CN111900331B - Composite negative pole piece, preparation method thereof and lithium ion battery - Google Patents
Composite negative pole piece, preparation method thereof and lithium ion battery Download PDFInfo
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- CN111900331B CN111900331B CN202010731359.1A CN202010731359A CN111900331B CN 111900331 B CN111900331 B CN 111900331B CN 202010731359 A CN202010731359 A CN 202010731359A CN 111900331 B CN111900331 B CN 111900331B
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- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 229910001416 lithium ion Inorganic materials 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 167
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 144
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 81
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- 230000008021 deposition Effects 0.000 claims abstract description 22
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- 229910002995 LiNi0.8Co0.15Al0.05O2 Inorganic materials 0.000 description 2
- 229910021543 Nickel dioxide Inorganic materials 0.000 description 2
- KLARSDUHONHPRF-UHFFFAOYSA-N [Li].[Mn] Chemical compound [Li].[Mn] KLARSDUHONHPRF-UHFFFAOYSA-N 0.000 description 2
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- QHGJSLXSVXVKHZ-UHFFFAOYSA-N dilithium;dioxido(dioxo)manganese Chemical compound [Li+].[Li+].[O-][Mn]([O-])(=O)=O QHGJSLXSVXVKHZ-UHFFFAOYSA-N 0.000 description 2
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- 229910009311 Li2S-SiS2 Inorganic materials 0.000 description 1
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- 229910009225 Li2S—P2S5—GeS2 Inorganic materials 0.000 description 1
- 229910009433 Li2S—SiS2 Inorganic materials 0.000 description 1
- 229910010850 Li6PS5X Inorganic materials 0.000 description 1
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- DETKHEZXMOBNHJ-UHFFFAOYSA-N [Co].[Ni].[Li].[Li] Chemical compound [Co].[Ni].[Li].[Li] DETKHEZXMOBNHJ-UHFFFAOYSA-N 0.000 description 1
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- NRJJZXGPUXHHTC-UHFFFAOYSA-N [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] Chemical compound [Li+].[O--].[O--].[O--].[O--].[Zr+4].[La+3] NRJJZXGPUXHHTC-UHFFFAOYSA-N 0.000 description 1
- SOXUFMZTHZXOGC-UHFFFAOYSA-N [Li].[Mn].[Co].[Ni] Chemical compound [Li].[Mn].[Co].[Ni] SOXUFMZTHZXOGC-UHFFFAOYSA-N 0.000 description 1
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- 238000010277 constant-current charging Methods 0.000 description 1
- 239000011889 copper foil Substances 0.000 description 1
- OPHUWKNKFYBPDR-UHFFFAOYSA-N copper lithium Chemical compound [Li].[Cu] OPHUWKNKFYBPDR-UHFFFAOYSA-N 0.000 description 1
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- CEMTZIYRXLSOGI-UHFFFAOYSA-N lithium lanthanum(3+) oxygen(2-) titanium(4+) Chemical compound [Li+].[O--].[O--].[O--].[O--].[Ti+4].[La+3] CEMTZIYRXLSOGI-UHFFFAOYSA-N 0.000 description 1
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- 239000011029 spinel Substances 0.000 description 1
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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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/134—Electrodes based on metals, Si or alloys
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
- H01M4/1395—Processes of manufacture of electrodes based on metals, Si or alloys
-
- 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
- H01M4/381—Alkaline or alkaline earth metals elements
- H01M4/382—Lithium
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/625—Carbon or graphite
-
- 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
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Manufacturing & Machinery (AREA)
- Secondary Cells (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention relates to a composite negative pole piece, a preparation method thereof and a lithium ion battery, wherein the negative pole piece comprises a current collector metal-metal lithium composite substrate and a carbon fiber-lithium-containing metal composite structure arranged on the current collector metal-metal lithium composite substrate; the carbon fiber-lithium-containing metal composite structure comprises a three-dimensional framework and lithium-containing metal, wherein the mass ratio of the three-dimensional framework to the lithium-containing metal is 1-18: 6; the three-dimensional skeleton comprises carbon fibers, a polymer, a surfactant and a toughening agent in a mass ratio of 60-80:10-30:1-5: 0-5. According to the composite negative pole piece, the metal lithium is filled in the three-dimensional framework, so that the composite negative pole piece with light weight and high strength is obtained, stable and uniform deposition of the metal lithium is facilitated under high current density, the complete uniformity of an SEI (solid electrolyte interphase) film is improved, the conditions of pulverization and lithium death of the lithium piece are improved, the growth of lithium dendrites can be inhibited to a certain degree, and meanwhile, the composite negative pole piece has good interface performance with an electrolyte.
Description
Technical Field
The invention belongs to the technical field of lithium ion batteries, and particularly relates to a composite negative pole piece, a preparation method thereof and a lithium ion battery.
Background
In recent years, with the rapid development of electric automobiles and high-end portable electronic devices, the requirement of people on the energy density of batteries is increasing, and at present, the lithium ion batteries using graphite as the negative electrode are difficult to meet the increasing specific energy requirement, so that the lithium metal negative electrode with high specific capacity enters the visual field of researchers. The specific capacity of lithium metal is 3860mAh/g, the electrochemical potential is-3.04V (vs standard hydrogen electrode), and the lithium metal is an ideal lithium battery negative electrode material. To use lithium metal as a negative electrode material for lithium ion batteries, we also need to overcome several difficulties: safety and cycle life. What plagues lithium metal negative electrodes is the generation of lithium dendrites. First, in the cycle process, lithium dendrites grow on the surface of lithium metal due to local polarization caused by non-uniform deposition of lithium ions on the surface of lithium metal, and when the lithium dendrites grow to a certain extent, the lithium dendrites may penetrate through a separator, causing a short circuit of a battery, thereby causing a safety problem. Second, if lithium dendrites break, a "dead lithium" is formed, resulting in a loss of battery capacity. Thirdly, on the way of industrial application, the traditional lithium metal negative electrode has poor mechanical properties and is not beneficial to the welding of a tab and the assembly of a large battery.
