CN107591511B - Composite membrane material for lithium battery and preparation method and application thereof - Google Patents
Composite membrane material for lithium battery and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a composite film material for a lithium battery, wherein the composite film material comprises a polymer film and a conductor particle layer coated on one side surface of the polymer film, wherein the conductor particle layer contains one or more of particles of an ionic conductor material, particles of an ionic-electronic mixed conductor material and particles of an electronic conductor material. The invention also provides a preparation method of the composite film material and application of the composite film material in a rechargeable metal lithium battery. In addition, the invention provides a liquid metal lithium battery and a solid metal lithium battery which comprise the composite film material.
Description
Technical Field
The invention belongs to the technical field of electrochemistry and new energy materials, and particularly relates to a composite membrane material for a lithium battery, and a preparation method and application thereof.
Technical Field
In recent years, the rapidly developing electric automobile and energy storage industry have put higher demands on the energy density, cost, cyclicity and safety of lithium ion batteries.
Metallic lithium anodes are considered fourth generation anodes with capacities up to 3860mAh/g and lower deposition potentials (-3.04V). The energy density of the battery can be improved to 300wh/kg by adopting the metal lithium as the cathode, the mileage anxiety of the electric automobile can be effectively relieved, and meanwhile, the lithium-free anode can be adopted, so that the cost of the battery is reduced.
The core problem of metallic lithium as a negative electrode is the infinite expansion of the negative electrode volume. Further, lithium metal as a negative electrode has the following problems: lithium deposition is not uniform during charging, and a large amount of lithium deposition locally accelerates volume expansion, thereby causing breakage of a solid electrolyte layer (SEI); lithium dendrites are formed, and the dendrites easily penetrate through a short circuit caused by a diaphragm; the dendrite has higher chemical reaction activity, is easy to react with the electrolyte and consumes the electrolyte; and the dissolution and separation of lithium at the root of the dendrite are easy to break the dendrite to form dead lithium, so that the energy efficiency of the battery bank is low.
Currently, common methods for protecting metals include the use of oxides, sulfide solid electrolytes, polymer solid electrolytes, liquid film-forming additives, and methods for modifying the lithium metal structure to reduce the effective current density and volume expansion.
Although the use of the solid electrolyte eliminates the side reaction between the lithium metal negative electrode and the solution, the oxide electrolyte membrane is fragile and is not easily fabricated into a high-capacity battery. In particular, micron thick ceramic plates, while blocking lithium dendrite growth, do not increase the cell energy density.
The sulfide electrolyte has higher conductivity and flexibility, and a better composite anode can be prepared by cold pressing, but the anode and the sulfide electrolyte are difficult to be uniformly mixed, and the sulfide electrolyte has high preparation conditions and poor air stability.
Although the polymer solid electrolyte has certain flexibility and can inhibit the growth of lithium dendrites, the conductivity of the polymer solid electrolyte is lower, and the internal resistance of the battery is higher.
Although the film-forming additive can effectively improve the energy storage efficiency of the battery and inhibit the growth of lithium dendrites, when the additive is exhausted, lithium deposition is not uniform, SEI is broken, and dendrites continue to grow. The electrolyte is consumed all the time, the internal resistance of the battery is obviously increased, the polarization is increased, and the capacity is attenuated.
Among lithium ion batteries, U.S. patent US6,432,586B1 issued on 8/13/2002 and U.S. patent application US2006/0008700a1 issued on 1/12/2006 disclose a porous substrate-based ceramic separator coated with an inorganic layer (e.g., alumina, silica, calcium carbonate, titania, etc.) that can effectively prevent internal short circuits caused by growth of dendrites inside the lithium ion battery and improve the safety performance of the lithium ion battery.
For a metal lithium battery, the dendrite growth phenomenon is more serious. The dendrite growth cannot be effectively prevented only by the ceramic-coated membrane technique.
In view of this, it is necessary to provide a membrane material which has good safety, high ionic conductivity and is easy to prepare on a large scale.
Disclosure of Invention
Therefore, in order to solve the above problems, the present invention provides a composite film material for a lithium battery, and a preparation method and applications thereof.
The purpose of the invention is realized by the following technical scheme.
In a first aspect, the present invention provides a composite film material for a lithium battery, wherein the composite film material comprises a polymer film and a conductor particle layer coated on one surface of the polymer film, wherein the conductor particle layer contains one or more of particles of an ionic conductor material, particles of an ionic-electronic mixed conductor material, and particles of an electronic conductor material.
According to the composite membrane material provided by the invention, the ion conductor material is selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-nLa3Zr2-nTanO12、Li7-nLa3Zr2-nNbnO12、Li7-2nLa3Zr2-nWnO12、Li7-2nLa3Zr2-nTenO12、Li7- 3nGenLa3Zr2O12And Li7-3nAlnLa3Zr2O12R is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2/3, z is more than or equal to 0 and less than or equal to 2, m is more than or equal to 0 and less than or equal to 2, and n is more than or equal to 0 and less than or equal to 0.6.
In some specific embodiments, the ionic conductor material is selected from Li1.5Al0.5Ge1.5(PO4)3、Li7P3S11、Li3PS4、Li0.5La0.5TiO3、LiZr0.5Ti1.5(PO4)3、Li1.4Al0.4Ti1.6(PO4)3And Li3.5Ge0.5P0.5S4One or more of (a).
As used herein, the term "ionic-electronic mixed conductor material" refers to a solid material interposed between an ionic conductor material and an electronic conductor material that has both ionic and electronic conductivity.
In some embodiments, the ion-electron mixed conductor material is one or more selected from the group consisting of natural graphite, artificial graphite, soft carbon, hard carbon, silicon, germanium, lithium titanate, titanium dioxide, copper oxide, zinc oxide, iron oxide, manganese oxide, tin oxide, stannous oxide, silicon oxide, iron sulfide, and ferrous sulfide.
