
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 claims 1
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 29
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 16
- 238000010438 heat treatment Methods 0.000 description 14
- XKTYXVDYIKIYJP-UHFFFAOYSA-N 3h-dioxole Chemical compound C1OOC=C1 XKTYXVDYIKIYJP-UHFFFAOYSA-N 0.000 description 11
- 229910013553 LiNO Inorganic materials 0.000 description 11
- 210000001787 dendrite Anatomy 0.000 description 8
- 230000008021 deposition Effects 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000003292 glue Substances 0.000 description 4
- 230000005484 gravity Effects 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 210000004027 cell Anatomy 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 2
- 229910052493 LiFePO4 Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000604 cryogenic transmission electron microscopy Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- -1 silver ions Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- MTAODLNXWYIKSO-UHFFFAOYSA-N 2-fluoropyridine Chemical compound FC1=CC=CC=N1 MTAODLNXWYIKSO-UHFFFAOYSA-N 0.000 description 1
- SBLRHMKNNHXPHG-UHFFFAOYSA-N 4-fluoro-1,3-dioxolan-2-one Chemical compound FC1COC(=O)O1 SBLRHMKNNHXPHG-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001290 LiPF6 Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 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 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- VAYGXNSJCAHWJZ-UHFFFAOYSA-N dimethyl sulfate Chemical compound COS(=O)(=O)OC VAYGXNSJCAHWJZ-UHFFFAOYSA-N 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- BHZCMUVGYXEBMY-UHFFFAOYSA-N trilithium;azanide Chemical compound [Li+].[Li+].[Li+].[NH2-] BHZCMUVGYXEBMY-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
- H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
- H01M10/0566—Liquid materials
- H01M10/0567—Liquid materials characterised by the additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—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
-
- 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
- H01M10/0569—Liquid materials characterised by the solvents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention discloses an enzyme electrolyte containing a silver nitrate additive for a lithium metal battery, which is obtained by dissolving silver nitrate serving as an additive in a conventional ether electrolyte for the lithium metal battery, wherein the mass ratio of the silver nitrate to the conventional ether electrolyte is 10-20: 1000; the silver nitrate is dehydrated before being added into the conventional ether electrolyte. The silver nitrate additive can obviously improve the ionic conductivity of ether electrolyte, and shows good cycle performance and coulombic efficiency when being used as the electrolyte of a lithium metal battery.
Description
(I) technical field
The invention relates to an ether electrolyte containing a silver nitrate additive for a lithium metal battery.
(II) background of the invention
The metallic lithium cathode is rapidly developed due to the low potential (minus 3.04V relative to the standard hydrogen electrode) and the high theoretical capacity (3860mA h g < -1 >), and is expected to become a high-capacity-density electrode material in the next generation energy storage system. However, lithium metal batteries have poor cyclability and potential safety problems due to the formation of lithium metal dendrites and their reaction with the electrolyte during cycling, which greatly hinders the commercial development and application of metal negative electrodes. The surface of the metal lithium electrode is covered with a layer of SEI film generated by the reaction with the electrolyte, and the passivation SEI film can protect the internal metal lithium from reacting with the electrolyte, so that the consumption of the electrolyte and the metal lithium is reduced. However, the large volume change of the lithium negative electrode during battery cycling will result in repeated breaking and regeneration of the SEI. As the number of cycles of the battery increases, the SEI continuously consumes lithium and electrolyte, resulting in a gradual decrease in the coulombic efficiency of the battery. On the other hand, Li dendrites are more likely to grow at the SEI film break-off, and the break-off of the SEI accelerates the growth of Li dendrites, eventually producing a large amount of dead lithium. As the number of battery cycles increases, the continued growth of lithium dendrites may penetrate the separator, causing safety problems such as battery shorting and even explosion. Therefore, inhibiting the growth of lithium dendrites is the first step in achieving commercial applications of metallic lithium electrodes. Numerous modification methods have been designed and studied to solve the problem of lithium dendrite formation and growth, including optimizing electrolyte composition, constructing artificial SEI, using advanced separators, preparing solid electrolytes, and designing three-dimensional frameworks. The ultimate goal of these methods is to improve SEI film stability, and the most convenient method is probably to construct stable SEI films by optimizing electrolyte components, such as 2-fluoropyridine, dimethyl sulfate, LiNO3RbF, vinylene carbonate, and high concentration electrolytes, among others. Lithium nitrate (LiNO)3) It is considered advantageous to enhance the SEI film and to improve the stability of the lithium metal anode. Several studies have shown LiNO3As additivesNO during SEI formation3 -Is reduced to LiNxOy and Li3N, both are good lithium ion conductors. Although LiNO was present3The concentration is limited, but the interface of the metallic lithium with the electrolyte can be significantly altered so that the metallic lithium is nucleated in a sphere rather than dendritic. Thus, LiNO3The additive plays a role in refining grains at the initial stage of lithium deposition, and can effectively inhibit the growth of lithium dendrites.
