CN114649502A - Liquid metal coating, preparation method thereof and application thereof in lithium-free metal lithium battery - Google Patents
Liquid metal coating, preparation method thereof and application thereof in lithium-free metal lithium battery Download PDFInfo
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- CN114649502A CN114649502A CN202011505797.2A CN202011505797A CN114649502A CN 114649502 A CN114649502 A CN 114649502A CN 202011505797 A CN202011505797 A CN 202011505797A CN 114649502 A CN114649502 A CN 114649502A
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Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
- H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/131—Electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1391—Processes of manufacture of electrodes based on mixed oxides or hydroxides, or on mixtures of oxides or hydroxides, e.g. LiCoOx
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/387—Tin or alloys based on tin
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
- H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
- H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
Abstract
The invention relates to a liquid metal coating, a preparation method thereof and application thereof in a lithium-free metal lithium battery. The liquid metal coating comprises a liquid metal layer of a gallium-based alloy that is liquid at room temperature; the liquid metal coating is used for a negative electrode coating of a lithium-free metal lithium battery; the gallium-based alloy includes: gallium-tin alloy or gallium-indium-tin alloy; the liquid metal coating is coated on the current collector, the coating thickness is less than 500nm, and the liquid metal loading capacity is less than 0.2mg/cm2。
Description
Technical Field
The invention relates to the technical field of materials, in particular to a liquid metal coating, a preparation method thereof and application thereof in a lithium-free metal lithium battery.
Background
Energy demand brought by environmental crisis and population growth caused by increasingly severe climate change is motivating global exploration of various forms of advanced energy storage technologies, and at present, lithium ion battery systems are taken as representative electrochemical energy storage, and become key elements of novel energy technology development due to higher conversion efficiency and flexibility. However, electrode materials based on an embedded reaction mechanism have been developed to the theoretical limit they can reach, and more new high energy density electrode materials are beginning to replace the conventional electrode materials for lithium batteries. Of the many high energy lithium battery systems, the closest commercial application is to match a high energy density layered transition metal oxide positive electrode with a lithium metal negative electrode, and their application will make the energy density of the lithium battery exceed 350Wh/kg and even 400Wh/kg, and thus have been receiving extensive attention from researchers. However, the ultra-high capacity is accompanied by a huge volume effect, which poses a challenge to the interfacial stability between the electrode and the electrolyte, and aggravates the irreversible side reaction between the electrode and the electrolyte. Thus, this battery system tends to be accompanied by lower first-week coulombic efficiency, and poorer cycle stability. For such a high energy system, the cycle life of the entire battery can be greatly improved by maintaining the interface stability between the lithium negative electrode and the electrolyte. Therefore, there are various proposals to promote uniform deposition of metallic lithium on the negative electrode.
These schemes can be mainly divided into two major categories, one category promotes uniform deposition of metallic lithium by regulating and controlling the electrochemical properties and mechanical properties of Solid Electrolyte Interface (SEI) films (or artificial SEI films); the other is to achieve uniform deposition of metallic lithium by controlling nucleation at the beginning of the metallic lithium process. These solutions do improve the first-cycle coulombic efficiency or the cycle stability of the battery properly, but they have some limitations: the performance improvement effect is not obvious, the material is unstable in the air, and the method is not compatible with the traditional battery production process. Therefore, it is very necessary to develop a novel lithium negative electrode modification technical scheme, so that the energy density of the lithium metal battery without the negative electrode is greatly improved on the basis of low cost and simple process.
Disclosure of Invention
The embodiment of the invention provides a liquid metal coating, a preparation method thereof and application thereof in a lithium-free metal lithium battery. The nucleation morphology of the metal lithium on the negative current collector is influenced by the liquid metal coating to become more orderly, the metal lithium is promoted to grow more compactly and uniformly on the negative electrode, the contact area between the metal lithium negative electrode and the electrolyte is reduced, the amount of irreversible side reaction at the interface is reduced, the loss amount of reversible lithium resources in each charge-discharge cycle is reduced, the cycle stability of the battery is improved, and the energy density is also improved.
In a first aspect, embodiments of the present invention provide a liquid metal coating for a lithium metal-free lithium battery, the liquid metal coating including a liquid metal layer of a gallium-based alloy that is liquid at room temperature; the liquid metal coating is used for a negative electrode coating of a lithium-free metal lithium battery;
the gallium-based alloy includes: gallium-tin alloy or gallium-indium-tin alloy;
the liquid metal coating is coated on the current collector, the coating thickness is less than 500nm, and the liquid metal loading capacity is less than 0.2mg/cm2。
Preferably, the current collector comprises a metallic current collector or a non-metallic current collector;
the metal current collector includes: copper, nickel, titanium, platinum, stainless steel, constantan and alloy materials thereof;
the non-metallic current collector includes: carbon film, carbon cloth, carbon paper, carbon fiber, graphene, MXene and conductive polymer nonmetal materials.