By encapsulating lithium metal in the pores of the porous conductive carriers, the volume change of the lithium electrode in the circulation process can be buffered, the complete uniformity of the SEI film is improved, and the carriers have large specific surface areas, so that the effective current density is greatly reduced, and the growth of dendritic crystals of the lithium-containing metal is slowed down. However, the prior art three-dimensional carrier materials tend to have a large self-weight (e.g., porous copper foil, copper foam, nickel foam, etc.), which greatly increases the weight of the electrode, thereby impairing the advantages of lithium metal as a high specific capacity electrode material. Secondly, since lithium metal is active in nature, it is very likely to undergo side reactions with an electrolyte, resulting in deterioration of integrity and compatibility of the system, thereby deteriorating the cycle of the full cell.
Therefore, it is highly desired to develop a lithium negative electrode having a strong strain resistance, suppressing the growth of lithium dendrites, and facilitating stable deposition.
Disclosure of Invention
The invention provides a composite negative pole piece, which is characterized in that the raw material composition and structure of the negative pole piece are designed, so that the negative pole and electrolyte have good interface compatibility, lithium ions are uniformly deposited, and the growth of lithium dendrites can be inhibited to a certain extent.
The invention also provides a preparation method of the composite negative pole piece, which has the advantages of simple process and convenient operation and is suitable for industrial application.
The invention also provides an all-solid-state lithium ion battery which is assembled by the composite negative pole piece, can inhibit dendritic crystals, can effectively relieve the volume strain of the battery in the circulating process, obviously prolongs the circulating life and greatly improves the circulating stability of the battery.
The technical scheme provided by the invention is as follows:
in a first aspect, the invention provides a composite negative electrode plate, which comprises a current collector metal-metal lithium composite substrate arranged on a current collector, and a carbon fiber-lithium-containing metal composite structure arranged on the current collector metal-metal lithium composite substrate;
the carbon fiber-lithium-containing metal composite structure comprises a three-dimensional framework and lithium-containing metal, wherein the mass ratio of the three-dimensional framework to the lithium-containing metal is 1-18: 6;
the three-dimensional skeleton comprises carbon fibers, a polymer, a surfactant and a toughening agent in a mass ratio of 60-80:10-30:1-5: 0-5.
According to the composite negative pole piece, the metal lithium is filled in the three-dimensional framework, so that the composite negative pole piece with light weight and high strength is obtained, stable and uniform deposition of the metal lithium is facilitated under high current density, the integrity and uniformity of an SEI (solid electrolyte interface) film are improved, the conditions of pulverization and lithium death of a lithium piece are improved, the growth of lithium dendrites can be inhibited to a certain degree, and meanwhile, the composite negative pole piece has good interface performance with an electrolyte.
The size, shape, structure, porosity and pore diameter of the three-dimensional lithium-conducting framework can be adjusted according to different models, and the three-dimensional lithium-conducting framework can be any one or combination of a regular columnar structure, a regular three-dimensional reticular structure, an irregular columnar structure or an irregular three-dimensional reticular structure. In an embodiment of the method of the present invention, the three-dimensional skeleton is obtained by 3D printing wires having a diameter of 0.1-0.8mm on the current collector metal-lithium containing metal composite substrate by a fused deposition technique.
In an embodiment of the method, the current collector metal-metal lithium composite substrate is obtained by compounding metal lithium with a current collector metal, wherein the compounding method can be one or more selected from cold pressing, hot pressing, melt blade coating, pulsed laser deposition, atomic deposition and vacuum evaporation.
The lithium-containing metal, the carbon fiber, the polymer, the surfactant and the toughening agent in the invention are all conventional substances in the field, can be self-made or commercially available, and the invention is not particularly limited to this.
In a specific embodiment of the present invention, the lithium-containing metal may be selected from at least one of metallic lithium or a lithium alloy, and the metallic lithium may be selected from one of molten metallic lithium, lithium powder, and a lithium ribbon, and the lithium alloy includes a Li-In alloy, a Li-Al alloy, a Li-Sn alloy, a Li-Mg alloy, and a Li-Ge alloy.
In a specific embodiment of the present invention, the polymer may be selected from one or more of acrylonitrile-butadiene-styrene plastic, polyethylene oxide, polylactic acid, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl chloride, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, and thermoplastic polyurethane; the toughening agent can be selected from one or a combination of more of cyclic anhydride type, epoxy type and oxazoline type; the current collector metal may be copper.
In a second aspect, the invention provides a preparation method of a composite negative electrode plate, which comprises the following steps:
pretreating carbon fibers, a polymer, a surfactant and a toughening agent in a mass ratio of 60-80:10-30:1-5:0-5 to prepare a wire. Specifically, the pretreatment step specifically comprises: mixing the carbon fiber, the polymer, the surfactant and the toughening agent in an organic solvent, stirring for homogenizing, removing the organic solvent and crushing.