Disclosure of the invention
The invention aims to provide an ether electrolyte containing a silver nitrate additive for a lithium metal battery, which is applied to protect a lithium metal anode and solves the problems that the conventional lithium metal battery generates random deposition of Li immediately after the beginning of circulation and is accompanied with the production of lithium dendrite.
The technical scheme adopted by the invention is as follows:
the invention provides an enzyme electrolyte containing a silver nitrate additive for a lithium metal battery, which is obtained by dissolving silver nitrate as an additive in a conventional ether electrolyte for the lithium metal battery, wherein the mass ratio of the silver nitrate to the conventional ether electrolyte is 10-20: 1000; the silver nitrate is dehydrated before being added into the conventional ether electrolyte.
Preferably, the purity of the silver nitrate is more than 99.9999%.
Preferably, the mass ratio of the silver nitrate to the conventional ether electrolyte is 10: 1000.
preferably, the silver nitrate removes moisture by: adding silver nitrate powder in H2O and O2And drying the mixture in an argon-filled glove box with the concentration of less than 0.01ppm for 24-48 h at the temperature of 130-180 ℃ in a dark high temperature. Further preferably dried at 150 ℃ in the dark for 24 h.
The conventional ether electrolyte is an ether electrolyte commonly used in lithium metal batteries, such as an electrolyte system with a main salt of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and a solvent of 4-methyl-1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME), wherein organic additives (such as vinylene carbonate, fluoroethylene carbonate and the like) and inorganic lithium salt (lithium salt), (lithium salt and dimethyl ether (dimethyl ether) (DME) can be selectively addedSuch as LiNO3、LiPF6Etc.) and the like. In the specific embodiment of the invention, the ether electrolyte adopts lithium bistrifluoromethanesulfonylimide (LiTFSI) as a main salt, 4-methyl-1, 3-Dioxolane (DOL) and 1, 2-Dimethoxyethane (DME) as solvents, and LiNO as an optional inorganic lithium salt3The electrolyte system of (1), which is as follows: 1M LiTFSI + 0-2 wt% LiNO3The solvent is DOL and DME in a volume ratio of 1: 1.
The ether electrolyte containing the silver nitrate additive can be prepared by the following steps:
(1) adding silver nitrate powder in H2O and O2Drying in an argon-filled glove box with the concentration of less than 0.01ppm for 24-48 h at the temperature of 130-180 ℃ in a dark place at high temperature, cooling to room temperature, and then carefully grinding for 15-30 min by using a mortar to obtain dry and fine silver nitrate powder;
(2) mixing the silver nitrate powder obtained in the step (1) with a conventional ether electrolyte, placing the mixture in a clean aluminum bottle, sealing the aluminum bottle, then placing the aluminum bottle in an environment at 30-50 ℃ for heat preservation for 3-6 h (preferably 3-5 h) to accelerate the dissolution of silver nitrate in the electrolyte, more preferably placing the aluminum bottle in an environment at 40 ℃ for heat preservation for 4h, and cooling the aluminum bottle to room temperature to obtain the ether electrolyte containing the silver nitrate additive.
The ether electrolyte containing the silver nitrate additive is used for the lithium metal battery, and the lithium metal battery is assembled by adopting a conventional method.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, silver nitrate is used as an additive of ether electrolyte, silver ions spontaneously undergo a displacement reaction with metal lithium after the silver nitrate is dissolved in the ether electrolyte, and dense and uniform simple substance silver particles are formed on the surface of a lithium sheet. Elemental silver can induce nucleation and growth of lithium, eventually forming a flat, lithium dendrite-free surface. The method is extremely simple and effective.