According to the composite film material provided by the invention, the electronic conductor material is one or more selected from carbon black, Ketjen carbon (KB), acetylene black, Super P, graphene, single-wall or multi-wall carbon nanotubes, copper powder, aluminum powder, ruthenium dioxide and molybdenum dioxide.
According to the composite film material provided by the present invention, the conductor particle layer contains particles of an ionic conductor material and particles of an electronic conductor material.
In some embodiments, the ionic conductor material may comprise 50 to 99.5 wt%, preferably 50 to 99 wt%, of the total amount of the ionic conductor material and the electronic conductor material. Likewise, in some embodiments, the electron conductor material may comprise from 0.5 to 50 wt%, preferably from 1 to 50 wt%, of the total amount of the ionic conductor material and the electron conductor material.
In the present invention, there is no particular requirement for the average particle diameter of the particles of the ionic conductor material, the particles of the ionic-electronic mixed conductor material, and/or the particles of the electronic conductor material. However, in some embodiments, the particles of the ionic conductor material, the particles of the ionic-electronic mixed conductor material and/or the particles of the electronic conductor material preferably have an average particle size of 10 to 1000nm, more preferably 10 to 500 nm.
For example, in some embodiments, the particles of the electron conductor material have an average particle size or diameter of 10 to 1000 nm; and in some embodiments, the electronic conductor material may be in the form of particles, fibers, tubes, or sheets.
According to the composite film material provided by the invention, the thickness of the conductor particle layer is 0.2-10 μm, and preferably 0.1-2 μm.
The composite membrane material provided by the invention has the total thickness of 1-100 μm, preferably 5-20 μm.
The composite film material according to the present invention, wherein the polymer film is a porous single layer film or a multi-layer film, and the material of each of the single layer film or the multi-layer film may be, independently of each other, Polyethylene (PE), polypropylene (PP), polyvinylidene fluoride (PVDF), polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP), Polyimide (PI), Polycarbonate (PC), polyethylene terephthalate, polybutylene terephthalate, polyether acetone, polyisophthaloyl isophthalamide, or cellulose (cellulose).
According to the composite film material provided by the invention, the total thickness of the single-layer film or the multilayer film is 0.1-50 μm, and the porosity is 5-80%. In some embodiments, the thickness of each layer of the multilayer film is independently from 0.1 to 30 μm.
In some embodiments, the polymer film is a non-porous polymer electrolyte film comprising a polymer substrate and a conductive lithium salt. The term "pore-free" as used herein generally refers to materials having a porosity of less than 1%.
In some embodiments, the polymeric substrate is one or more selected from the group consisting of polyethylene oxide (PEO), polypropylene oxide (PPO), Polycarbonate (PC), polyvinylidene fluoride (PVDF), polymethyl methacrylate (PMMA), polyacrylonitrile, perfluorosulfonic acid membrane (Nafion), and sulfonated polyether ether ketone (SPEEK).
In some embodiments, the electrically conductive lithium salt is one or more selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonimide), lithium bis fluorosulfonimide and lithium bis (oxalato) borate.
In some embodiments, the conductive lithium salt comprises 1 to 10 wt% of the polymer electrolyte membrane.
According to the composite membrane material provided by the invention, the other side surface of the polymer membrane is coated with the positive electrode side coating, and the positive electrode side coating is selected from one or more of the following materials:
(1) particles of a second ion conductor material, which may be the same as or different from the particles of the ion conductor material in the conductor particle layer, and which are selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-2n-jAnLa3Zr2-jBjO12And Li7-2n-2jAnLa3Zr2-jCjO12Wherein r is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2/3, z is more than or equal to 0 and less than or equal to 2, m is more than or equal to 0 and less than or equal to 2, n is more than or equal to 0 and less than or equal to 3, j is more than or equal to 0 and less than or equal to 2, A is Ge and/or Al, B is Nb and/.
In some embodiments, the particles of the second ionic conductor material have an average particle size of 10 to 500 nm.
In some embodiments, the second ion conductor material is applied at a thickness of 0.2 to 10 μm, preferably 0.5 to 2 μm.
(2) One or more particles selected from the group consisting of alumina, magnesia, zinc oxide, titanium oxide, lithium titanate, lithium phosphate, lithium fluoride and lithium iron phosphate, having an average particle diameter of 10 to 500nm, and being coated with a thickness of 0.2 to 10 μm, preferably 0.5 to 2 μm, on the positive electrode side.
(3) The polymer modification layer is selected from a polyvinylidene fluoride-hexafluoropropylene modification layer, a polyvinylidene fluoride modification layer, a polycarbonate modification layer, a polyethylene oxide modification layer, a polypropylene oxide modification layer or a polydimethylsiloxane modification layer, and the thickness of the polymer modification layer is 0.2-10 mu m, preferably 0.2-2 mu m.
According to the composite film material provided by the present invention, the layer of conductor particles and/or the positive electrode-side coating each independently contains a binder.
In some embodiments, the binder is one or more selected from the group consisting of carboxymethylcellulose, polyvinylidene fluoride, polymethyl methacrylate, pectin, polyamide, polyimide, lithium Polyacrylate (PAALI).
In some embodiments, the binders each independently comprise 0.5 to 20 wt%, preferably 0.5 to 5 wt% of the layer of conductor particles and/or the positive side coating.
In a second aspect, the invention provides a preparation method of the composite membrane material, wherein the method comprises the following steps:
(1) mixing one or more of particles of an ionic conductor material, particles of an ionic-electronic mixed conductor material, and particles of an electronic conductor material with a solvent and optionally a binder to form a slurry;
preferably, the solvent is one or more selected from N-methylpyrrolidone, acetonitrile, acetone, N-dimethylformamide, water, ethanol, and the like;
preferably, the solvent is used in an amount of 80 to 98 wt%.