The organic solvent may be selected from those conventional in the art as long as it can dissolve the polymer, and may be, for example, one or more of Acetonitrile (ACN), N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), acetone, dichloromethane, chloroform, xylene, and Tetrahydrofuran (THF). During the stirring process, the homogeneity degree of the raw material in the solvent can be controlled by controlling the stirring temperature, the rotation speed and the time, wherein the stirring temperature can be further determined according to the boiling point of the organic solvent, for example, the stirring temperature can be 25-150 ℃, the rotation speed can be 300-1000rpm, and the stirring time can be 3-24 h.
When the organic solvent is removed, the drying process can be carried out in vacuum, for example, the drying process can be carried out at 30-200 deg.C, 40-150 deg.C, or 50-130 deg.C for 6-48h, or 10-24h, and the drying temperature and time can be adjusted according to the properties of the organic solvent.
In the embodiment of the invention, in order to ensure that the three-dimensional skeleton is well formed and has no air holes and crack defects, the wire with the diameter of about 0.1-0.8mm can be obtained by controlling the parameters of the wire-making process. The diameter of the wire material is controlled by controlling the wire discharging speed and the wire manufacturing temperature. For example, the filament discharging speed can be 5-30cm/min, and the filament making temperature can be 80-235 ℃.
And compounding the metal lithium on the current collector to obtain the current collector metal-metal lithium composite substrate. Specifically, the method for compounding the lithium metal can be selected from one or more of cold pressing, hot pressing, melt blade coating, pulsed laser deposition, atomic deposition and vacuum evaporation.
And 3D printing on the current collector metal-lithium-containing metal composite substrate by a Fused Deposition Modeling (FDM) technology according to a pre-designed three-dimensional framework model to obtain the three-dimensional framework.
Filling the three-dimensional framework gap with lithium-containing metal, and preparing a carbon fiber-lithium-containing metal composite structure by pressure forming to obtain the composite negative pole piece, wherein the mass ratio of the three-dimensional framework to the lithium-containing metal is 1-18: 6.
According to the preparation method of the composite negative pole piece, the three-dimensional framework is obtained through 3D printing, and is combined with the fused deposition technology (FDM), so that the three-dimensional framework is combined with the metal lithium, the volume change of the lithium pole in the circulation process can be buffered, the increase of the thickness of the negative pole piece in the charging/discharging process is avoided, and the short circuit risk caused by the penetration of lithium dendrites can be further avoided.
In a third aspect, the invention provides a lithium ion battery, which is prepared from the composite negative electrode plate.
The lithium ion battery can be manufactured by adopting a conventional winding or laminating process, and specifically, the lithium ion battery can be obtained by sequentially winding or laminating a positive pole piece, a diaphragm and a negative pole piece together, and performing vacuum packaging and tab welding.
The separator may be any one selected from a polymer electrolyte, an oxide electrolyte, and a sulfide electrolyte, and may be a commercially available liquid electrolyte. Specifically, the polymer electrolyte may be selected from polymer all-solid-state electrolytes containing lithium salts; such as polycarbonate, polyethylene oxide, polyethylene glycol, polylactic acid, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, thermoplastic polyurethane, polymethyl methacrylate, polyvinyl acetate, and copolymerized derivatives thereof; the oxide electrolyte may be selected from one of Lithium Lanthanum Titanium Oxide (LLTO), Lithium Lanthanum Zirconium Oxide (LLZO), Lithium Aluminum Titanium Phosphorus (LATP), Lithium Aluminum Germanium Phosphorus (LAGP) and element doping systems thereof; the sulfide electrolyte may be selected from Li2S-SiS2、Li2S-P2S5、Li2S-P2S5-GeS2、Li6PS5X(X＝Cl，Br，I)。
The positive pole piece comprises a positive pole material, a conductive agent and a binder. The active substance in the positive electrode material can be selected from one or a combination of more of lithium iron phosphate chemical system materials, lithium cobaltate chemical system materials, lithium nickel cobalt manganese chemical system materials, lithium nickel cobalt aluminum chemical system materials, lithium nickel cobalt manganese aluminum chemical system materials, lithium nickel cobalt aluminum tungsten chemical system materials, lithium manganese rich chemical system materials, lithium nickel cobalt lithium chemical system materials, lithium nickel magnesium acid chemical system materials, lithium nickelate chemical system materials, spinel lithium manganese chemical system materials and nickel cobalt tungsten chemical system materials.
The conductive agent may be one or more selected from conductive carbon black (SP), ketjen black, acetylene black, Carbon Nanotubes (CNT), graphene, and flake graphite.
The binder can be one or more selected from polytetrafluoroethylene, polyvinylidene fluoride and polyvinylidene fluoride-hexafluoropropylene.
The lithium ion battery can inhibit the generation of dendrites, can effectively relieve the volume strain of the battery in the circulation process, has small resistance change after 100 cycles of circulation, obviously prolongs the circulation life, and greatly improves the circulation stability of the battery.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
Fig. 1 is a schematic structural diagram of a composite negative electrode sheet according to embodiments 1, 2, and 3 of the present invention;
fig. 2 is a schematic structural diagram of the composite negative electrode sheet of embodiments 4, 5, and 6 of the present invention;
fig. 3 is a schematic diagram of the cycling stability of the lithium symmetric battery of example 7 of the present invention at room temperature.
Detailed Description
The following detailed description of embodiments of the invention is intended to be illustrative, and not to be construed as limiting the invention.
The invention is described in detail below by means of specific examples:
the test methods for each example and comparative example are as follows:
1. AC impedance at room temperature
1) Lithium ion battery AC impedance test
The test was carried out using the Shanghai Chenghua CHI600E electrochemical workstation, with the parameters set: the amplitude is 10mV, and the frequency range is 0.1 Hz-3 MHz.