(3) The silver nitrate additive can remarkably improve the ionic conductivity of ether electrolyte, so that the silver nitrate additive shows good cycle performance and coulombic efficiency when being used as the electrolyte of a lithium metal battery.
(IV) description of the drawings
FIG. 1 is the electrolyte of example 1 and a conventional ether electrolyte (1M LiTFSI in DOL: DME: 1 Vol% with 1% LiNO)3Ether electrolyte) of the lithium iron phosphate lithium metal battery;
fig. 2 is an SEM image of lithium deposition after 2 cycles for a lithium metal battery assembled with the electrolyte of example 1.
FIG. 3 is a conventional ether electrolyte (1M LiTFSI in DOL: DME: 1 Vol% with 1% LiNO)3Ethereal electrolyte) SEM images of lithium deposition after 2 cycles of the assembled lithium metal battery.
FIG. 4 is a graph of the deposition of 1mA h cm after 1 cycle for a battery using the electrolyte of example 1-2Cryo-TEM images of lithium morphology.
FIG. 5 is a graph showing the use of a conventional ether electrolyte (1M LiTFSI in DOL: DME: 1 Vol% with 1% LiNO)3Ether electrolyte) deposited 1mA h cm after 1 cycle-2Cryo-TEM images of lithium morphology.
(V) detailed description of the preferred embodiments
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions of the embodiments of the present application will be clearly and completely described below, but the scope of the present invention is not limited thereto. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The room temperature of the invention is 25-30 ℃. The silver nitrate powder used in the examples was from sigma reagent having a purity of 99.9999%.
Example 1
(1) At H2O and O2Filling 0.1g of silver nitrate powder into an argon-filled glove box with the content of less than 0.01ppm, filling a small crucible with a cover, placing the small crucible on a heating table in the glove box, setting the temperature of the heating table to be 150 ℃, and heating for 24 hours (shading treatment); grinding the silver nitrate powder cooled to room temperature with mortar for 20min to obtain dried fine silver nitrate powder. The obtained silver nitrate powder was mixed with 1M LiTFSI in DOL: DME: 1 Vol% with 1% LiNO at a specific gravity of 10mg/g3Ether electrolyte was mixed and filled in a clean aluminum bottle. Sealing and taking out the aluminum bottle filled with the electrolyte by using sealing glue, putting the aluminum bottle in a water bath kettle at the temperature of 40 ℃ for heat preservation for 4 hours to accelerate the dissolution of silver nitrate in the electrolyte, and cooling to obtain the ether electrolyte with silver nitrate as an additive.
(2) Assembling lithium metal battery by using ether electrolyte obtained in step (1)
Mixing LiFePO4Mixing conductive carbon black (Super P) and polyvinylidene fluoride according to the mass ratio of 8:1:1, adding a proper amount of N-methyl pyrrolidone, stirring by using a stirrer, and preparing into uniform slurry. Coating the slurry on an aluminum current collector, putting the aluminum current collector loaded with LiFePO4 in a vacuum oven at 60 ℃ for drying for 12h, taking out, and tabletting by using a tabletting machine under the pressure of 10 Mpa to finish the preparation of a positive plate with the diameter of 12 mm. Then, a lithium sheet with a diameter of 12mm was used as a negative electrode, a polypropylene film (Celgard 2300) was used as a separator, and the electrolyte prepared in step (1) and 1M LiTFSI in DOL containing no silver nitrate additive, DME: 1 Vol% with 1% LiNO, were used separately3The ether electrolyte was used to assemble the cell. And the battery is assembled according to the sequence of the positive electrode shell, the positive electrode plate, the diaphragm, the lithium plate, the foamed nickel and the negative electrode shell. The resulting cells were subjected to cycling tests on a novice cell tester at a current density of 1C, and the results are shown in fig. 1.
Fig. 1 is a cycle performance curve of a corresponding battery at a 1C cycle rate, which shows that the battery assembled by the electrolyte obtained in example 1 has good cycle performance at 1C, and the coulombic efficiency is as high as 99.8%, and it can be seen that the discharge capacity of the lithium metal battery prepared in example 1 after 400 cycles at 1C is close to 140mAh/g, and the cycle performance is excellent.