(2) Coating the slurry prepared in step (1) on one surface of a polymer film, and removing the solvent to form a conductive particle layer.
According to the present invention, there is provided a method, wherein the method further comprises the following step (3): and coating the other side surface of the polymer film with a positive electrode side coating.
In the present invention, the positive electrode side coating material may be coated by preparing a slurry. In preparing the positive electrode-side coating material, a binder may be used as such, and may be the same as or different from the binder used in step (1), and is not particularly limited herein.
According to the present invention, there is provided a method wherein the binder is one or more selected from the group consisting of carboxymethyl cellulose, polyvinylidene fluoride, polymethyl methacrylate, pectin, polyamide, polyimide and lithium Polyacrylate (PAALI).
According to the present invention, there is provided a method wherein the binder is each independently 0.5 to 20 wt%, preferably 0.5 to 5 wt% of the layer of conductor particles and/or the positive electrode-side coating.
Additionally, the preparation of the slurry is known to those skilled in the art and can be carried out by any known technique. For example, the slurry may be formed by physical mixing.
In a third aspect, the invention provides the use of the composite film material in a rechargeable lithium metal battery.
According to some embodiments of the present invention, there is provided a rechargeable lithium metal battery, wherein the rechargeable lithium metal battery includes a negative electrode, the composite film material, a positive electrode, and a liquid electrolyte, wherein the conductor particle layer faces the negative electrode.
In some embodiments, the positive electrode comprises one or more lithium-containing positive electrode materials of lithium iron phosphate, lithium manganese iron phosphate, lithium cobaltate, lithium nickelate, lithium manganate, lithium nickel cobalt aluminate, lithium-rich layered oxide, or lithium nickel manganate; and in other embodiments, the positive electrode comprises one or more of manganese oxide, vanadium oxide, chromium oxide, iron oxide, manganese fluoride, iron phosphate, manganese phosphate, graphite fluoride, graphite oxide, iron sulfate, nickel manganese oxide, iron cobalt manganese complex oxide, iron sulfide, manganese sulfide, cobalt sulfide, nickel sulfide, titanium sulfide, sulfur carbon, lithium sulfide, and vanadium oxide compounds.
In some embodiments, the positive electrode may further include a binder, a conductive additive, a solid electrolyte, or the like.
In some embodiments, the negative electrode includes an active thin film formed of metallic lithium, a lithium alloy, or a composite containing metallic lithium.
In some embodiments, the lithium alloy comprises a lithium alloy comprising aluminum, magnesium, boron, silicon, tin.
In some embodiments, examples of the metal lithium-containing composites include physical mixtures of metal lithium with carbon, silicon, aluminum, copper, tin, and copper nitride, lithium copper nitrogen, lithium iron nitrogen, lithium manganese nitrogen, lithium cobalt nitrogen, and Li7MP3(wherein M ═ Ti, V, or Mn).
In some embodiments, the lithium metal negative electrode film has a thickness of 2 to 100 μm. The lithium metal negative electrode film can be directly used or pressed on a conductive foil, a mesh or a porous film, and the material of the conductive foil, the mesh or the porous film comprises carbon, copper, titanium, stainless steel, nickel and the like.
In some embodiments, the rechargeable lithium metal battery further comprises a liquid electrolyte that can be converted, in whole or in part, to a solid electrolyte during charging and discharging of the lithium battery, wherein the liquid electrolyte comprises a lithium salt, an organic solvent, and a film-forming additive.
In some embodiments, the lithium salt is one or more selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonimide), lithium bis-fluorosulfonimide, lithium bis-oxalato-borate, and lithium perchlorate.
In some embodiments, the concentration of the lithium salt in the liquid electrolyte is from 0.1 to 1 mol/L.
In some embodiments, the organic solvent is one or more selected from the group consisting of Ethyl Methyl Carbonate (EMC), gamma-valerolactone (gamma-VL), gamma-butyrolactone (gamma-BL), dimethyl carbonate (DMC), Propylene Carbonate (PC), diethyl carbonate (DEC), Ethylene Carbonate (EC), ethylene glycol dimethyl ether (DME), (di, tri, tetra) ethylene glycol dimethyl ether, 1, 3-Dioxolane (DOL), Tetrahydrofuran (THF), dimethyl sulfoxide (DMSO), and Acetonitrile (AN).
In some embodiments, the film-forming additive is one or more selected from the group consisting of Ethylene Sulfite (ES), Propylene Sulfite (PS), Vinylene Carbonate (VC), dimethyl sulfite (DMS), diethyl sulfite (DES), 1, 2-trifluoroacetoxyethane (BTE), ethylene vinylene carbonate (VEC), fluoroethylene carbonate (FEC), Cyclohexylbenzene (CHB), Succinonitrile (SN), Adiponitrile (AND), 1, 3-propanesultone (1,3-PS), fluoromethyl carbonate (FMC), diphenyl disulfide, biphenyl, anthracene, AND phenanthrene.
In some embodiments, the liquid electrolyte may also include interfacial wetting agents such as fluoroethers, flame retardant additives such as phosphate esters, and ionic liquids, among others.
According to an embodiment of the present invention, there is provided a liquid metal lithium battery manufactured by charging and discharging the rechargeable metal lithium battery.
According to an embodiment of the present invention, there is provided a solid state lithium metal battery manufactured by charging and discharging the rechargeable lithium metal battery.
The liquid metal lithium battery and the solid metal lithium battery contain the above solid electrolyte membrane.
In some embodiments, the liquid metal lithium battery or the solid metal lithium battery may be prepared by a method comprising:
(1) assembling a lithium metal battery, wherein the composite film material serves as a separator of the lithium battery, and the conductor particle layer faces a negative electrode; and
(2) and charging and discharging the assembled metal lithium battery to form the lithium ion battery.
In some embodiments, the charging and discharging may be performed under heating and vacuum conditions in a stepwise constant current or constant voltage manner.
Without wishing to be bound by theory, it is believed that, after the battery is assembled, the charging and discharging formation is performed under heating and vacuum conditions in a stepwise constant current or constant voltage manner, which is advantageous for reducing the liquid electrolyte added in the rechargeable metal lithium battery when the potential of the surface of the particles in the conductor particle layer on the interface side of the metal lithium electrode and the composite film material and on the side of the composite film material facing the metal lithium electrode is lower than the electrochemical window of the electrolyte, and a Solid Electrolyte (SEI) layer is generated in situ in the gaps of the particles of the ionic conductor material, the particles of the ionic-electronic mixed conductor material, or the particles of the electronic conductor material in the conductor particle layer, and the SEI can fill the gaps in the composite film material to convert the porous separator into a dense solid electrolyte film. The formed compact layer can prevent the liquid electrolyte from contacting with the metallic lithium, can inhibit dendritic crystal growth, and can regulate and control the distribution of lithium ions so as to ensure that the lithium deposition is more uniform, the conductor particle layer and the SEI composite diaphragm also have higher conductivity, and the polarization of the battery is lower.
In some embodiments, the porosity of the formed film is less than 10%, and may even be less than 4%.
In some embodiments, during the charging and discharging formation process, the current density of the constant current operation is 0.01-10C, the constant voltage operation can be divided into 1-3 voltage sections, the temperature can be 20-150 ℃, and the vacuum degree can be controlled at normal pressure-1 Pa.
After the battery is assembled, the charging and discharging formation can be carried out in a segmented constant-current or constant-voltage mode under the heating and vacuum conditions, after the liquid electrolyte is converted into the solid electrolyte, the liquid electrolyte such as carbonates and ethers can be further added, and the secondary charging and discharging formation can be further carried out.
Compared with the prior art, the invention has at least the following advantages:
(1) the composite membrane material for the lithium battery can be formed into an in-situ generated solid electrolyte membrane through charging and discharging, is simple to operate, can be compatible with the existing battery manufacturing process, and further reduces the production cost of the solid metal lithium battery;
(2) the composite membrane material for the lithium battery can effectively inhibit the growth of lithium dendrite and the piercing of the lithium dendrite on a diaphragm, reduces further chemical reaction between metal lithium and electrolyte, can effectively protect a metal lithium electrode, reduces the pulverization of lithium and improves the safety of the lithium battery.
Drawings
Embodiments of the invention are described in detail below with reference to the attached drawing figures, wherein:
FIG. 1 is a Scanning Electron Microscope (SEM) picture of the surface of the composite film material of example 1 of the present application before charge-discharge cycling;
FIG. 2 is a Scanning Electron Microscope (SEM) picture of a cross section of a composite film material of example 1 of the present application before charge-discharge cycling;
FIG. 3 is a Scanning Electron Microscope (SEM) picture of a solid electrolyte membrane generated after 100 weeks of cycling in a lithium ion battery containing the composite membrane material of example 1 of the present application;
FIG. 4 is a Scanning Electron Microscope (SEM) picture of the cross section of a solid electrolyte membrane generated after 100 weeks of cycling in a lithium ion battery containing the composite membrane material of example 1 of the present application;
FIG. 5 is a graph showing the charge and discharge curves of a lithium metal battery containing the composite film material of example 1 of the present application for 50, 100, 150 and 200 weeks;
fig. 6 is a Scanning Electron Microscope (SEM) picture of the surface of a base film coated with non-ionic conductive particles facing the negative electrode side after a lithium metal battery containing the composite film material of comparative example 1 is cycled for 100 weeks;
fig. 7 is a Scanning Electron Microscope (SEM) picture of a cross section of a base film coated with non-ionic conductive particles on the side facing the negative electrode after a lithium metal battery containing the composite film material of comparative example 1 is cycled for 100 weeks.
Detailed Description
The present invention is described in further detail below with reference to specific embodiments, which are given for the purpose of illustration only and are not intended to limit the scope of the invention.
In the following examples, the materials used are as follows:
TABLE 1 Polymer Membrane materials
| Polymer film numbering | Composition of |
| |
Polypropylene (PP) |
| Polymer film 2 | Polyethylene (PE) |
| Polymer film 3 | Polyvinylidene fluoride (PVDF) |
| Polymer film 4 | Polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP) |
| Polymer film 5 | Polyimide, polyimide resin composition and polyimide resin composition |
| Polymer film 6 | Polyether imide |
| Polymer film 7 | Polycarbonate resin |
| Polymer film 8 | Poly-aramid fiber |
| Polymer film 9 | Cellulose, process for producing the same, and process for producing the same |
| Polymer film 10 | Polyethylene oxide (PEO) |
| Polymer film 11 | Polybutylene terephthalate |
| Polymer film 12 | Polyether acetone |
| Polymer film 13 | Polyacrylonitrile |
| Polymer film 14 | Perfluorosulfonic acid membrane (Nafion) |
| Polymer film 15 | Sulfonated polyether ether ketone (SPEEK) |
Surface 2 particles used in layer of conductor particles facing the negative side
TABLE 3 Positive electrode side coating
| Positive electrode side coating 11 | Li1.4Al0.4Ti1.6(PO4)3 |
| Positive electrode side coating 12 | Li6.75La3Zr1.75Ta0.5O12 |
TABLE 4 conductive lithium salts in Polymer films
| Conductive lithium salt numbering | Composition of |
| |
Lithium hexafluorophosphate (LiPF)6) |
| Lithium salt 2 | Lithium bis (trifluoromethylsulfonimide) (LiN (CF)3SO2)2) |
| Lithium salt 3 | Lithium tetrafluoroborate (LiBF)4) |
| Lithium salt 4 | Lithium perchlorate (LiClO)4) |
| Lithium salt 5 | Lithium triflate LiCF3SO3) |
| Lithium salt 6 | Li(CF3SO2)3) |
| Lithium salt 7 | Lithium hexafluoroarsenate (LiAsF)6) |
| Lithium salt 8 | Lithium bis (oxalato) borate (LiBOB) |
TABLE 5.1 organic solvents in liquid electrolytes
| Numbering of organic solvents | Composition of |
| |
Methyl ethyl carbonate (EMC) |
| Solvent 2 | Dimethyl carbonate (DMC) |
| Solvent 3 | Dimethyl carbonate (DMC) |
| Solvent 4 | Carbonic acid (di) ethyl ester (DEC) |
| Solvent 5 | Carbonic acidVinyl Ester (EC) |
| Solvent 6 | Ethylene glycol dimethyl ether (DME):1, 3-Dioxolane (DOL) ═ 1:1 (volume ratio) |
| Solvent 7 | Propylene Carbonate (PC) |
| Solvent 8 | Tetrahydrofuran (THF) |
| Solvent 9 | Dimethyl carbonate (DMC): ethylene Carbonate (EC) 1:1 (volume ratio) |
| Solvent 10 | Dimethyl carbonate (DEC): ethylene Carbonate (EC) 1:1 (volume ratio) |
TABLE 5.2 film-Forming additives in liquid electrolytes
| Numbering of film-forming additives | Composition of |
| |
Ethylene Sulfite (ES) |
| Additive 2 | Vinylene Carbonate (VC) |
TABLE 6 Positive electrode Material
| Numbering of positive electrode materials | Composition of |
| |
Lithium cobaltate |
| Cathode material 2 | Lithium iron phosphate |
| Cathode material 3 | Lithium manganate |
| Cathode material 4 | Lithium nickel cobalt manganese oxide |
| Cathode material 5 | Lithium nickel cobalt aluminate |
| Positive electrode material 6 | Lithium-rich layered oxides |
| Positive electrode material 7 | Lithium nickel manganese oxide |
| Positive electrode material 8 | MnO2 |
| Cathode material 9 | FeS2 |
| Positive electrode material 10 | FeF3 |
| Cathode material 11 | S |
| Positive electrode material 12 | Iron phosphate |
| Positive electrode material 13 | O2 |
| Cathode material 14 | Iron silicate |
Preparing a composite membrane material:
(1) mixing one or more of particles of an ion-electron mixed conductor material, particles of an electron conductor material, particles of an ion conductor material with a binder and a solvent to form a slurry;
the solvent is selected from N-methyl pyrrolidone, acetonitrile, acetone, N-dimethylformamide, water and ethanol, the mass fraction of the solvent in the slurry is 80% -98%, and binders, solvents and the use amount of the solvents are shown in table 7.
(2) Coating the slurry prepared in step (1) on one side surface of a polymer film, and drying to remove the solvent, thereby forming a conductor particle layer; and
(3) the other surface of the polymer film was coated with a slurry of a positive electrode side coating material, and the solvent was dried to remove the solvent, wherein the binder, the solvent and the amount thereof used for each positive electrode side coating material pair are shown in table 8.
TABLE 7
TABLE 8
In the following examples, the base film (composite film material) used was composed of a polymer film, particles coated on the layer of conductor particles on the side of the polymer film facing the negative electrode, ion conductor particles or non-ion conductive particles coated on the side of the polymer film facing the positive electrode. The kind, thickness, porosity, particle kind of the conductive particle layer coated facing the negative electrode side, particle size, coating thickness, coating kind facing the positive electrode side, particle size, coating thickness, and total porosity of the base film of the polymer film are shown in table 9.
TABLE 9
Example 1
Example 1 provides a rechargeable lithium metal battery and a solid-state lithium metal battery prepared therefrom. In particular, the amount of the solvent to be used,
(1) assembling a rechargeable lithium metal battery, wherein the composite film material serves as a separator of the lithium battery, and the conductor particle layer faces the negative electrode; and
(2) and charging and discharging the assembled metal lithium battery to form the lithium ion battery.
The assembly of the simulated battery isIn a glove box containing argon, the composite membrane material is numbered as a basic membrane 1 in Table 9, the positive electrode is a lithium cobaltate electrode, the counter electrode is metal lithium, and the lithium salt is LiPF6The lithium salt concentration is 1mol/L, and the organic solvent is EC: DMC 1:1 (i.e., solvent 9).
A constant-current charge-discharge mode test was carried out using a charge-discharge instrument with a charge cut-off voltage of 4.2V and a discharge cut-off voltage of 3.0V at a current density of 10C and a test temperature of 25 ℃. After 100 weeks, the cell was disassembled in an argon glove box, and the surface morphology of the generated solid electrolyte membrane and the metal lithium electrode was observed.
Fig. 1 shows a Scanning Electron Microscope (SEM) picture of the surface of the composite film material of example 1 before charge-discharge cycling. Fig. 3 shows a Scanning Electron Microscope (SEM) image of a solid electrolyte membrane produced after 100 weeks of cycling in a lithium ion battery containing the composite membrane material of example 1. As can be seen from fig. 1 and 3, the solid electrolyte membrane is grown in situ on the particles of the conductive particle layer and covers the conductive particle layer on the surface of the base film.
Fig. 2 shows a Scanning Electron Microscope (SEM) picture of a cross section of the composite film material of example 1 before charge-discharge cycling. Fig. 4 shows a Scanning Electron Microscope (SEM) image of a cross section of a solid electrolyte membrane produced after 100 weeks of cycling in a lithium ion battery containing the composite membrane material of example 1. As can be seen from the cross-sectional Scanning Electron Micrographs (SEM) of fig. 2 and 4, the solid electrolyte membrane grows in situ in the gaps between the particles of the conductive particle layer.
The above results indicate that, in the process of charging and discharging of the lithium battery, on the negative electrode side of the metal lithium battery, the liquid electrolyte is gradually converted into a solid electrolyte material having ion conductivity on the base film through an electrochemical reaction, thereby producing a solid electrolyte film.
Fig. 5 shows the charge and discharge curves of the solid-state lithium metal battery containing the composite film material of example 1 for 50, 100, 150 and 200 weeks. As can be seen from fig. 5, the battery has high coulombic efficiency and excellent cycle performance.
Examples 2 to 31
Examples 2-31 of the present application provide rechargeable lithium metal batteries and solid-state lithium metal batteries prepared therefrom. In particular, the amount of the solvent to be used,
(1) assembling a rechargeable lithium metal battery, wherein the composite film material serves as a separator of the lithium battery, and the conductor particle layer faces the negative electrode; and
(2) and charging and discharging the assembled metal lithium battery to form the lithium ion battery.
The assembly of the simulated cell was carried out in a glove box containing argon, the number of the composite membrane materials was 2-31 corresponding to the base membrane in table 9, the counter electrode was metallic lithium, and the lithium salt, solvent, additive and positive electrode material used were as shown in table 10, wherein the lithium salt concentration was 1mol/L and the additive concentration was 2 wt%. Also, table 10 shows the operating temperature and charge-discharge voltage ranges of the battery.
Watch 10
SEM images of the surfaces and cross sections of the composite membrane materials numbered as the base membranes 2 to 31 before the charge and discharge cycles and after the 100-week cycle were observed by SEM, which showed that the solid electrolyte membranes were grown in situ on the surfaces of the base membranes 2 to 31, the solid electrolyte membranes were grown in situ on and covering the particles of the conductive particle layer, and the solid electrolyte membranes were grown in situ in the gaps between the particles of the conductive particle layer.
Examples 32 to 46
Embodiments 32 to 46 of the present invention provide rechargeable lithium metal batteries and solid-state lithium metal batteries prepared therefrom. In particular, the amount of the solvent to be used,
(1) assembling a rechargeable lithium metal battery, wherein the composite film material serves as a separator of the lithium battery, and the conductor particle layer faces the negative electrode; and
(2) and charging and discharging the assembled metal lithium battery to form the lithium ion battery.
The assembly of the simulated cells was carried out in a glove box containing argon, the composite membrane materials were numbered 32-46 for the base membranes in Table 9, the counter electrode was lithium metal, and the lithium salt was LiPF6The lithium salt concentration is 1mol/L, and the organic solvent is EC: DMC 1:1 (i.e., solvent 9).
A constant-current charge-discharge mode test was carried out using a charge-discharge instrument with a charge cut-off voltage of 4.2V and a discharge cut-off voltage of 3.0V at a current density of 10C and a test temperature of 25 ℃.
SEM images of the surface and cross section of the composite film material before the charge-discharge cycle and after 100 cycles of the cycle were observed by SEM, which showed that the solid electrolyte film was generated in situ on the surface of the base film, the solid electrolyte film was grown in situ on and covering the particles of the conductor particle layer, and the solid electrolyte film was grown in situ in the gaps between the particles of the conductor particle layer.
The above results indicate that, in the process of charging and discharging of the lithium battery, on the negative electrode side of the metal lithium battery, the liquid electrolyte is gradually converted into a solid electrolyte material having ionic and/or electronic conductivity on the base film through electrochemical reaction, thereby producing the solid electrolyte film.
Comparative example 1
Comparative example 1 is intended to illustrate that when the base film is coated with a non-ionic conductive particle coating layer on the surface facing the negative electrode side, the solid electrolyte cannot be generated in situ.
Wherein, comparative example 1 polymer film is polypropylene (PP) film, PP film's thickness is 20um, and the porosity is 10% -20%, is at the base film one side coating non-ionic conduction particle (aluminium oxide, particle size is 10um) facing the negative pole, and its thickness is 5 um.
A simulated battery is assembled in a glove box containing argon, wherein the positive electrode is a lithium cobaltate electrode, the counter electrode is metal lithium, and the electrolyte contains 1mol/L LiPF62 wt% additive 2 and solvent 9.
A constant-current charge-discharge mode test was carried out using a charge-discharge instrument with a charge cut-off voltage of 4.2V and a discharge cut-off voltage of 3.0V at a current density of 10C and a test temperature of 60 ℃. After the circulation for 100 weeks, the battery is disassembled in an argon glove box, and the surface appearance of the composite membrane material and the metal lithium electrode is observed.
Fig. 6 shows a Scanning Electron Microscope (SEM) picture of the surface of the base film coated with the non-ionic conductive particles facing the negative electrode side after the lithium metal battery containing the composite film material of comparative example 1 was cycled for 100 weeks. As shown in fig. 6, the solid electrolyte membrane is not generated in situ on the base membrane side next to the negative electrode.
Fig. 7 shows a Scanning Electron Microscope (SEM) picture of a cross section of a base film coated with non-ionic conductive particles on the side facing the negative electrode after a lithium metal battery comprising the composite film material of comparative example 1 was cycled for 100 weeks. As shown in fig. 7, no solid electrolyte membrane was produced between the alumina particles of the non-ionic conductive material.
The above-mentioned embodiments are intended to illustrate the objects, technical solutions and advantages of the present invention in further detail, and 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 (41)
1. A rechargeable lithium metal battery, wherein the rechargeable lithium metal battery comprises a negative electrode, a composite film material and a positive electrode, wherein the composite film material comprises a polymer film and a conductor particle layer coated on one surface of the polymer film, wherein the conductor particle layer contains particles of an ion conductor material and particles of an electron conductor material, and wherein the ion conductor material accounts for 50-99.5 wt% of the total amount of the ion conductor material and the electron conductor material, and wherein the conductor particle layer faces the negative electrode,
wherein the ion conductor material is selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-nLa3Zr2-nTanO12、Li7-nLa3Zr2- nNbnO12、Li7-2nLa3Zr2-nWnO12、Li7-2nLa3Zr2-nTenO12、Li7-3nGenLa3Zr2O12And Li7-3nAlnLa3Zr2O12Wherein r is 0. ltoreq. r.ltoreq.1, x is 0. ltoreq. x.ltoreq.2, y is 0. ltoreq. y.ltoreq. 2/3, z is 0. ltoreq. z.ltoreq.2, m is 0. ltoreq. m.ltoreq.2, n is 0. ltoreq. n.ltoreq.0.6, and
the electronic conductor material is one or more selected from carbon black, graphene, single-wall or multi-wall carbon nano tubes, copper powder, aluminum powder, ruthenium dioxide and molybdenum dioxide.
2. The rechargeable lithium metal battery of claim 1, wherein the ionic conductor material is selected from Li1.5Al0.5Ge1.5(PO4)3、Li7P3S11、Li3PS4、Li0.5La0.5TiO3、LiZr0.5Ti1.5(PO4)3、Li1.4Al0.4Ti1.6(PO4)3And Li3.5Ge0.5P0.5S4One or more of (a).
3. The rechargeable lithium metal battery of claim 1, wherein the carbon black is ketjen carbon, acetylene black, or Super P.
4. The rechargeable metallic lithium battery of any of claims 1-3, wherein the ionic conductor material comprises 50-99 wt% of the total of the ionic conductor material and the electronic conductor material.
5. The rechargeable metallic lithium battery of any of claims 1-3, wherein the electronic conductor material comprises 0.5-50 wt% of the total of the ionic conductor material and the electronic conductor material.
6. The rechargeable metallic lithium battery of any of claims 1-3, wherein the electronic conductor material comprises 1-50 wt% of the total of the ionic conductor material and the electronic conductor material.
7. The rechargeable metallic lithium battery of any of claims 1-3, wherein the particles of the ionic conductor material and/or the particles of the electronic conductor material have an average particle size of 10-1000 nm.
8. The rechargeable metallic lithium battery of any of claims 1-3, wherein the particles of the ionic conductor material and/or the particles of the electronic conductor material have an average particle size of 10-500 nm.
9. The rechargeable lithium metal battery of any of claims 1-3, wherein the thickness of the layer of conductor particles is 0.2-10 μm.
10. The rechargeable metallic lithium battery of any of claims 1-3, wherein the thickness of the layer of conductor particles is 0.1-2 μm.
11. The rechargeable lithium metal battery of any of claims 1-3, wherein the total thickness of the composite film material is 1-100 μm.
12. The rechargeable lithium metal battery of any of claims 1-3, wherein the total thickness of the composite film material is 5-20 μm.
13. The rechargeable lithium metal battery of any one of claims 1-3, wherein the polymer film is a perforated single or multilayer film, and each film of the single or multilayer film independently comprises polyethylene, polypropylene, polyvinylidene fluoride-hexafluoropropylene, polyimide, polycarbonate, polyethylene terephthalate, polybutylene terephthalate, polyether acetone, polyisophthaloyl metaphenylene diamine, or cellulose; or
The polymer membrane is a non-porous polymer electrolyte membrane comprising a polymer substrate and a conductive lithium salt, wherein the polymer substrate is one or more selected from the group consisting of polyethylene oxide, polypropylene oxide, polycarbonate, polyvinylidene fluoride, polymethyl methacrylate, polyacrylonitrile, perfluorosulfonic acid membrane, and sulfonated polyether ether ketone; and wherein the electrically conductive lithium salt is one or more selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonylidine), lithium bis (fluorosulfonylimide) and lithium bis (oxalato) borate.
14. The rechargeable lithium metal battery of claim 13, wherein the single or multilayer film has a total thickness of 0.1 to 50 μ ι η and a porosity of 5 to 80%.
15. The rechargeable lithium metal battery of claim 13, wherein each layer of the multilayer film independently has a thickness of 0.1 to 30 μ ι η.
16. The rechargeable lithium metal battery of claim 13, wherein the conductive lithium salt comprises 1-10 wt% of the polymer electrolyte membrane.
17. The rechargeable lithium metal battery of any one of claims 1-3, wherein the other side surface of the polymer film is coated with a positive side coating selected from one or more of the following materials:
(1) particles of a second ion conductor material selected from Li4-rGe1-rPrS4、Li7P3S11、Li3PS4、Li1+xAlxGe2-x(PO4)3、Li3yLa2/3-yTiO3、LiZr2-zTiz(PO4)3、Li1+mAlmTi2-m(PO4)3、Li7-2n-jAnLa3Zr2-jBjO12And Li7-2n- 2jAnLa3Zr2-jCjO12Wherein r is more than or equal to 0 and less than or equal to 1, x is more than or equal to 0 and less than or equal to 2, y is more than or equal to 0 and less than or equal to 2/3, z is more than or equal to 0 and less than or equal to 2, m is more than or equal to 0 and less than or equal to 2, n is more than or equal to 0 and less than or equal to 3, j is more than or equal to 0 and less than or equal to 2, A is Ge and/or Al, B is Nb and/;
(2) one or more particles selected from the group consisting of aluminum oxide, magnesium oxide, zinc oxide, titanium oxide, lithium titanate, lithium phosphate, lithium fluoride and lithium iron phosphate, having an average particle diameter of 10 to 500nm, and a coated positive-electrode-side coating having a thickness of 0.2 to 10 μm; and
(3) the polymer modification layer is selected from a polyvinylidene fluoride-hexafluoropropylene modification layer, a polyvinylidene fluoride modification layer, a polycarbonate modification layer, a polyethylene oxide modification layer, a polypropylene oxide modification layer or a polydimethylsiloxane modification layer, and the thickness of the polymer modification layer is 0.2-10 mu m.
18. The rechargeable lithium metal battery of claim 17, wherein the particles of the second ionic conductor material have an average particle size of 10-500 nm.
19. The rechargeable lithium metal battery of claim 17, wherein the second ionic conductor material is coated to a thickness of 0.2-10 μ ι η.
20. The rechargeable lithium metal battery of claim 17, wherein the second ionic conductor material is coated to a thickness of 0.5-2 μ ι η.
21. The rechargeable lithium metal battery of claim 17, wherein the positive electrode-side coating has a thickness of 0.5-2 μm.
22. The rechargeable metallic lithium battery of claim 17, wherein the polymer modification layer has a thickness of 0.2-2 μ ι η.
23. The rechargeable lithium metal battery of claim 17, wherein the layer of conductor particles and/or the positive side coating each independently comprise a binder.
24. The rechargeable lithium metal battery of claim 23, wherein the binder is one or more selected from the group consisting of carboxymethyl cellulose, polyvinylidene fluoride, polymethyl methacrylate, pectin, polyamide, polyimide, and lithium polyacrylate.
25. The rechargeable lithium metal battery of claim 23, wherein the binders each independently comprise 0.5-20 wt% of the conductor particle layer and/or the positive side coating.
26. The rechargeable lithium metal battery of claim 23, wherein the binders each independently comprise 0.5-5 wt% of the conductor particle layer and/or the positive side coating.
27. The rechargeable lithium metal battery of claim 1, further comprising a liquid electrolyte that is converted in whole or in part to a solid electrolyte during charging and discharging of the lithium battery, wherein the liquid electrolyte comprises a lithium salt, an organic solvent, and a film-forming additive.
28. The rechargeable lithium metal battery of claim 27, wherein the lithium salt is one or more selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium hexafluoroarsenate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethylsulfonimide), lithium bis-fluorosulfonimide, lithium bis-oxalato-borate, and lithium perchlorate.
29. The rechargeable lithium metal battery of claim 27, wherein the concentration of lithium salt in the liquid electrolyte is 0.1-1 mol/L.
30. The rechargeable lithium metal battery of claim 27, wherein the organic solvent is one or more selected from the group consisting of ethyl methyl carbonate, gamma-valerolactone, gamma-butyrolactone, dimethyl carbonate, propylene carbonate, diethyl carbonate, ethylene glycol dimethyl ether, (di, tri, tetra) ethylene glycol dimethyl ether, 1, 3-dioxolane, tetrahydrofuran, dimethyl sulfoxide, and acetonitrile.
31. The rechargeable lithium metal battery of claim 27, wherein the film-forming additive is one or more selected from the group consisting of ethylene sulfite, propylene sulfite, vinylene carbonate, dimethyl sulfite, diethyl sulfite, 1, 2-trifluoroacetoethane, ethylene vinylene carbonate, fluoroethylene carbonate, cyclohexylbenzene, succinonitrile, adiponitrile, 1, 3-propane sultone, fluoromethyl carbonate, diphenyl disulfide, biphenyl, anthracene, and phenanthrene.
32. A method of making a rechargeable lithium metal battery according to any of claims 1 to 31, wherein the method comprises the steps of:
(a) preparing the composite membrane material:
(1) mixing particles of an ionic conductor material and particles of an electronic conductor material with a solvent and optionally a binder to form a slurry, wherein the ionic conductor material comprises 50-99.5 wt% of the total amount of the ionic conductor material and the electronic conductor material; and
(2) coating the slurry prepared in the step (1) on one side surface of a polymer film, and removing the solvent to form a conductor particle layer; and
(b) the rechargeable lithium metal battery is assembled with the composite film material as a separator of the lithium battery and the conductor particle layer facing the negative electrode.
33. The method according to claim 32, wherein the solvent is one or more selected from the group consisting of N-methylpyrrolidone, acetonitrile, acetone, N-dimethylformamide, water and ethanol.
34. The method of claim 32, wherein the solvent is used in an amount of 80-98 wt%.
35. The method of claim 32, wherein the binder is one or more selected from the group consisting of carboxymethyl cellulose, polyvinylidene fluoride, polymethyl methacrylate, pectin, polyamide, polyimide, and lithium polyacrylate.
36. The method of claim 32 wherein the binder comprises 0.5-20 wt% of the layer of conductor particles.
37. The method of claim 32 wherein the binder comprises 0.5-5 wt% of the layer of conductor particles.
38. The method of any one of claims 32-37, wherein step (a) further comprises step (3) of: and coating the other side surface of the polymer film with a positive electrode side coating.
39. The method according to claim 38, wherein the positive electrode-side coating contains a binder, and the binder is used in an amount of 0.5 to 20 wt%.
40. The method of claim 39, wherein the binder is present in an amount of 0.5 to 5 wt%.
41. A liquid lithium metal battery or a solid lithium metal battery manufactured by charging and discharging the rechargeable lithium metal battery according to any one of claims 1 to 31.
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