2) Lithium symmetric battery cycling test
Adopting Wuhan blue battery test equipment;
and (3) testing conditions are as follows: at 1mA/cm2The current density of the lithium symmetrical battery is subjected to constant current charging and discharging tests, and the alternating current impedance of the lithium symmetrical battery is tested when the lithium symmetrical battery is circulated for 50 circles and 400 circles respectively.
2. Cycle life test
The test instrument is Wuhan blue battery test equipment;
and (3) testing conditions are as follows: in the case where the initial capacity was substantially the same, the number of cycles at which the capacity had decayed to 80% of the initial value was measured at 25 ℃ and 0.2C/0.2C.
3. Battery short circuit rate test
During the cycle life test, the battery failed or was short-circuited, and it was marked as a short circuit, indicating that it could not be charged and discharged normally. Battery short-circuit rate ═ number of short-circuited batteries/total number of batteries measured × 100%.
Example 1
Embodiment 1 provides a composite negative electrode plate and a lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fibers, PLA, a surfactant and a toughening compatilizer according to a mass ratio of 5.3:1.8:0.2:0.1, then placing the mixture into a beaker, adding a certain amount of trichloromethane, uniformly stirring the mixture at 35 ℃ for 3 hours at a rotating speed of 500rpm to form a homogeneous solution, fully volatilizing the solvent from the stirred slurry to obtain a blocky solid, drying the blocky solid in vacuum at 50 ℃ for 12 hours, and shearing and grinding the blocky solid to obtain a granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 163 ℃, drawing the wires at the speed of 10cm/min by a tractor, and coiling the extruded wires with the diameter of 0.40 mm.
(3) Cold-pressing the metal lithium foil and a Cu current collector into a Li-Cu laminated structure substrate, performing three-dimensional modeling according to the preset design, and then printing a three-dimensional framework on the Li-Cu composite substrate by utilizing a Fused Deposition Modeling (FDM) technology.
(4) Heating metal lithium to a molten state, filling and wrapping the metal lithium in the three-dimensional framework, wherein the mass ratio of the three-dimensional framework to the filled metal lithium is 1:5, cooling and pressurizing to obtain the layered lithium composite negative pole piece with a smooth and flat surface, which is shown in the specification of 1.
2. Soft package solid lithium ion battery
Was coated with lithium cobaltate (95 wt%), acetylene black (2.5 wt%), PVDF (2.5 wt%) to an areal density of 10mg/cm2The positive pole piece is matched with a polyoxyethylene-based polymer electrolyte and a three-dimensional metal lithium composite negative pole piece, and the soft package solid lithium ion battery is manufactured by adopting the existing lamination process.
Comparative example 1
Comparative example 1 proposes a soft-packed solid-state lithium ion battery, the preparation method of which comprises the following steps:
was coated with lithium cobaltate (95 wt%), acetylene black (2.5 wt%), PVDF (2.5 wt%) to an areal density of 10mg/cm2The positive pole piece is matched with polyoxyethylene-based polymer electrolyte and a traditional metal lithium piece, and the soft-package solid lithium ion battery is manufactured by adopting the existing lamination process.
Example 2
Embodiment 2 provides a composite negative electrode plate and a soft-package polymer lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fiber, Polycaprolactone (PCL) and a surfactant according to a mass ratio of 6:1.8:0.1, placing the mixture into a beaker, adding a certain amount of ACN, uniformly stirring the mixture at 48 ℃ for 3 hours at a rotating speed of 1000rpm to form a homogeneous solution, fully volatilizing the solvent from the stirred slurry to obtain a blocky solid, drying the blocky solid in vacuum at 59 ℃ for 18 hours, and shearing and grinding the blocky solid to obtain a granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 73 ℃, drawing the wires at a speed of 22cm/min by a drawing machine, and coiling the extruded wires with the diameter of 0.80 mm.
(3) Hot-pressing the metal lithium foil and the Cu current collector into a Li-Cu layered structure substrate, performing three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on the Li-Cu composite substrate by utilizing a Fused Deposition Modeling (FDM) technology.
(4) And filling and wrapping the purchased metal lithium powder in the three-dimensional framework, wherein the mass ratio of the three-dimensional framework to the filled metal lithium is 1:1, cooling and pressurizing to obtain the metal lithium composite negative pole piece with a smooth and flat surface, which is shown in 1.
2. Soft-package polymer solid lithium ion battery
With LiNi0.5Co0.3Mn0.2O2(94 wt%), Super-P (2.9 wt%), PVDF-HFP (3.1 wt%) were coated to an areal density of 10mg/cm2The anode plate is matched with commercially purchased LiPF6The lithium ion battery is characterized by comprising a/EC/DEC electrolyte and a three-dimensional metal lithium composite negative pole piece, and the soft-package polymer lithium ion battery is manufactured by adopting the conventional winding process.
Comparative example 2
Comparative example 2 proposes a soft-packed polymer lithium ion battery, the preparation method of which comprises the following steps:
with LiNi0.5Co0.3Mn0.2O2(94 wt%), Super-P (2.9 wt%), PVDF-HFP (3.1 wt%) were coated to an areal density of 10mg/cm2The anode plate is matched with commercially purchased LiPF6And the metal lithium foil and the Cu current collector are hot-pressed into a Li-Cu layered structure substrate by the aid of the EC/DEC electrolyte, and the soft-package polymer lithium ion battery is manufactured by the aid of an existing winding process.
Example 3
Embodiment 3 provides a composite negative electrode plate and an all-solid-state grinding tool lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Carbon fiber, acrylonitrile-butadiene-styrene plastic (ABS), a surfactant and a toughening compatilizer are mixed according to the mass ratio of 5.1:1.3: 0.15: and (2) uniformly mixing the components in a ratio of 0.05, putting the mixture into a beaker, adding a certain amount of dichloromethane, uniformly stirring the mixture at room temperature at a rotating speed of 800rpm for 6 hours to form a homogeneous solution, fully volatilizing the solvent to obtain a blocky solid from the slurry after stirring, drying the blocky solid in vacuum at 50 ℃ for 11 hours, and shearing and grinding the blocky solid to obtain the precursor of the granular 3D printing material.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 226 ℃, drawing the wires at the speed of 28cm/min by a drawing machine, and coiling the extruded wires with the diameter of 0.30 mm.
(3) The method comprises the steps of compounding metal lithium and a Cu current collector into a Cu-Li substrate by adopting a melting blade coating method, carrying out three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on the Li-Cu composite substrate by utilizing a Fused Deposition Modeling (FDM).
(4) And filling and wrapping the Li-In alloy (1:1) In the three-dimensional framework In a cold pressing mode, wherein the mass ratio of the three-dimensional framework to the filled Li-In alloy is 1:3, and thus the layered lithium composite negative pole piece with a smooth and flat surface is obtained, as shown In 1.
2. Lithium ion battery for all-solid-state grinding tool
Coated with lithium iron phosphate (90 wt%), CNT (6 wt%), polyvinylidene fluoride (4 wt%) to an areal density of 10mg/cm2The positive pole piece is matched with Li6PS5And assembling the Cl sulfide inorganic electrolyte and the three-dimensional layered lithium alloy composite negative pole piece into the all-solid-state grinding tool battery.
Comparative example 3
Comparative example 3 proposes an all-solid-state abrasive tool battery, the preparation method of which comprises the steps of:
coated with lithium iron phosphate (90 wt%), CNT (6 wt%), polyvinylidene fluoride (4 wt%) to an areal density of 10mg/cm2The positive pole piece is matched with Li6PS5And assembling the Cl sulfide inorganic electrolyte and the traditional Li-In alloy cathode into the all-solid-state grinding tool lithium ion battery.
Example 4
Embodiment 4 provides a composite negative electrode plate and a lithium ion battery, and the preparation method thereof comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fibers, Thermoplastic Polyurethane (TPU), a surfactant and a toughening compatilizer according to the mass ratio of 7.9:2.8:0.3:0.11, putting the mixture into a beaker, adding a certain amount of DMF (dimethyl formamide), uniformly stirring for 7 hours at the rotation speed of 550rpm at 75 ℃ to form a homogeneous solution, fully volatilizing the solvent to obtain a blocky solid from the slurry after stirring, drying for 15 hours in vacuum at 118 ℃, and shearing and grinding the blocky solid to obtain the granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 164 ℃, drawing the wires at the speed of 12cm/min by a drawing machine, and coiling the extruded wires with the diameter of 0.40 mm.
(3) The method comprises the steps of taking a commercially available Li-Cu composite belt as a substrate, carrying out three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on the Li-Cu composite substrate by utilizing a Fused Deposition Modeling (FDM) technology.
(4) Heating the Li-Al alloy to a molten state, filling and wrapping the Li-Al alloy in the three-dimensional framework, wherein the mass ratio of the three-dimensional framework to the filled Li-Al is 2:1, cooling and pressurizing to obtain the layered lithium metal composite negative pole piece with a smooth and flat surface, as shown in 2.
2. Lithium ion battery cell
With LiNi0.8Co0.15Al0.05O2(86 wt%), ketjen black (7 wt%), polytetrafluoroethylene (7 wt%) were coated to an areal density of 10mg/cm2The positive pole piece is matched with the LLZO oxide inorganic electrolyte and the layered metal lithium composite negative pole piece to assemble the lithium ion battery.
Comparative example 4
Comparative example 4 proposes a soft-packed monolithic cell whose preparation method comprises the following steps:
with LiNi0.8Co0.15Al0.05O2(86 wt%), ketjen black (7 wt%), polytetrafluoroethylene (7 wt%) were coated to an areal density of 10mg/cm2The anode plate is matched with LLZO oxide inorganic electrolyte and a traditional Li-Al alloy cathode to assemble the lithium ion battery.
Example 5
Embodiment 5 provides a composite negative electrode plate and a soft-package solid-state lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fibers, acrylonitrile-butadiene-styrene (ABS), a surfactant and a toughening compatilizer according to the mass ratio of 5.8:2.3:0.27:0.2, putting the mixture into a beaker, adding a certain amount of DMF, uniformly stirring at the rotating speed of 850rpm at 40 ℃ for 5 hours to form a homogeneous solution, fully volatilizing the solvent to obtain a blocky solid from the slurry after stirring, drying in vacuum at 50 ℃ for 6 hours, and shearing and grinding the blocky solid to obtain a granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 207 ℃, drawing the wires at the speed of 6cm/min by a drawing machine, and coiling the extruded wires with the diameter of 0.20 mm.
(3) Uniformly covering metal lithium on a Cu current collector by utilizing an atomic deposition technology, carrying out three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on a Li-Cu composite substrate by utilizing a fused deposition technology (FDM).
(4) And (3) wrapping the cold-pressed metal lithium in the three-dimensional framework in a filling manner, wherein the mass ratio of the three-dimensional framework to the filled metal lithium is 2:5, so that the layered metal lithium composite negative pole piece with a smooth and flat surface can be obtained, as shown in 2.
2. Soft package solid lithium ion battery
With lithium manganate (LiMnO)2) (93 wt%), ketjen black (3 wt%), polyvinylidene fluoride (4 wt%) were coated to an areal density of 10mg/cm2The anode plate is matched with commercially purchased LiPF6the/EC/DMC electrolyte and the layered metal lithium composite negative pole piece are manufactured into the soft-package solid-state lithium ion battery by adopting the traditional lamination process.
Comparative example 5
Comparative example 5 proposes a soft-packed solid-state lithium ion battery, the preparation method of which comprises the following steps:
with lithium manganate (LiMnO)2) (93 wt%), ketjen black (3 wt%), polyvinylidene fluoride (4 wt%) were coated to an areal density of 10mg/cm2The anode plate is matched with commercially purchased LiPF6EC/DMC electrolyte, three-dimensional carbonThe fiber-metal lithium cathode is manufactured into a soft package solid lithium ion battery by adopting a traditional lamination process.
Example 6
Embodiment 6 provides a composite negative electrode plate and a soft-package solid-state lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fiber, polyethylene oxide (PEO), polylactic acid (PLA) and a surfactant according to the mass ratio of 6.3:0.7:1.8:0.17, placing the mixture into a beaker, adding a certain amount of chloroform, uniformly stirring the mixture at the rotating speed of 900rpm at the temperature of 35 ℃ for 10 hours to form a homogeneous solution, fully volatilizing the solvent to obtain a blocky solid from the slurry after stirring, drying the blocky solid in vacuum at the temperature of 52 ℃ for 15 hours, and shearing and grinding the blocky solid to obtain a granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 138 ℃, drawing the wires at the speed of 9cm/min by a drawing machine, and coiling the extruded wires with the diameter of 0.55 mm.
(3) Uniformly covering metal lithium on a Cu current collector by using a vacuum evaporation and transition technology, carrying out three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on a Li-Cu composite substrate by using a Fused Deposition Modeling (FDM) technology.
(4) Heating the metal lithium to a molten state, filling and wrapping the metal lithium in the three-dimensional framework, wherein the mass ratio of the three-dimensional framework to the filled metal lithium is 1:4, cooling and pressurizing to obtain the metal lithium composite negative pole piece with a smooth and flat surface, as shown in 2.
2. Soft package solid lithium ion battery
With lithium nickelate (Li)2NiO2) (80 wt%), conductive carbon black (5 wt%), graphene (5 wt%) and polyvinylidene fluoride (10 wt%) are coated to have an areal density of 10mg/cm2The positive pole piece is matched with a polycarbonate-based polymer electrolyte and a layered metal lithium alloy composite negative pole piece, and the soft package solid lithium ion battery is manufactured by adopting a traditional lamination process.
Comparative example 6
Comparative example 6 provides a composite negative electrode plate and a soft-package solid-state lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Commercially available foamed nickel flakes were thoroughly cleaned to ensure removal of impurities and dirt, vacuum dried and cold pressed to smooth surfaced flakes for use.
(2) Heating the metal lithium to a molten state, filling and wrapping the metal lithium in a foam nickel structure framework, wherein the mass ratio of the foam nickel to the filled metal lithium is 1:4, and pressurizing after cooling to obtain the metal lithium composite negative pole piece with a smooth and flat surface.
2. Soft package solid lithium ion battery
With lithium nickelate (Li)2NiO2) (80 wt%), conductive carbon black (5 wt%), graphene (5 wt%) and polyvinylidene fluoride (10 wt%) are coated to have an areal density of 10mg/cm2The positive pole piece is matched with a polycarbonate-based polymer electrolyte and a foamed nickel-lithium alloy composite negative pole piece, and the soft-package solid lithium ion battery is manufactured by adopting a traditional lamination process.
Example 7
Embodiment 7 provides a composite negative electrode plate and a soft-package solid-state lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fiber, Polycaprolactone (PCL), polyvinyl chloride (PVC), a surfactant and a toughening compatilizer according to the mass ratio of 7.1:1.1:0.3:0.1:0.14, putting the mixture into a beaker, adding a certain amount of THF, uniformly stirring at the rotating speed of 650rpm at 65 ℃ for 4 hours to form a homogeneous solution, fully volatilizing the solvent to obtain a blocky solid from the slurry after stirring, drying in vacuum at 59 ℃ for 24 hours, and shearing and grinding the blocky solid to obtain the granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 96 ℃, the traction is performed by a traction machine at the speed of 15cm/min, the diameter of the extruded wires is 0.35mm, and the wires are coiled.
(3) And hot-pressing the metal lithium on a Cu current collector, performing three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on the Li-Cu composite substrate by utilizing a Fused Deposition Modeling (FDM) technology.
(4) And (3) hot-pressing, filling and wrapping the lithium belt in the three-dimensional framework, wherein the mass ratio of the three-dimensional framework to the filled metal lithium is 1:2, and thus the layered lithium composite negative pole piece with smooth and flat surface can be obtained.
2. Soft package solid lithium ion battery
With LiNi0.6Co0.6Mn0.2O2(91 wt%), Super-P (5 wt%), PVDF-HFP (4 wt%) were coated to an areal density of 10mg/cm2The positive pole piece is matched with a polycaprolactone-based polymer electrolyte and a layered metal lithium composite negative pole piece, and the soft-package solid lithium ion battery is manufactured by adopting a traditional winding process.
Comparative example 7
Comparative example 7 proposes a soft-packed solid-state lithium ion battery, the preparation method of which comprises the following steps:
with LiNi0.6Co0.6Mn0.2O2(91 wt%), Super-P (5 wt%), PVDF-HFP (4 wt%) were coated to an areal density of 10mg/cm2The positive pole piece is matched with polycaprolactone-based polymer electrolyte and a traditional metal lithium negative pole, and a traditional winding process is adopted to manufacture the soft package solid lithium ion battery.
Example 8
Embodiment 8 provides a composite negative electrode plate and a soft-package lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Uniformly mixing carbon fiber, Thermoplastic Polyurethane (TPU), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP) and a surfactant according to the mass ratio of 8:1.1:0.9:0.22, putting the mixture into a beaker, adding a certain amount of NMP, uniformly stirring at the rotating speed of 700rpm at 65 ℃ for 8 hours to form a homogeneous solution, fully volatilizing the solvent to obtain a blocky solid from the slurry after stirring, drying in vacuum at 140 ℃ for 14 hours, and shearing and grinding the blocky solid to obtain the granular 3D printing material precursor.
(2) Shearing and grinding the granular 3D printing material precursor, feeding the precursor into a screw extruder, blending and preparing wires, wherein the wire preparing temperature is 168 ℃, drawing the wires at the speed of 20cm/min by a drawing machine, and coiling the extruded wires with the diameter of 0.60 mm.
(3) The method comprises the steps of taking a commercially available Li-Cu composite tape as a substrate, carrying out three-dimensional modeling according to a preset design, and then printing a three-dimensional framework on the Li-Cu composite substrate by utilizing a Fused Deposition Modeling (FDM) technology.
(4) And (3) wrapping the lithium belt in the three-dimensional framework in a cold-pressing filling manner, wherein the mass ratio of the three-dimensional framework to the filled metal lithium is 1:2.5, so that the metal lithium composite negative pole piece with a smooth and flat surface can be obtained.
2. Soft package lithium ion battery
Coated with lithium cobaltate (96 wt%), CNT (2.1 wt%), polyvinylidene fluoride (1.9 wt%) to an areal density of 10mg/cm2The anode plate is matched with commercially purchased LiPF6the/EC/DMC/EMC electrolyte and the layered metal lithium composite negative pole piece are manufactured into the soft package lithium ion battery by adopting the traditional lamination process.
Comparative example 8
Comparative example 8 provides a composite negative electrode plate and a soft-package lithium ion battery, and the preparation method comprises the following steps:
1. preparation of composite negative pole piece
(1) Commercially available copper foam is thoroughly cleaned to ensure removal of impurities and dirt, vacuum dried and cold pressed into a flat surface sheet for later use.
(2) And (3) fully filling and wrapping the lithium belt in a foamy copper structure framework after cold pressing, wherein the mass ratio of foamy copper to filled metal lithium is 1:2.5, and thus the metal lithium composite negative pole piece with a smooth and flat surface can be obtained.
2. Solid lithium ion battery
Coated with lithium cobaltate (96 wt%), CNT (2.1 wt%), polyvinylidene fluoride (1.9 wt%) to an areal density of 10mg/cm2The anode plate is matched with commercially purchased LiPF6The soft package lithium is manufactured by adopting the traditional lamination process for preparing a composite negative pole piece of a/EC/DMC/EMC electrolyte and a foam copper lithium alloyAn ion battery.
The negative pole pieces of the examples 1 to 8 and the comparative examples 1 to 8 of the invention are used as electrodes, and the negative pole pieces and the corresponding electrolytes in the examples or the comparative examples are assembled into the lithium symmetrical battery.
The cycle life of the lithium symmetric battery of example 7 at room temperature was measured, and the results are shown in fig. 3.
The resistance at room temperature, the resistance after 50 cycles and the resistance after 400 cycles and the cycle life of the lithium symmetrical batteries according to examples 1 to 8 of the present invention and comparative examples 1 to 8 were measured, respectively, and the results are shown in table 1.
TABLE 1
The ac impedance at room temperature, the ac impedance after 100 cycles, the cycle life and the battery short-circuit rate of the lithium ion batteries of examples 1 to 8 of the present invention and comparative examples 1 to 8 were measured, respectively, and the results are shown in table 2.
TABLE 2
The lithium symmetric battery of example 7 was subjected to a cycle stability test at room temperature, and as a result, as shown in fig. 3, the voltage plateau of the lithium symmetric battery of example 7 exhibited good stability and no short circuit occurred within 500 cycles of the cycle. It is shown that the interface between the negative electrode sheet prepared in example 7 of the present invention and the electrolyte has good stability, and can well inhibit the growth of lithium dendrites.
As shown in table 1, the present invention compares the ac impedance and cycle life of the negative electrode sheets of examples 1 to 8 and comparative examples 1 to 8 by preparing the negative electrode sheet into a lithium symmetric battery. It can be seen that the lithium symmetric batteries of examples 1-8, relative to comparative examples 1-8, still exhibited good stability and cycle life after 50 and 400 cycles without short-circuiting. The lithium symmetric batteries of comparative examples 1 to 8 have large room temperature alternating current impedance, the alternating current impedance is also significantly increased after 50 cycles and 400 cycles, the cycle life is also significantly shorter than that of the lithium symmetric batteries of examples 1 to 8, and a short circuit occurs, which shows that the negative electrode plate of the embodiment of the invention also has good capability of inhibiting the growth of lithium dendrites.
As can be seen from table 2, the lithium ion batteries prepared in examples 1 to 8 of the present invention have lower resistance and maintain good stability after 100 cycles compared to the lithium ion batteries prepared in comparative examples 1 to 8, while the lithium ion batteries prepared in comparative examples 1 to 8 have higher resistance and significantly increased resistance after 100 cycles. Meanwhile, compared with the comparative examples 1 to 8, the cycle life of the lithium ion battery is remarkably prolonged, the short circuit rate of the battery is almost zero, and the generation of lithium dendrite can be inhibited. In conclusion, the composite negative pole piece with light weight and high strength is obtained by filling the metal lithium in the three-dimensional framework, stable and uniform deposition of the metal lithium is facilitated under high current density, the integrity and uniformity of the SEI film are improved, the conditions of pulverization and lithium death of the lithium piece are improved, the growth of lithium dendrites can be inhibited to a certain degree, and meanwhile, the composite negative pole piece has good interface performance with electrolyte. The lithium ion battery can inhibit the generation of dendrites, can effectively relieve the volume strain of the battery in the circulation process, has small resistance change after 100 cycles of circulation, obviously prolongs the circulation life, and greatly improves the circulation stability of the battery.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. The composite negative pole piece is characterized by comprising a current collector metal-metal lithium composite substrate and a carbon fiber-lithium-containing metal composite structure arranged on the current collector metal-metal lithium composite substrate;
the carbon fiber-lithium-containing metal composite structure comprises a three-dimensional framework and lithium-containing metal, wherein the mass ratio of the three-dimensional framework to the lithium-containing metal is 1-18: 6;
the three-dimensional skeleton comprises carbon fibers, a polymer, a surfactant and a toughening agent in a mass ratio of 60-80:10-30:1-5: 0-5;
the three-dimensional framework is obtained by 3D printing a wire with the diameter of 0.1-0.8mm on the current collector metal-metal lithium composite substrate through a fused deposition technology.
2. The composite negative electrode sheet according to claim 1, wherein the three-dimensional skeleton is a columnar structure and/or a three-dimensional network structure.
3. The composite negative electrode plate as claimed in any one of claims 1 to 2, wherein the current collector metal-metal lithium composite substrate is obtained by compounding metal lithium with a current collector metal, and the compounding method is one or more of cold pressing, hot pressing, melt blade coating, pulsed laser deposition, atomic deposition and vacuum evaporation.
4. The composite negative electrode sheet according to claim 1 or 2, wherein the lithium-containing metal is selected from at least one of metallic lithium selected from one of molten metallic lithium, lithium powder and lithium ribbon, or lithium alloy including Li-In alloy, Li-Al alloy, Li-Sn alloy, Li-Mg alloy and Li-Ge alloy.
5. The composite negative electrode sheet of claim 3, wherein the lithium-containing metal is selected from at least one of metallic lithium selected from one of molten metallic lithium, lithium powder, and lithium ribbon, or lithium alloy including Li-In alloy, Li-Al alloy, Li-Sn alloy, Li-Mg alloy, and Li-Ge alloy.
6. The composite negative electrode plate of claim 1 or 2, wherein the polymer is selected from one or more of acrylonitrile-butadiene-styrene plastic, polyethylene oxide, polylactic acid, polyvinylidene fluoride, polyvinyl alcohol, polyvinyl chloride, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, and thermoplastic polyurethane; and/or
The toughening agent is selected from one or a combination of more of cyclic anhydride type, epoxy type and oxazoline type; and/or
The current collector metal is copper.
7. The preparation method of the composite negative pole piece is characterized by comprising the following steps:
pretreating carbon fibers, a polymer, a surfactant and a toughening agent in a mass ratio of 60-80:10-30:1-5:0-5 to prepare a wire material;
compounding metal lithium on a current collector to obtain a current collector metal-metal lithium composite substrate;
3D printing is carried out on the current collector metal-metal lithium composite substrate through a fused deposition technology to obtain a three-dimensional framework;
filling the three-dimensional framework gap with lithium-containing metal, and preparing a carbon fiber-lithium-containing metal composite structure by pressure forming to obtain the composite negative pole piece, wherein the mass ratio of the three-dimensional framework to the lithium-containing metal is 1-18: 6.
8. The preparation method according to claim 7, wherein the pretreatment step is specifically: mixing the carbon fiber, the polymer, the surfactant and the toughening agent in an organic solvent, stirring for homogenizing, removing the organic solvent and crushing.
9. The preparation method according to claim 7 or 8, wherein the method for compounding the metallic lithium on the current collector is one or more selected from cold pressing, hot pressing, melt blade coating, pulsed laser deposition, atomic deposition and vacuum evaporation.
10. A lithium ion battery prepared from the composite negative electrode plate of any one of claims 1 to 6.
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| CN114512674A (en) * | 2020-11-16 | 2022-05-17 | 比亚迪股份有限公司 | Negative pole piece and metal lithium battery |
| CN114270574A (en) * | 2021-03-30 | 2022-04-01 | 宁德新能源科技有限公司 | Negative electrode material, negative electrode sheet, electrochemical device, and electronic device |
| CN115832323A (en) * | 2021-11-18 | 2023-03-21 | 宁德时代新能源科技股份有限公司 | Metallic lithium negative electrode, secondary battery, battery module, battery pack, and electric device |
| CN114497465B (en) * | 2022-03-31 | 2022-07-22 | 宁德新能源科技有限公司 | Preparation method of pole piece, electrochemical device and electronic device |
| CN115976500B (en) * | 2023-02-13 | 2024-01-19 | 北京纯锂新能源科技有限公司 | Lithium-based high-entropy alloy coating, preparation method and metal lithium battery |
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