Example 2
(1) At H2O and O2Taking 0.1g of silver nitrate powder in an argon-filled glove box with the content of less than 0.01ppm, filling the silver nitrate powder into a small crucible with a cover, placing the small crucible on a heating table in the glove box, setting the temperature of the heating table to be 160 ℃, and heating for 24 hours (shading treatment); the silver nitrate powder cooled to room temperature after the completion of heating was carefully ground with a mortarGrinding for 20min to obtain dry fine silver nitrate powder. The obtained silver nitrate powder was mixed with 1M LiTFSI in DOL, DME: 1 Vol% with 1% LiNO at a specific gravity of 20mg/g3The ether electrolyte was mixed and filled in a clean aluminum bottle. Sealing and taking out the aluminum bottle filled with the electrolyte by using sealing glue, putting the aluminum bottle in a water bath kettle at 40 ℃ for 5 hours to accelerate the dissolution of silver nitrate in the electrolyte, and cooling to obtain the ether electrolyte taking silver nitrate as an additive.
(2) The method of the embodiment 1 is the same, the ether electrolyte containing the silver nitrate additive prepared in the step (1) is used for assembling the lithium metal battery, and the method of the embodiment 1 is used for detecting, the discharge capacity after 1C circulation for 350 times is close to 130mAh/g, and the circulation performance is good.
Example 3
(1) At H2O and O2Filling 0.1g of silver nitrate powder into an argon-filled glove box with the content of less than 0.01ppm, filling a small crucible with a cover, placing the small crucible on a heating table in the glove box, setting the temperature of the heating table to be 180 ℃, and heating for 36h (shading treatment); the silver nitrate powder cooled to room temperature after completion of heating was finely ground with a mortar for 15min to obtain a dry fine silver nitrate powder. The obtained silver nitrate powder was mixed with 1M LiTFSI in DOL, DME: 1 Vol% with 2% LiNO at a specific gravity of 5mg/g3The ether electrolyte was mixed and filled in a clean aluminum bottle. Sealing and taking out the aluminum bottle filled with the electrolyte by using sealing glue, putting the aluminum bottle in a water bath kettle at 35 ℃ for heat preservation for 3 hours to accelerate the dissolution of silver nitrate in the electrolyte, and cooling to obtain the ether electrolyte taking silver nitrate as an additive.
(2) The method of the embodiment 1 is the same, the ether electrolyte containing the silver nitrate additive prepared in the step (1) is used for assembling the lithium metal battery, the method of the embodiment 1 is used for detecting, the discharge capacity after 1C circulation for 200 times is close to 120mAh/g, and the circulation performance is general.
Example 4
(1) At H2O and O2Filling 0.1g of silver nitrate powder into an argon-filled glove box with the content of less than 0.01ppm, filling a small crucible with a cover, placing the small crucible on a heating table in the glove box, setting the temperature of the heating table to be 130 ℃, and heating for 48 hours (shading treatment); cooling toThe silver nitrate powder at room temperature was finely ground with a mortar for 30min to obtain a dry fine silver nitrate powder. The obtained silver nitrate powder was mixed with 1M LiTFSI in DOL: DME: 1 Vol% with 0% LiNO at a specific gravity of 50mg/g3The ether electrolyte was mixed and filled in a clean aluminum bottle. Sealing and taking out the aluminum bottle filled with the electrolyte by using sealing glue, putting the aluminum bottle in a water bath kettle at 45 ℃ for 5 hours to accelerate the dissolution of silver nitrate in the electrolyte, and cooling to obtain the ether electrolyte taking silver nitrate as an additive.
(2) In the same way as the example 1, when the ether electrolyte containing the silver nitrate additive prepared in the step (1) is used for assembling a lithium metal battery and the detection is carried out in the same way as the example 1, the discharge capacity after 1C circulation for 200 times is close to 100mAh/g, and the circulation performance is poor.
Claims (8)
1. An enzyme-like electrolyte for a lithium metal battery containing a silver nitrate additive, characterized in that: the ether electrolyte containing the silver nitrate additive is obtained by dissolving silver nitrate as an additive in a conventional ether electrolyte for a lithium metal battery, wherein the mass ratio of the silver nitrate to the conventional ether electrolyte is 10-20: 1000; the silver nitrate is dehydrated before being added into the conventional ether electrolyte.
2. The enzyme-based electrolyte for lithium metal batteries containing silver nitrate additive of claim 1, characterized in that: the mass ratio of the silver nitrate to the conventional ether electrolyte is 10: 1000.