In a second aspect, embodiments of the present invention provide a lithium-free negative electrode comprising a liquid metal coating for a lithium metal-free lithium battery as described in the first aspect above.
In a third aspect, an embodiment of the present invention provides a preparation method of the lithium-free negative electrode according to the second aspect, where the preparation method includes:
dripping a proper amount of liquid metal of gallium-based alloy on the surface of a current collector, repeatedly coating the liquid metal by using a scraper to uniformly disperse the liquid metal on the surface of the current collector, and removing the redundant liquid metal to form a liquid metal coating with the thickness of less than 500 nm; wherein the gallium-based alloy comprises: gallium-tin alloy or gallium-indium-tin alloy;
the liquid metal loading of the liquid metal coating is less than 0.2mg/cm2。
In a fourth aspect, an embodiment of the present invention provides a method for preparing a lithium-free negative electrode according to the second aspect, where the method includes:
dropping a proper amount of liquid metal droplets into an organic solvent, and ultrasonically dispersing to disperse the liquid metal droplets into micron-sized droplets which are suspended in the organic solvent to form a liquid metal suspension; the organic solvent comprises any one of alcohols, ethers, alkanes or halogenated derivatives thereof;
uniformly spraying the liquid metal suspension on the surface of the current collector, and coating once by using a scraper after the organic solvent is volatilized, so that micron-sized liquid metal droplets are thoroughly and uniformly spread on the surface of the current collector to form a liquid metal suspension with the thickness of less than 500nm and the liquid metal loading capacity of less than 0.2mg/cm2The liquid metal coating of (2).
In a fifth aspect, an embodiment of the present invention provides a lithium-free metal lithium battery, including: a positive electrode, an electrolyte, a separator, and the lithium-free negative electrode described in the second aspect above or the lithium-free negative electrode obtained by the production method described in the third or fourth aspect above.
Preferably, the positive electrode comprises a positive electrode material, conductive carbon, a binder and a positive electrode current collector; the active material loading capacity of the anode material in the anode is 5-30mg/cm2(ii) a The specific area capacity of the positive electrode is 1-6mAh/cm2(ii) a The anode material comprises one or more of a layered oxide, a spinel structure oxide and a polyanion compound; wherein the layered oxide has a crystal structure of alpha-NaFeO2Form (III) has the molecular formula LiM1O2M1 is one or more of transition metals, and the LiM1O2The method specifically comprises the following steps: LiCoO2、LiNiO2、LiMnO2、LiNi1/2Mn1/2O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One or more of the above; the spinel-structured oxide is a spinel-structured oxide with a crystal structure of LiM22O4M2 is one or more of transition metals, and the LiM22O4The method specifically comprises the following steps: LiMn2O4、LiNi1/2Mn3/2O4One or more of the above; the polyanion-type compound is specifically a cathode material containing polyanion, and the cathode material containing polyanion comprises: LiFePO4、LiMnPO4、Li2FeSiO4、Li2MnSiO4、LiFeSO4F、LiMnSO4One or more of F.
Preferably, the positive electrode further includes: conductive additives and binders;
the conductive additive specifically comprises: acetylene black;
the binder specifically includes: polyvinylidene fluoride (PVDF).
Preferably, the electrolyte comprises one or two of a liquid electrolyte and a solid electrolyte;
wherein the liquid electrolyte comprises: any one of conventional electrolyte, high-salt-concentration electrolyte, local high-salt-concentration electrolyte and perfluorinated electrolyte;
the solid electrolyte includes any one of a polymer solid electrolyte, an oxide solid electrolyte, a lithium phosphorus oxygen nitrogen (LiPON) type solid electrolyte, and a sulfide solid electrolyte.
Preferably, the electrolyte with high salt concentration is an electrolyte with salt concentration more than or equal to 4M; wherein electrolyte salt in the high-salt-concentration electrolyte is LiFSI, LiTFSI and LiPF6One or more of, LiDFOB; the solvent is ethylene glycol dimethyl ether (DME), 1,3 Dioxolane (DOL), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), and carbonic acidOne or more of Propylene (PC), fluoroethylene carbonate (FEC);
the local high-salt-concentration electrolyte is an electrolyte obtained by diluting the high-salt-concentration electrolyte in a specific solvent; wherein the specific solvent is a solvent which has no solubility to the electrolyte salt, and comprises one or more of bis-trifluoroethyl ether and tetrafluoroethyl tetrafluoropropyl ether;
the perfluorinated electrolyte comprises fluorine electrolyte salt and a fluorinated solvent; wherein the fluorine-containing electrolyte salt comprises LiFSI, LiTFSI, LiPF6One or more of, LiDFOB; the fluorinated solvent includes one or more of FEC, fluoroethyl methyl carbonate (FEMC), 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether (HFE), bis (2,2, 2-trifluoroethyl) ether (BTFE).
According to the liquid metal coating for the lithium-free metal lithium battery provided by the embodiment of the invention, the nucleation morphology of the metal lithium on the negative electrode current collector is influenced by the liquid metal coating to become more ordered, and the metal lithium is promoted to grow more compactly and uniformly on the negative electrode. The improved growth behavior reduces the contact area between the lithium metal cathode and the electrolyte, so that the amount of irreversible side reactions at the interface is reduced, the loss amount of reversible lithium resources in each charge-discharge cycle is reduced, the first-cycle coulombic efficiency of the lithium-free lithium metal cathode is effectively improved, and the cycle stability of the battery is also improved. The higher capacity retention rate also enables the battery to still provide a higher capacity after multiple cycles, and has very positive significance for the commercial application of the lithium metal battery without the negative electrode. And the preparation method of the liquid metal coating is simple in process, good in compatibility with the existing battery assembly process, and very easy to realize large-scale production and application.
Drawings
The technical solutions of the embodiments of the present invention are further described in detail with reference to the accompanying drawings and embodiments.
Fig. 1 is a graph comparing charge and discharge curves of a high energy density lithium secondary battery having a negative electrode coated with a liquid metal according to example 1 of the present invention with a lithium secondary battery of comparative example 1;
fig. 2 is a graph comparing the cycle stability of a high energy density lithium secondary battery having a negative electrode coated with a liquid metal according to example 1 of the present invention with that of a lithium secondary battery of comparative example 1;
FIG. 3 is a scanning electron microscope comparison of the negative electrode having a liquid metal coating according to example 1 of the present invention and the negative electrode of a lithium secondary battery according to comparative example 1;
fig. 4 is a cross-sectional scanning electron microscope comparison of the negative electrode having a liquid metal coating layer provided in example 1 of the present invention and the negative electrode of the lithium secondary battery of comparative example 1.
Detailed Description
The invention is further illustrated by the following figures and specific examples, but it should be understood that these examples are for the purpose of illustration only and are not to be construed as in any way limiting the present invention, i.e., as in no way limiting its scope.
The liquid metal coating for the lithium-free metal lithium battery comprises a liquid metal layer of gallium-based alloy which is liquid at room temperature; the liquid metal coating is used for a negative electrode coating of a lithium-free metal lithium battery;
wherein the gallium-based alloy includes: gallium-tin alloy, gallium-indium-tin alloy, and the like;
the liquid metal coating is coated on the current collector, the coating thickness is less than 500nm, and the liquid metal loading capacity is less than 0.2mg/cm2。
The liquid metal coating is coated on a current collector to form the lithium-free negative electrode. Specifically, it can be prepared in at least two different ways as follows.
The first mode is as follows: dripping a proper amount of liquid metal of gallium-based alloy on the surface of a current collector, repeatedly coating the liquid metal by using a scraper to uniformly disperse the liquid metal on the surface of the current collector, and removing the redundant liquid metal to form a liquid metal coating with the thickness of less than 500 nm; the liquid metal loading of the liquid metal coating is less than 0.2mg/cm2。
The second way is: dropping proper amount of liquid metal liquid into organic solvent, ultrasonic dispersing under 20 KHz-130KHz, 20 minutes, dispersing the liquid metal droplets into micron-sized droplets, and suspending the micron-sized droplets in an organic solvent to form a liquid metal suspension; the organic solvent comprises any one of alcohols, ethers, alkanes or halogenated derivatives thereof; wherein, the alcohol can comprise ethanol and glycol, the ether can comprise glycol dimethyl ether, diethyl ether and the like, the alkane can comprise cyclohexane, hexane and the like, and the halogenated solvent can comprise tetrachloromethane, trichloromethane, dichloromethane and the like. Then, evenly spraying the liquid metal suspension on the surface of the current collector, after the organic solvent is volatilized, coating once by using a scraper to ensure that micron-sized liquid metal droplets are thoroughly and evenly spread on the surface of the current collector to form a liquid metal suspension with the thickness of less than 500nm and the liquid metal loading capacity of less than 0.2mg/cm2The liquid metal coating of (2).
A current collector for a lithium-free anode includes: a metallic current collector or a non-metallic current collector;
the metal current collector includes: metals or alloy materials with electrochemical stability under low potential, such as copper, nickel, titanium, platinum, stainless steel, constantan and the like; preferably, 10-20 micron copper foil is used.
The non-metallic current collector includes: carbon film, carbon cloth, carbon paper, carbon fiber, graphene, MXene, conductive polymer and other non-metallic materials which are electrochemically stable at a low potential.
The above lithium-free negative electrode may be used in a lithium-free metal lithium battery. The lithium-free metal lithium battery further includes: positive electrode, electrolyte, and separator.
The positive electrode comprises a positive electrode material, conductive carbon, a binder and a positive electrode current collector; the active material loading capacity of the anode material in the anode is 5-30mg/cm2(ii) a The specific area capacity of the positive electrode is 1-6mAh/cm2(ii) a The anode material comprises one or more of a layered oxide, a spinel structure oxide and a polyanion compound; wherein the layered oxide has a crystal structure of alpha-NaFeO2Form (III) has the molecular formula LiM1O2M1 is one or more of transition metals, LiM1O2The method specifically comprises the following steps: LiCoO2、LiNiO2、LiMnO2、LiNi1/2Mn1/2O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One or more of the above; the spinel-structured oxide is spinel-structured oxide with a molecular formula of LiM22O4M2 is one or more of transition metals, LiM22O4The method specifically comprises the following steps: LiMn2O4、LiNi1/2Mn3/2O4One or more of the above; the polyanionic compound is specifically a positive electrode material containing polyanion, and comprises: LiFePO4、LiMnPO4、Li2FeSiO4、Li2MnSiO4、LiFeSO4F、LiMnSO4One or more of F.
The positive electrode may further include: conductive additives and binders; the conductive additive specifically includes: acetylene black; the binder specifically includes: polyvinylidene fluoride (PVDF).
The electrolyte comprises one or two of liquid electrolyte and solid electrolyte;
wherein the liquid electrolyte comprises: any one of conventional electrolyte, high-salt-concentration electrolyte, local high-salt-concentration electrolyte and perfluorinated electrolyte;
the conventional electrolyte is a common electrolyte in lithium batteries.
The electrolyte with high salt concentration is the electrolyte with salt concentration more than or equal to 4M; wherein electrolyte salt in the high-salt-concentration electrolyte is LiFSI, LiTFSI and LiPF6One or more of LiDFOB; the solvent is one or more of ethylene glycol dimethyl ether (DME), 1,3 Dioxolane (DOL), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC);
the local high-salt-concentration electrolyte is obtained by diluting the high-salt-concentration electrolyte in a specific solvent; wherein the specific solvent is a solvent which has no solubility to the electrolyte salt, and specifically comprises one or more of bis (trifluoroethyl) ether and tetrafluoroethyl tetrafluoropropyl ether;
the perfluorinated electrolyte comprises fluorine electrolyte salt and a fluorinated solvent; wherein the fluorine-containing electrolyte salt comprises LiFSI, LiTFSI, LiPF6One or more of, LiDFOB; the fluorinated solvent includes one or more of FEC, fluoroethyl methyl carbonate (FEMC), 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether (HFE), bis (2,2, 2-trifluoroethyl) ether (BTFE).
The solid electrolyte includes any one of a polymer solid electrolyte, an oxide solid electrolyte, a lithium phosphorus oxygen nitrogen (LiPON) type solid electrolyte, and a sulfide solid electrolyte.
The diaphragm is selected from common diaphragms of lithium batteries.
According to the liquid metal coating for the lithium-free metal lithium battery provided by the embodiment of the invention, the nucleation morphology of the metal lithium on the negative electrode current collector is influenced by the liquid metal coating to become more ordered, and the metal lithium is promoted to grow more compactly and uniformly on the negative electrode. The improved growth behavior reduces the contact area between the lithium metal cathode and the electrolyte, so that the amount of irreversible side reactions at the interface is reduced, the loss amount of reversible lithium resources in each charge-discharge cycle is reduced, the first-cycle coulombic efficiency of the lithium-free lithium metal cathode is effectively improved, and the cycle stability of the battery is also improved. The higher capacity retention rate also enables the battery to still provide a higher capacity after multiple cycles, and has very positive significance for the commercial application of the lithium metal battery without the negative electrode. And the preparation method of the liquid metal coating is simple in process, good in compatibility with the existing battery assembly process, and very easy to realize large-scale production and application.
In order to better understand the technical solution provided by the present invention, the following describes a specific process for preparing a lithium-free negative electrode having a liquid metal coating for a lithium-free metal lithium battery by applying the method provided by the above-mentioned embodiment of the present invention, and a method and battery characteristics for applying the same to a lithium-free metal lithium battery, respectively, by using a plurality of specific examples.
Example 1
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6gLi [ Ni ]0.8Co0.1Mn0.1]O2Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml N-methylpyrrolidone (NMP) solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) An appropriate weight of GaInSn liquid metal droplets (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) were dropped on the surface of a copper foil having a thickness of 10 μm, and the liquid metal was repeatedly applied using a doctor blade to uniformly disperse the liquid metal on the surface of the copper foil. Then, repeatedly blade-coating the copper foil by using a scraper to remove the redundant liquid metal, wherein the thickness of the obtained liquid metal coating is 270nm, and the liquid metal loading is 0.14mg/cm2。
(5) And (3) in a glove box filled with argon, using the copper foil modified by the liquid metal coating obtained in the step (4) as a negative electrode, using Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the step (5) was allowed to stand for 3 hours, the electrochemical performance of the cell was measured on a novice cell test system at a current density of 0.1C (1C-20 mA/g) and a test temperature of 25 ℃.
To better illustrate the performance and characteristics of the liquid metal coating layer of the present example and the lithium metal-free negative electrode and the lithium metal-free lithium battery comprising the liquid metal coating layer, the following comparative example 1 is used for comparison.
Comparative example 1
The comparative example 1 provides a preparation method and performance test of a common lithium-free metal lithium battery.
(1) 9.6g of Li [ Ni ]0.8Co0.1Mn0.1]O2(NCM811) adding the anode material and 0.2g of acetylene black into an agate ball milling tank, and carrying out ball milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) And (3) assembling the lithium secondary battery soft package battery with the positive electrode obtained in the step (3) in a glove box filled with argon by taking copper foil with the thickness of 10 microns as a negative electrode, Celgard3501 as a diaphragm and 6M LiFSI DME solution as an electrolyte.
(5) After the cell obtained in the above step (4) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Fig. 1 is a graph comparing charge and discharge curves of a high energy density lithium secondary battery having a negative electrode coated with a liquid metal according to example 1 of the present invention with a lithium secondary battery of comparative example 1; fig. 2 is a graph comparing the cycle stability of a high energy density lithium secondary battery having a negative electrode coated with a liquid metal according to example 1 of the present invention with that of a lithium secondary battery of comparative example 1; as can be seen from the comparison graph of the charge and discharge curves in fig. 1, the lithium secondary battery of example 1 has higher first-cycle coulombic efficiency and higher first-cycle discharge capacity than the lithium secondary battery of comparative example 1 under the same test conditions as the lithium secondary battery of comparative example 1, and in 50 cycles, as shown in fig. 2, the specific discharge capacity retention rate of example 1 is much higher than that of the lithium secondary battery of comparative example 1, which illustrates that the cycle stability of the high-energy density lithium secondary battery can be increased by modifying the negative electrode with the liquid metal coating.
FIG. 3 is a scanning electron microscope comparison of the negative electrode having a liquid metal coating according to example 1 of the present invention and the negative electrode of a lithium secondary battery according to comparative example 1; fig. 4 is a cross-sectional scanning electron microscope comparison of the negative electrode having a liquid metal coating layer provided in example 1 of the present invention and the negative electrode of the lithium secondary battery of comparative example 1. As can be seen from the comparison graph of the scanning electron microscope in fig. 3, after the negative electrode in example 1 is modified by the liquid metal coating, the deposition of the metal lithium is more compact and uniform, which indicates that the liquid metal coating improves the coulombic efficiency of the battery by improving the deposition morphology of the metal lithium. As can be seen from the comparison of the cross-sectional scanning electron microscope in fig. 4, the negative electrode of example 1 is modified by the liquid metal coating, and is thinner than the negative electrode of comparative example 1 in which the same amount of lithium metal is deposited, which again indicates that the liquid metal coating can promote the compact deposition of lithium metal.
Example 2
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g of Li [ Ni ]0.8Co0.1Mn0.1]O2Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 250-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) Liquid metal droplets of GaInSn liquid metal (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) In appropriate weight were dropped In ethylene glycol dimethyl ether (DME), and then dispersed ultrasonically at 100KHz for 20 minutes to disperse large liquid metal droplets into micron-sized small droplets and suspended In an organic solvent. Uniformly spraying the liquid metal suspension on the surface of the copper foil, and coating once by using a scraper after the organic solvent is volatilized, so that liquid metal droplets are thoroughly and uniformly spread on the surface of the copper foil, and obtaining a liquid metal coatingHas a thickness of 78nm and a liquid metal loading of 0.04mg/cm2。
(5) And (3) in a glove box filled with argon, using the copper foil modified by the liquid metal coating obtained in the step (4) as a negative electrode, using Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the above step (5) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Example 3
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g LiFePO4(LFP) adding the anode material and 0.2g of acetylene black into an agate ball milling tank, and carrying out ball milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 150-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) A suitable weight of GaInSn liquid metal (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) was dropped on the surface of a copper foil having a thickness of 10 μm, and the liquid metal was repeatedly applied using a doctor blade to uniformly disperse the liquid metal on the surface of the copper foil. Then, repeatedly blade-coating the copper foil by using a scraper to remove the redundant liquid metal, wherein the thickness of the obtained liquid metal coating is 270nm, and the liquid metal loading is 0.14mg/cm2。
(5) And (3) in a glove box filled with argon, using the copper foil modified by the liquid metal coating obtained in the step (4) as a negative electrode, using Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the step (5) was allowed to stand for 3 hours, the electrochemical performance of the cell was measured on a novice cell test system at a current density of 0.1C (1C-20 mA/g) and a test temperature of 25 ℃.
Example 4
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g LiFePO4Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) Liquid metal droplets of GaInSn liquid metal (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) In appropriate weight were dropped In ethylene glycol dimethyl ether (DME), and then dispersed ultrasonically at 100KHz for 20 minutes to disperse large liquid metal droplets into micron-sized small droplets and suspended In an organic solvent. Uniformly spraying the liquid metal suspension on the surface of the copper foil, and coating once by using a scraper after the organic solvent is volatilized, so that liquid metal droplets are thoroughly and uniformly spread on the surface of the copper foil, the thickness of the obtained liquid metal coating is 78nm, and the liquid metal loading capacity is 0.04mg/cm2。
(5) And (3) in a glove box filled with argon, using the copper foil modified by the liquid metal coating obtained in the step (4) as a negative electrode, using Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the above step (5) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Example 5
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g LiCoO2(LCO) anode material and 0.2g acetylene black are added into an agate ball milling tank and ball milled for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) An appropriate weight of GaInSn liquid metal droplets (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) were dropped on the surface of a copper foil having a thickness of 10 μm. Then, repeatedly blade-coating the copper foil by using a scraper to remove the redundant liquid metal, wherein the thickness of the obtained liquid metal coating is 270nm, and the liquid metal loading is 0.14mg/cm2。
(5) And (3) in a glove box filled with argon, using the copper foil modified by the liquid metal coating obtained in the step (4) as a negative electrode, using Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the above step (5) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Example 6
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g LiCoO2The anode material and 0.2g of acetylene black were added to an agate jar mill at 35rpmBall milling for 3 hours at the rotating speed of (1);
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) Liquid metal droplets of GaInSn liquid metal (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) of appropriate weight were dropped In ethylene glycol dimethyl ether (DME), and then dispersed by ultrasonic dispersion at 100KHz for 20 minutes to disperse large liquid metal droplets into micron-sized small droplets and suspended In an organic solvent. Uniformly spraying the liquid metal suspension on the surface of the copper foil, and coating once by using a scraper after the organic solvent is volatilized, so that liquid metal droplets are thoroughly and uniformly spread on the surface of the copper foil, the thickness of the obtained liquid metal coating is 78nm, and the liquid metal loading capacity is 0.04mg/cm2。
(5) And (4) in a glove box filled with argon, using the liquid metal coating modified copper foil obtained in the step (4) as a negative electrode, Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the above step (5) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Example 7
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g of Li [ Ni ]0.8Co0.1Mn0.1]O2Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micron scraper, drying for 10 hours by blowing at 55 ℃, rolling, cutting into 3-4 cm square pieces to obtain the positive pole piece, wherein the loading capacity of active substances is 25mg/cm2；
(4) A suitable weight of liquid metal of GaSn (Ga: Sn 70%: 30%, alloy melting point 25 ℃) was dropped on the surface of a copper foil having a thickness of 10um, and the liquid metal was repeatedly applied using a doctor blade to uniformly disperse the liquid metal on the surface of the copper foil. Then, repeatedly blade-coating the copper foil by using a scraper to remove the redundant liquid metal, wherein the thickness of the obtained liquid metal coating is 270nm, and the liquid metal loading is 0.14mg/cm2。
(5) And (3) in a glove box filled with argon, using the copper foil modified by the liquid metal coating obtained in the step (4) as a negative electrode, using Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the above step (5) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Example 8
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g of Li [ Ni ]0.8Co0.1Mn0.1]O2Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, then degassing the mixture for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 200-micron scraper, and carrying out air blast drying at 55 DEG CDrying for 10 hours, rolling and cutting into 3 x 4cm square pieces to obtain the positive pole piece with the active substance loading of 15mg/cm2；
(4) An appropriate weight of GaInSn liquid metal droplets (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) were dropped on the surface of the copper foil, and the liquid metal was repeatedly applied using a doctor blade to uniformly disperse the liquid metal on the surface of the copper foil. Then, repeatedly blade-coating the copper foil by using a scraper to remove the redundant liquid metal, wherein the thickness of the obtained liquid metal coating is 270nm, and the liquid metal loading is 0.14mg/cm2。
(5) And (4) in a glove box filled with argon, using the liquid metal coating modified copper foil obtained in the step (4) as a negative electrode, Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the step (5) was allowed to stand for 3 hours, the electrochemical performance of the cell was measured on a novice cell test system at a current density of 0.1C (1C-20 mA/g) and a test temperature of 25 ℃.
Example 9
This example provides the preparation and performance testing of a high energy density lithium secondary battery with a liquid metal coated negative electrode.
(1) 9.6g of Li [ Ni ]0.8Co0.1Mn0.1]O2Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 100-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of active substances is 5mg/cm2；
(4) An appropriate weight of liquid metal droplets of GaInSn (Ga: In: Sn: 68.5%: 21.5%: 10%, alloy melting point 8 ℃) was dropped on the thickness 1And (3) coating liquid metal on the surface of the copper foil with the thickness of 0um repeatedly by using a scraper, so that the liquid metal is uniformly dispersed on the surface of the copper foil. Then, repeatedly blade-coating the copper foil by using a scraper to remove the redundant liquid metal, wherein the thickness of the obtained liquid metal coating is 270nm, and the liquid metal loading is 0.14mg/cm2。
(5) And (4) in a glove box filled with argon, using the liquid metal coating modified copper foil obtained in the step (4) as a negative electrode, Celgard3501 as a diaphragm, using a 6M LiFSI DME solution as an electrolyte, and assembling the positive electrode obtained in the step (3) into the lithium secondary battery soft package battery.
(6) After the cell obtained in the step (5) was allowed to stand for 3 hours, the electrochemical performance of the cell was measured on a novice cell test system at a current density of 0.1C (1C-20 mA/g) and a test temperature of 25 ℃.
To further illustrate the performance and characteristics of the liquid metal coating of this example and the lithium metal free negative electrode and lithium metal free lithium battery comprising the liquid metal coating, comparative examples 2, 3 are set forth below.
Comparative example 2
This comparative example 2 provides a preparation method and performance test for a general lithium-free metal lithium battery compared with examples 3 and 4.
(1) 9.6g LiFePO4Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) And (3) assembling the lithium secondary battery soft package battery with the positive electrode obtained in the step (3) in a glove box filled with argon by taking copper foil as a negative electrode, Celgard3501 as a diaphragm and 6M LiFSI DME solution as an electrolyte.
(5) After the cell obtained in the above step (4) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
Comparative example 3
This comparative example 3 provides a preparation method and performance test for a general lithium-free metal lithium battery compared with examples 5 and 6.
(1) 9.6g LiCoO2Adding the anode material and 0.2g of acetylene black into an agate ball-milling tank, and carrying out ball-milling for 3 hours at the rotating speed of 35 rpm;
(2) 0.2g PVDF was dissolved in 6ml NMP solvent;
(3) mixing the material obtained in the step (1) and the solution obtained in the step (2), adding the mixture into a mixer, mixing the mixture for 15 minutes at the rotating speed of 2000rpm, degassing for 5 minutes at the rotating speed of 2000rpm, coating the obtained slurry on a carbon-coated aluminum foil by using a 300-micrometer scraper, carrying out air blast drying at 55 ℃ for 10 hours, rolling, cutting into 3 x 4cm square pieces to obtain a positive pole piece, wherein the loading capacity of an active substance is 25mg/cm2；
(4) And (3) assembling the lithium secondary battery soft package battery with the positive electrode obtained in the step (3) in a glove box filled with argon by taking copper foil as a negative electrode, Celgard3501 as a diaphragm and 6M LiFSI DME solution as an electrolyte.
(5) After the cell obtained in the above step (4) was allowed to stand for 3 hours, the electrochemical performance was measured on a novice cell test system at a current density of 0.1C (1C: 20mA/g) and a test temperature of 25 ℃.
The comparison of the performance of the lithium batteries without lithium negative electrodes in examples 1 to 9 and comparative examples 1 to 3 described above is detailed in table 1 below.
TABLE 1
As can be seen from the comparison of the above embodiments, the lithium-free metal lithium battery adopting the technical scheme of the invention has better specific discharge capacity retention rate and cycling stability.
The above-mentioned embodiments, objects, technical solutions and advantages of the present invention are further described in detail, it should be understood that the above-mentioned embodiments are only examples of the present invention, and are not intended to limit the scope of the present invention, and any modifications, equivalent substitutions, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (10)
1. A liquid metal coating for a lithium metal free lithium battery, the liquid metal coating comprising a liquid metal layer of a gallium based alloy that is liquid at room temperature; the liquid metal coating is used for a negative electrode coating of a lithium-free metal lithium battery;
the gallium-based alloy includes: gallium-tin alloy or gallium-indium-tin alloy;
the liquid metal coating is coated on the current collector, the coating thickness is less than 500nm, and the liquid metal loading capacity is less than 0.2mg/cm2。
2. The liquid metal coating of claim 1, wherein the current collector comprises a metallic current collector or a non-metallic current collector;
the metal current collector includes: copper, nickel, titanium, platinum, stainless steel, constantan and alloy materials thereof;
the non-metallic current collector includes: carbon film, carbon cloth, carbon paper, carbon fiber, graphene, MXene and conductive polymer nonmetal material.
3. A lithium-free negative electrode comprising the liquid metal coating for a lithium-free metal battery as claimed in claim 1 or 2.
4. A method of preparing the lithium-free negative electrode of claim 3, comprising:
dripping a proper amount of liquid metal of gallium-based alloy on the surface of a current collector, repeatedly coating the liquid metal by using a scraper to uniformly disperse the liquid metal on the surface of the current collector, and removing the redundant liquid metal to form a liquid metal coating with the thickness of less than 500 nm; wherein the gallium-based alloy comprises: gallium-tin alloy or gallium-indium-tin alloy;
the liquid metal loading of the liquid metal coating is less than 0.2mg/cm2。
5. A method of preparing the lithium-free negative electrode of claim 3, comprising:
dropping a proper amount of liquid metal droplets into an organic solvent, and ultrasonically dispersing to disperse the liquid metal droplets into micron-sized droplets which are suspended in the organic solvent to form a liquid metal suspension; the organic solvent comprises any one of alcohols, ethers, alkanes or halogenated derivatives thereof;
uniformly spraying the liquid metal suspension on the surface of the current collector, and coating once by using a scraper after the organic solvent is volatilized, so that micron-sized liquid metal droplets are thoroughly and uniformly spread on the surface of the current collector to form a liquid metal suspension with the thickness of less than 500nm and the liquid metal loading capacity of less than 0.2mg/cm2The liquid metal coating of (2).
6. A lithium-free metal lithium battery, comprising: a positive electrode, an electrolyte, a separator, and a lithium-free negative electrode according to claim 3 or a lithium-free negative electrode obtained by the production method according to claim 4 or 5.
7. The lithium metal-free lithium battery of claim 6,
the positive electrode comprises a positive electrode material, conductive carbon, a binder and a positive electrode current collector; the loading capacity of the active substance of the anode material in the anode is 5-30mg/cm2(ii) a The specific area capacity of the positive electrode is 1-6mAh/cm2(ii) a The anode material comprises one or more of a layered oxide, a spinel structure oxide and a polyanion compound; wherein the layered oxide has a crystal structure of alpha-NaFeO2The molecular formula of the form is LiM1O2M1 isOne or more of transition metals, the LiM1O2The method specifically comprises the following steps: LiCoO2、LiNiO2、LiMnO2、LiNi1/2Mn1/2O2、LiNi1/3Co1/3Mn1/3O2、LiNi0.5Co0.2Mn0.3O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2One or more of the above; the spinel-structured oxide is a spinel-structured oxide with a crystal structure of LiM22O4M2 is one or more of transition metals, and the LiM22O4The method specifically comprises the following steps: LiMn2O4、LiNi1/2Mn3/2O4One or more of the above; the polyanion-type compound is specifically a cathode material containing polyanion, and the cathode material containing polyanion comprises: LiFePO4、LiMnPO4、Li2FeSiO4、Li2MnSiO4、LiFeSO4F、LiMnSO4One or more of F.
8. The lithium metal free lithium battery of claim 7, wherein the positive electrode further comprises: conductive additives and binders;
the conductive additive specifically includes: acetylene black;
the binder specifically includes: polyvinylidene fluoride (PVDF).
9. The lithium metal free lithium battery of claim 6, wherein the electrolyte comprises one or both of a liquid electrolyte, a solid electrolyte;
wherein the liquid electrolyte comprises: any one of conventional electrolyte, high-salt-concentration electrolyte, local high-salt-concentration electrolyte and perfluorinated electrolyte;
the solid electrolyte includes any one of a polymer solid electrolyte, an oxide solid electrolyte, a lithium phosphorus oxygen nitrogen (LiPON) type solid electrolyte, and a sulfide solid electrolyte.
10. The lithium metal-free lithium battery of claim 9,
the high-salt-concentration electrolyte is an electrolyte with the salt concentration more than or equal to 4M; wherein electrolyte salt in the high-salt-concentration electrolyte is LiFSI, LiTFSI and LiPF6One or more of LiDFOB; the solvent is one or more of ethylene glycol dimethyl ether (DME), 1,3 Dioxolane (DOL), dimethyl carbonate (DMC), Ethyl Methyl Carbonate (EMC), Ethylene Carbonate (EC), Propylene Carbonate (PC) and fluoroethylene carbonate (FEC);
the local high-salt-concentration electrolyte is an electrolyte obtained by diluting the high-salt-concentration electrolyte in a specific solvent; wherein the specific solvent is a solvent which has no solubility to the electrolyte salt, and comprises one or more of bis-trifluoroethyl ether and tetrafluoroethyl tetrafluoropropyl ether;
the perfluorinated electrolyte comprises fluorine electrolyte salt and fluorinated solvent; wherein the fluorine-containing electrolyte salt comprises LiFSI, LiTFSI, LiPF6One or more of, LiDFOB; the fluorinated solvent includes one or more of FEC, fluoroethyl methyl carbonate (FEMC), 1,2, 2-tetrafluoroethyl-2, 2, 2-trifluoroethyl ether (HFE), bis (2,2, 2-trifluoroethyl) ether (BTFE).
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| JP2001250543A (en) * | 2000-03-08 | 2001-09-14 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN110911689A (en) * | 2019-10-31 | 2020-03-24 | 南方科技大学 | Current collector and preparation method thereof, electrode plate and secondary battery |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001250543A (en) * | 2000-03-08 | 2001-09-14 | Sanyo Electric Co Ltd | Lithium secondary battery |
| CN110911689A (en) * | 2019-10-31 | 2020-03-24 | 南方科技大学 | Current collector and preparation method thereof, electrode plate and secondary battery |
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| CN115613027A (en) * | 2022-10-19 | 2023-01-17 | 四川大学 | Coating containing liquid metal and preparation method and application thereof |
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