3. the enzyme-based electrolyte for lithium metal batteries containing silver nitrate additive of claim 1, characterized in that: the silver nitrate removes moisture by the following method: adding silver nitrate powder in H2O and O2And drying the mixture in an argon-filled glove box with the concentration of less than 0.01ppm for 24-48 h at the temperature of 130-180 ℃ in a dark high temperature.
4. The enzyme-based electrolyte for lithium metal batteries containing silver nitrate additive of claim 3, characterized in that: silver nitrate powderEnding in H2O and O2Drying in an argon-filled glove box with the concentration of less than 0.01ppm for 24 hours at 150 ℃ in a dark high temperature.
5. The enzyme-based electrolyte for lithium metal batteries containing silver nitrate additive of claim 1, characterized in that: the conventional ether electrolyte adopts an electrolyte system of which the main salt is bis (trifluoromethanesulfonimide) lithium and the solvent is 4-methyl-1, 3-dioxolane and 1, 2-dimethoxyethane.
6. The enzyme-like electrolyte for lithium metal batteries containing silver nitrate additive of claim 5, characterized in that: the conventional ether electrolyte also contains inorganic lithium salt LiNO3。
7. The enzyme-based electrolyte for lithium metal batteries containing silver nitrate additive of claim 1, characterized in that: the solutes of the conventional ether electrolyte are 1M LiTFSI and 0-2 wt% LiNO3The solvent is 4-methyl-1, 3-dioxolane and 1, 2-dimethoxyethane in a volume ratio of 1: 1.
8. The enzyme-based electrolyte for lithium metal batteries containing silver nitrate additive of claim 1, characterized in that: the ether electrolyte containing the silver nitrate additive is prepared by the following steps:
(1) adding silver nitrate powder in H2O and O2Drying the mixture in an argon-filled glove box with the concentration of less than 0.01ppm for 24-48 h at the temperature of 130-180 ℃ in a dark high temperature, cooling to room temperature, and then carefully grinding the mixture for 15-30 min by using a mortar to obtain dried fine silver nitrate powder;
(2) mixing the silver nitrate powder obtained in the step (1) with a conventional ether electrolyte, filling the mixture into a clean aluminum bottle, sealing the aluminum bottle, then placing the aluminum bottle in an environment with the temperature of 30-50 ℃ for 3-6 hours to accelerate the dissolution of silver nitrate in the electrolyte, and cooling to room temperature to obtain the ether electrolyte containing the silver nitrate additive.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111387355.7A CN114094180A (en) | 2021-11-22 | 2021-11-22 | Ether electrolyte containing silver nitrate additive for lithium metal battery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111387355.7A CN114094180A (en) | 2021-11-22 | 2021-11-22 | Ether electrolyte containing silver nitrate additive for lithium metal battery |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114094180A true CN114094180A (en) | 2022-02-25 |
Family
ID=80302818
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111387355.7A Pending CN114094180A (en) | 2021-11-22 | 2021-11-22 | Ether electrolyte containing silver nitrate additive for lithium metal battery |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114094180A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732295A (en) * | 2017-10-12 | 2018-02-23 | 燕山大学 | A kind of solid oxide electrolyte and its low-temperature sintering method based on halogenation lithium doping |
| CN108539272A (en) * | 2018-05-10 | 2018-09-14 | 清华大学 | A kind of electrolyte of lithium metal battery |
| CN110880618A (en) * | 2018-09-06 | 2020-03-13 | 中南大学 | Lithium metal battery, negative electrode, electrolyte and preparation of lithium metal battery |
| CN111129593A (en) * | 2019-12-25 | 2020-05-08 | 广东工业大学 | Additive of secondary lithium metal battery electrolyte, electrolyte and preparation method |
| CN111313086A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium ion battery |
| CN112164803A (en) * | 2020-11-03 | 2021-01-01 | 天目湖先进储能技术研究院有限公司 | Three-dimensional dielectric polyacrylonitrile/nano silver-lithium composite material and preparation method thereof |
| CN112271332A (en) * | 2020-10-26 | 2021-01-26 | 全球能源互联网研究院有限公司 | Metal lithium battery and modified electrolyte thereof |
| CN113258140A (en) * | 2021-07-07 | 2021-08-13 | 北京壹金新能源科技有限公司 | Lithium secondary battery electrolyte and preparation method and application thereof |
-
2021
- 2021-11-22 CN CN202111387355.7A patent/CN114094180A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732295A (en) * | 2017-10-12 | 2018-02-23 | 燕山大学 | A kind of solid oxide electrolyte and its low-temperature sintering method based on halogenation lithium doping |
| CN108539272A (en) * | 2018-05-10 | 2018-09-14 | 清华大学 | A kind of electrolyte of lithium metal battery |
| CN110880618A (en) * | 2018-09-06 | 2020-03-13 | 中南大学 | Lithium metal battery, negative electrode, electrolyte and preparation of lithium metal battery |
| CN111313086A (en) * | 2019-12-24 | 2020-06-19 | 安徽圣格能源科技有限公司 | Electrolyte and lithium ion battery |
| CN111129593A (en) * | 2019-12-25 | 2020-05-08 | 广东工业大学 | Additive of secondary lithium metal battery electrolyte, electrolyte and preparation method |
| CN112271332A (en) * | 2020-10-26 | 2021-01-26 | 全球能源互联网研究院有限公司 | Metal lithium battery and modified electrolyte thereof |
| CN112164803A (en) * | 2020-11-03 | 2021-01-01 | 天目湖先进储能技术研究院有限公司 | Three-dimensional dielectric polyacrylonitrile/nano silver-lithium composite material and preparation method thereof |
| CN113258140A (en) * | 2021-07-07 | 2021-08-13 | 北京壹金新能源科技有限公司 | Lithium secondary battery electrolyte and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107645016B (en) | A kind of lithium sulphur electrolyte and preparation method thereof of cathode lithium protection | |
| CN110635116B (en) | Lithium ion battery cathode material, preparation method thereof, cathode and lithium ion battery | |
| CN108258241A (en) | A kind of cathode of lithium battery for inhibiting lithium dendrite growth using ZIF-8 porous carbon materials | |
| CN111430640A (en) | Preparation and application of titanium-based metal organic framework modified diaphragm | |
| Gao et al. | Preparation and modification of MIL-101 (Cr) metal organic framework and its application in lithium-sulfur batteries | |
| CN111082038A (en) | Low-boron-content lithium-boron alloy electrode material for lithium battery and application | |
| CN107240693A (en) | Phosphorous doped silicon graphite composite material and negative material and lithium ion battery containing it | |
| CN103855430B (en) | A kind of preparation method of lithium rechargeable battery | |
| CN114512721A (en) | Lithium ion battery non-aqueous electrolyte and lithium ion battery | |
| CN113299894A (en) | MnF2@ NC lithium ion battery cathode material and preparation method and application thereof | |
| CN109193041A (en) | A kind of lithium ion battery that high temperature cyclic performance is excellent | |
| CN115663393B (en) | Chlorine-end-group MXene ink-based diaphragm for lithium metal battery and preparation method thereof | |
| CN108987673B (en) | Lithium negative electrode containing conductive protection film and preparation method and application thereof | |
| CN109244417B (en) | Preparation method of composite positive electrode material of lithium-sulfur battery with nanosheet layered structure | |
| CN110970651B (en) | Metal-sulfur battery | |
| CN110993902A (en) | Lithium-sulfur battery with positively charged organic small molecule positive electrode additive | |
| CN115849367A (en) | Sodium-ion battery negative electrode material based on natural graphite raw material, preparation method of sodium-ion battery negative electrode material and sodium-ion battery | |
| CN101478062A (en) | Composite electrolytic solution for lithium ionic battery, preparation and use thereof | |
| CN114975957A (en) | Sulfur/glucose mesoporous carbon sphere lithium sulfur battery positive electrode material and preparation method thereof | |
| CN114094180A (en) | Ether electrolyte containing silver nitrate additive for lithium metal battery | |
| CN113764822A (en) | High-ionic-conductivity composite coating film for lithium primary battery and preparation method thereof | |
| CN110021752B (en) | Lithium, aluminum and fluorine co-doped lithium iron phosphate cathode material and preparation method thereof | |
| CN108987803B (en) | Lithium metal negative electrode film-forming electrolyte for lithium-sulfur battery and additive thereof | |
| CN113675396A (en) | Composite lithium cobalt oxide positive electrode material, preparation method and lithium ion battery | |
| CN115360356B (en) | Modified lithium cladding structure and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |