CN111554971A - Wire and application thereof - Google Patents

Wire and application thereof Download PDF

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Publication number
CN111554971A
CN111554971A CN202010394293.1A CN202010394293A CN111554971A CN 111554971 A CN111554971 A CN 111554971A CN 202010394293 A CN202010394293 A CN 202010394293A CN 111554971 A CN111554971 A CN 111554971A
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CN
China
Prior art keywords
wire
lithium
electrolyte
solid
wire material
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CN202010394293.1A
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Chinese (zh)
Inventor
张赵帅
赵伟
李素丽
李俊义
徐延铭
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Zhuhai Cosmx Battery Co Ltd
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Zhuhai Cosmx Battery Co Ltd
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Priority to CN202010394293.1A priority Critical patent/CN111554971A/en
Publication of CN111554971A publication Critical patent/CN111554971A/en
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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
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0085—Immobilising or gelification of electrolyte
    • 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

Abstract

The invention provides a wire and application thereof, wherein the wire comprises the following components in percentage by mass: the wire comprises the following components in percentage by mass: 50-90% of polymer electrolyte, 1-30% of ceramic particles, 5-40% of lithium salt and 1-15% of additive. The wire is not only suitable for fused deposition modeling technology, but also has excellent mechanical property and ion conductivity, so that the wire can be used as a raw material for 3D printing for printing of solid electrolyte.

Description

Wire and application thereof
Technical Field
The invention relates to a wire material, in particular to a wire material and application thereof, and belongs to the technical field of secondary batteries.
Background
The all-solid-state battery uses the non-flammable solid electrolyte to replace flammable electrolyte in the traditional lithium ion battery, thereby fundamentally avoiding potential safety hazards. In addition, the good mechanical property of the solid electrolyte can effectively inhibit the growth in the lithium metal negative electrode, thereby greatly reducing the short circuit risk caused by the penetration of dendrites, enabling the metal lithium to be used as the negative electrode material of the lithium ion battery, and effectively improving the energy density of the lithium ion battery. Among them, the solid electrolyte is classified into an inorganic solid electrolyte, an organic solid electrolyte and a composite electrolyte, and the composite electrolyte includes an organic polymer and an inorganic substance, so that the advantages of the inorganic solid electrolyte and the organic solid electrolyte can be taken into consideration, thereby having excellent ion conductivity and mechanical properties.
However, the preparation method of the composite solid electrolyte is complex, low in automation degree, long in preparation period, high in process requirement, and poor in stability caused by manual operation.
The 3D printing technology is called a rapid prototyping technology, an additive manufacturing technology, etc., and among them, the fused deposition modeling technology is widely used because it has advantages of low manufacturing cost due to no use of laser, high utilization rate of raw materials, no chemical change in the modeling process, low modeling cost, etc.
Therefore, if the 3D printing technology can be applied to the preparation of the composite solid electrolyte, the diversity of the space structure of the composite electrolyte can be increased, and the production time and the cost of the composite solid electrolyte can be greatly saved.
Disclosure of Invention
The invention provides a wire which is not only suitable for fused deposition modeling technology, but also has excellent mechanical properties and ion conductivity, and therefore can be used as a raw material for 3D printing for printing of solid electrolyte.
The invention also provides a solid electrolyte which is obtained by printing the wire material serving as a raw material through a 3D printing technology, and the solid electrolyte not only has the advantages of low preparation cost, short preparation period and the like, but also has shape diversity and mechanical flexibility.
The invention also provides a lithium ion battery which comprises the solid electrolyte, so that the lithium ion battery is low in production cost and good in safety performance and cycle performance.
The invention provides a wire, which comprises the following components in percentage by mass: 50-90% of polymer electrolyte, 1-30% of ceramic particles, 5-40% of lithium salt and 1-15% of additive.
The wire material further comprises a toughening compatibilizer of 5% or less by mass.
The wire as described above, wherein the diameter of the wire is 0.2-0.8 mm.
The filament material as described above, wherein the polymer electrolyte is at least one selected from acrylonitrile-butadiene-styrene plastic, polyethylene oxide, polylactic acid, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, thermoplastic polyurethane, polymethyl methacrylate, and polyvinyl acetate.
The wire as described above, wherein the ceramic particles are selected from at least one of oxides, carbides, and nitrides.
The wire as described above, wherein the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonimide, lithium dioxalate, lithium difluorooxalate, lithium trifluoromethanesulfonate and lithium bistrifluoromethylsulfonyl imide.
The wire material as described above, wherein the additive auxiliary agent is selected from an electrolyte and/or an ionic liquid.
The wire material as described above, wherein the toughening compatibilizer is at least one selected from a cyclic anhydride type toughening compatibilizer, an epoxy type toughening compatibilizer, and an oxazoline type toughening compatibilizer.
The invention also provides a solid electrolyte, which is obtained by printing the wire material of any one of the above as a raw material by a fused deposition modeling technology.
The invention also provides a lithium ion battery, and the electrolyte of the lithium ion battery is the solid electrolyte.
The wire provided by the invention comprises the polymer electrolyte, the ceramic particles, the lithium salt and the additive with specific contents, not only has excellent mechanical properties and ion conductivity, but also is suitable for fused deposition molding technology, so that the wire can be used as a raw material for 3D printing to print the solid electrolyte, the preparation cost of the solid composite electrolyte can be reduced, the preparation process of the solid composite electrolyte is simplified, the solid electrolytes with different structures, sizes and mechanical properties can be rapidly obtained, and a lithium ion transmission channel is artificially designed, so that the requirement of a rapidly developed secondary battery is met.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The first aspect of the invention provides a wire material, which comprises the following components in percentage by mass: 50-90% of polymer electrolyte, 1-30% of ceramic particles, 5-40% of lithium salt and 1-15% of additive.
The wire of the present invention is a strip material having a length extremely large relative to its cross-sectional diameter, which is suitable as a material for 3D printing.
The wire material has good uniformity due to the composition, is not only suitable for fused deposition molding technology, but also can be used as a raw material to be extruded at a nozzle of a fused deposition molding device, and has excellent mechanical property and ionic conductivity, so that the wire material can be used as the raw material to print a composite solid electrolyte. The inventor analyzes the phenomenon, and thinks that the addition of the ceramic particles can change the pH value of the system, the formed ion-ceramic complex compound enhances the solubility of lithium salt, thereby improving the ionic conductivity, and the ceramic particles can also further improve the conductivity by increasing the transmission channel of lithium ions; in addition, the addition of the ceramic particles also increases the surface area of the polyelectrolyte, prevents local recrystallization of polymer chains during cooling, and realizes optimization of mechanical strength while improving ionic conductivity.
Further, the wire material also comprises a toughening compatilizer, and the mass percentage content of the toughening compatilizer in the wire material is not more than 5%. The toughening compatibilizer can be at least one of a cyclic anhydride type toughening compatibilizer, an epoxy type toughening compatibilizer, and an oxazoline type toughening compatibilizer.
In one embodiment, the cross-sectional (perpendicular to the length direction) diameter of the wire of the present invention is 0.2 to 1.8 mm.
In order to further ensure the mechanical property of the wire material, the polymer electrolyte is selected from at least one of acrylonitrile-butadiene-styrene plastics, polyethylene oxide, polylactic acid, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, thermoplastic polyurethane, polymethyl methacrylate and polyvinyl acetate.
Further, the ceramic particles of the present invention are selected from at least one of oxides, carbides, and nitrides. The ceramic particles may be in the nano-or micro-scale and may be in any of spherical, plate-like, and short rod-like shapes.
Wherein the oxide can be at least one selected from alumina, silicon dioxide, titanium dioxide, magnesium oxide, zinc oxide, zirconium oxide, calcium oxide and copper oxide, and further the alumina can be α -Al with different crystal forms2O3、β-Al2O3、γ-Al2O3。
The carbide may be one or two of silicon carbide and boron carbide.
The nitride may be at least one of silicon nitride, boron nitride, and aluminum nitride.
Further, the lithium salt of the present invention is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium dioxalate, lithium difluorooxalate, lithium trifluoromethanesulfonate, and lithium bistrifluoromethylsulfonyl imide.
In the wire of the present invention, the additive is selected from an electrolyte and/or an ionic liquid. The electrolyte can be a commercially available electrolyte for a lithium ion battery, and the ionic liquid is at least one selected from quaternary ammonium ionic liquids, imidazole ionic liquids, pyrrole ionic liquids and pyridine ionic liquids.
The wire of the present invention can be obtained by a method comprising the following processes:
and sequentially adding the polymer electrolyte, the lithium salt, the addition auxiliary agent and the ceramic particles into an organic solvent for stirring, volatilizing the organic solvent in a mixed system, grinding the obtained solid, and carrying out wire making treatment on the ground particles to obtain the wire material.
In order to ensure the mixing uniformity of the polymer electrolyte and the ceramic particles in the mixed system, the polymer electrolyte can be firstly added into the organic solvent, then the first stirring is carried out to dissolve and disperse the polymer electrolyte in the solvent to the maximum extent, then the lithium salt and the addition agent are added in the second stirring state until the polymer electrolyte is uniformly dispersed, finally the ceramic particles are added, and the third stirring is carried out to obtain the mixed system.
And carrying out heat treatment on the mixed system to volatilize the organic solvent in the mixed system, carrying out vacuum drying on the obtained solid matter, and then carrying out grinding treatment to obtain the granular 3D printing material precursor.
And finally, blending and preparing wires from the 3D printing material precursor by using an extruder, and drawing at a certain speed by using a tractor to obtain wires with uniform sizes and coiling the wires.
Further, if the wire contains the toughening compatibilizer, the toughening compatibilizer may be added in the step of mixing the polymer electrolyte and the organic solvent.
In the above preparation process, the organic solvent is at least one selected from Acetonitrile (ACN), N-methylpyrrolidone (NMP), Dimethylformamide (DMF), dimethyl sulfoxide (DMSO), acetone, dichloromethane, chloroform, xylene, and Tetrahydrofuran (THF);
the temperatures of the first stirring, the second stirring and the third stirring can be respectively 25-150 ℃, and the boiling point of the organic solvent is further determined; the rotation speeds of the first stirring, the second stirring and the third stirring can be respectively 300-1000 rpm; the total time period of the first stirring, the second stirring and the third stirring may be 3 to 24 hours.
The vacuum drying temperature can be 30-200 deg.C, further 40-150 deg.C, further 50-130 deg.C, and the vacuum drying time can be 6-48 hr, further 10-24 hr.
When the blending is used for preparing the silk, the silk discharging speed is 5-30cm/min, the silk preparing temperature can be 80-235 ℃, and the silk preparing diameter is 0.2-0.8 mm.
In a second aspect, the invention provides a solid electrolyte, which is obtained by printing the wire material of the first aspect by fused deposition modeling.
Specifically, the solid electrolyte is obtained by printing with a fused deposition modeling technology by taking a wire as a raw material according to preset printing data. The preset print data may be obtained by three-dimensional modeling using software such as 3d max, Maya, CAD, and the like, and it can be understood that the preset print data differs depending on the size, shape, and structure of the solid electrolyte.
The solid electrolyte of the present invention uses wire material as raw material, and thus has excellent mechanical performance and ion conducting performance. In addition, the solid electrolyte is printed by the 3D technology, the time cost for preparing the solid electrolyte can be controlled, and a lithium ion transmission channel can be artificially designed by a wire material and a fused deposition molding technology, so that the solid electrolyte has various shapes and anisotropic mechanical properties, the requirements of different secondary batteries are met, and the market competitiveness is improved.
In a third aspect, the invention provides a lithium ion battery, wherein the electrolyte of the lithium ion battery is the solid electrolyte of the second aspect.
It can be understood that the lithium ion battery of the present invention includes a positive electrode sheet and a negative electrode sheet in addition to the solid electrolyte, wherein the solid electrolyte is spaced between the positive electrode sheet and the negative electrode sheet.
The positive plate at least comprises a positive material, a conductive agent and a binder, wherein the positive active material in the positive material is selected from LiCoO2、LiFePO4、LiNi0.3Co0.3Mn0.3O2、LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.2Mn0.2O2、LiNi0.8Co0.1Mn0.1O2、LiNi0.8Co0.15Al0.05O2、LiNi0.5Mn1.5O4At least one of (1);
the conductive agent is at least one selected from Acetylene Black (AB), conductive carbon black (Super-P), Ketjen Black (KB), Carbon Nanotubes (CNT) and graphene;
the binder is at least one selected from polyvinylidene fluoride (PVDF), sodium carboxymethylcellulose (CMC) and Sodium Alginate (SA).
The negative electrode material in the negative electrode sheet can be one of a graphite negative electrode, a silicon negative electrode and a silicon-carbon negative electrode of a metal lithium sheet, a metal lithium alloy and a copper foil current collector.
The lithium ion battery is manufactured by adopting a universal winding and laminating process, and specifically, the lithium ion battery can be obtained by winding or laminating a positive plate, a solid electrolyte and a negative plate in sequence, and performing vacuum packaging and tab welding.
Since the lithium ion battery of the present invention includes the solid electrolyte of the aforementioned first aspect, the production cost is low and the safety performance and cycle performance are good.
Hereinafter, the wire of the present invention will be described in detail by way of specific examples.
Example 1
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polylactic acid): 65.65 percent
Ceramic particles (ceramic powder ZrO)2)：8.90％
Lithium salt (lithium bistrifluoromethylsulfonyl imide): 20.31
The balance is added with an auxiliary agent (pyridine ionic liquid).
The wire of this example was obtained according to the following preparation method:
1. placing 23.6g of polylactic acid (PLA, Mw about 60000) in a beaker, dissolving in a certain amount of chloroform, and uniformly stirring at 35 ℃ and 500rpm for 3h to form a homogeneous solution;
2. adding 7.3g of lithium bis (trifluoromethyl) sulfonyl imide and 1.85g of pyridine ionic liquid into the homogeneous solution, and continuing to stir for 1 hour uniformly;
3. 3.2g of ceramic powder ZrO was further added to the system2Stirring for 3h until the dispersion is uniform;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 50 ℃ for 14h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the wire precursor into a screw extruder, blending and making wires, wherein the wire making temperature is 161 ℃, drawing the wires at the speed of 10cm/min by a tractor, the diameter of the extruded wires is 0.40mm, forming wires with uniform size, and coiling the wires for later use;
example 2
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polycaprolactone, polyethylene oxide): 59.17 percent
Ceramic particles (gamma-Al)2O3)：13.76％
Lithium salt (lithium difluorooxalato borate): 21.79 percent
Adding an auxiliary agent (imidazole ionic liquid): 4.82 percent
The balance of toughening compatilizer (epoxy toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 18g of polycaprolactone (PCL, the Mw of which is about 80000), 7.8g of polyethylene oxide (PEO, the Mw of which is about 500W) and 0.2g of epoxy toughening compatibilizer into a beaker for sufficient mechanical mixing, then dissolving into a certain amount of ACN, heating in a water bath at 52 ℃, and uniformly stirring at the rotating speed of 1000rpm for 4 hours to form a homogeneous solution;
2. adding 9.5g of lithium difluoro (oxalato) borate (LiDFOB) and 2.1g of imidazole ionic liquid into the homogeneous solution, and continuing to stir for 1 hour;
3.6g of ceramic powder gamma-Al is continuously added into the system2O3Continuously stirring for 2h until the dispersion is uniform;
4. fully volatilizing the solvent, vacuum-drying the obtained solid at 58 ℃ for 18h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 78 ℃, the traction is carried out by a traction machine at the speed of 22cm/min, the diameter of the extruded wire material is 0.80mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 3
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (thermoplastic polyurethane): 62.09 percent
Ceramic particles (titanium dioxide): 7.58 percent
Lithium salt (lithium perchlorate): 20.94 percent
The balance being additive (LiPF)6EC/DMC Forming electrolyte).
The wire of this example was obtained according to the following preparation method:
1. placing 17.2g of thermoplastic polyurethane (TPU, Mw of about 70000) in a beaker, then dissolving in a certain amount of DMF, heating in a water bath at 80 ℃, and uniformly stirring at the rotating speed of 550rpm for 7 hours to form a homogeneous solution;
2. to the homogeneous solution was added 5.8g of lithium perchlorate (LiClO)4) And 2.6g of LiPF6Continuing to stir the electrolyte formed by the EC/DMC for 2 hours uniformly;
3. 2.1g of ceramic powder titanium dioxide (TiO) was further added to the system2) Stirring for 3h until the dispersion is uniform;
4. fully volatilizing the solvent, vacuum-drying the obtained solid at 120 ℃ for 16h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 162 ℃, the traction is carried out by a traction machine at the speed of 12cm/min, the diameter of the extruded wire material is 0.40mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 4
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (acrylonitrile-butadiene-styrene plastic, polyvinyl acetate): 57.65 percent
Ceramic particles (silica): 17.92 percent
Lithium salt (lithium hexafluorophosphate): 15.22 percent
Adding an auxiliary agent (pyrrole ionic liquid): 8.79 percent
The balance of toughening compatilizer (cyclic anhydride type toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 29.6g of acrylonitrile-butadiene-styrene (ABS), 4.5g of polyvinyl acetate (PVAc, Mw is about 100000) and 0.25g of cyclic anhydride type toughening compatibilizer into a beaker for sufficient mechanical mixing, then dissolving into a certain amount of acetone, stirring at 40 ℃, and uniformly stirring at 1000rpm for 5 hours to form a homogeneous solution;
2. to the homogeneous solution was added 9g of lithium hexafluorophosphate (LiPF)6) And 5.2g of pyrrole ionic liquid, and stirring uniformly for 2 hours;
3. 10.6g of ceramic powder Silica (SiO) was further added to the system2) Stirring for 3h until the dispersion is uniform;
4. fully volatilizing the solvent to obtain a solid matter, drying the solid matter for 6 hours in vacuum at 50 ℃, and shearing and grinding the solid matter to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 205 ℃, the traction is carried out by a traction machine at the speed of 15cm/min, the diameter of the extruded wire material is 0.4mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 5
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (acrylonitrile-butadiene-styrene plastic): 52.65 percent
Ceramic particles (boron nitride): 12.65 percent
Lithium salt (lithium dioxalate borate): 22.45 percent
The balance being additive (LiPF)6Electrolyte formed by EC/DEC).
The wire of this example was obtained according to the following preparation method:
1. placing 12.9g of acrylonitrile-butadiene-styrene (ABS) plastic in a beaker, then dissolving in a certain amount of dichloromethane, heating in a water bath at 25 ℃, and uniformly stirring at the rotating speed of 900rpm for 6 hours to form a homogeneous solution;
2. to the homogeneous solution were added 5.5g of lithium bis (oxalato) borate (LiBOB) and 3g of LiPF6Continuing to stir the electrolyte formed by the EC/DEC for 2 hours uniformly;
3. continuously adding 3.1g of ceramic powder Boron Nitride (BN) into the system, and stirring for 3 hours until the mixture is uniformly dispersed;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 50 ℃ for 10h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 225 ℃, the traction is carried out by a traction machine at the speed of 30cm/min, the diameter of the extruded wire material is 0.70mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 6
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polylactic acid, polymethyl methacrylate): 61.96 percent
Ceramic particles (zinc oxide): 13.77 percent
Lithium salt (lithium bis (trifluoromethylsulfonyl) imide): 13.60 percent
Addition aid (quaternary amine ionic liquid): 9.29 percent
The balance of toughening compatilizer (epoxy toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 32g of polylactic acid (PLA, Mw is about 60000), 4g of polymethyl methacrylate (PMMA, Mw is about 35000) and 0.8g of epoxy toughening compatibilizer in a beaker for sufficient mechanical mixing, then dissolving in a certain amount of trichloromethane, stirring at 30 ℃, and uniformly stirring at the rotating speed of 400rpm for 13h to form a homogeneous solution;
2. to the homogeneous solution was added 7.9g of lithium bis (trifluoromethylsulfonyl) imide LiN (CF)3SO2)2And 5.4g of quaternary amine ionic liquid, and stirring uniformly for 4 hours;
3. continuously adding 8g of ceramic powder zinc oxide (ZnO) into the system, and stirring for 6 hours until the mixture is uniformly dispersed;
4. fully volatilizing the solvent, vacuum-drying the obtained solid at 40 ℃ for 48h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and making the wire material, wherein the making temperature is 155 ℃, the traction is carried out by a traction machine at the speed of 20cm/min, the diameter of the extruded wire material is 0.2mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 7
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polycaprolactone): 42.13 percent
Ceramic particles (aluminum nitride): 38.74 percent
Lithium salt (lithium bistrifluoromethylsulfonyl imide, lithium tetrafluoroborate): 17.43 percent
The balance is added with an auxiliary agent (pyridine ionic liquid).
The wire of this example was obtained according to the following preparation method:
1. placing 8.7g of polycaprolactone (PCL, Mw of 80000) in a beaker, then dissolving in a certain amount of ACN, heating in a water bath at 50 ℃, and uniformly stirring at the rotating speed of 300rpm for 4 hours to form a homogeneous solution;
2. to the homogeneous solution was added 2.5g of lithium bistrifluoromethylsulphonylimide (LiTFSI), 1.1g of lithium tetrafluoroborate (LiBF)4) And 0.35g of pyridine ionic liquid, and stirring uniformly for 2 hours;
3. continuously adding 8g of ceramic powder aluminum nitride (AlN) into the system, and stirring for 3.5 hours until the mixture is uniformly dispersed;
4. fully volatilizing the solvent to obtain a solid matter, drying the solid matter in vacuum at 60 ℃ for 24 hours, and shearing and grinding the solid matter to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 61 ℃, the traction is carried out by a traction machine at the speed of 6cm/min, the diameter of the extruded wire material is 0.70mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 8
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polyvinyl alcohol, polyacrylonitrile): 67.38 percent
Ceramic particles (silicon carbide): 5.02 percent
Lithium salt (lithium tetrafluoroborate): 19.00 percent
Adding an auxiliary agent (pyrrole ionic liquid): 7.89 percent
The balance of toughening compatilizer (oxazoline toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 16g of polyvinyl alcohol (PVA, Mw is about 47000), 2.8g of polyacrylonitrile (PAN, Mw is about 150000) and 0.2g of oxazoline toughening compatibilizer in a beaker for sufficient mechanical mixing, then dissolving in a certain amount of DMSO, stirring under a heating condition of 65 ℃, and uniformly stirring at the rotating speed of 500rpm for 6h to form a homogeneous solution;
2. to the homogeneous solution was added 5.3g of lithium tetrafluoroborate (LiBF)4) And 2.2g of pyrrole ionic liquid, and stirring uniformly for 3 hours;
3. continuously adding 1.4g of silicon carbide (SiC) into the system, and stirring for 1h until the silicon carbide is uniformly dispersed;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 180 ℃ for 12h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 235 ℃, the traction is carried out by a traction machine at the speed of 8cm/min, the diameter of the extruded wire material is 0.5mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 9
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (thermoplastic polyurethane, vinylidene fluoride-hexafluoropropylene copolymer): 50.42 percent
Ceramic particle (α -Al)2O3)：15.86％
Lithium salt (lithium bistrifluoromethylsulfonyl imide): 21.81 percent
Addition of auxiliaries (LiPF)6EC/DMC-forming electrolyte): 9.92 percent
The balance of toughening compatilizer (epoxy toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 15g of thermoplastic polyurethane (TPU, Mw of about 70000), 2.8g of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP, Mw of about 500000) and 0.7g of epoxy toughening compatibilizer into a beaker for sufficient mechanical mixing, then dissolving into a certain amount of NMP, heating in a water bath at 70 ℃, and uniformly stirring for 8 hours at the rotating speed of 700rpm to form a homogeneous solution;
2. to the homogeneous solution were added 7.7g of lithium bistrifluoromethylsulfonimide (LiTFSI) and 3.5g of LiPF6Continuing to stir the electrolyte formed by the EC/DMC for 5 hours uniformly;
3. 5.6g of ceramic powder α -Al was further added to the system2O3Stirring for 4h until the dispersion is uniform;
4. fully volatilizing the solvent, vacuum-drying the obtained solid at 150 ℃ for 24h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and making the wire material, wherein the making temperature is 167 ℃, drawing the wire material by a tractor at the speed of 24cm/min, the diameter of the extruded wire material is 0.6mm, forming the wire material with uniform size, and coiling the wire material for later use.
Example 10
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polypropylene 100): 60.18 percent
Ceramic particles (magnesium oxide): 9.14 percent
Lithium salt (lithium difluorooxalato borate): 22.12 percent
The balance is added with an auxiliary agent (imidazole ionic liquid).
The wire of this example was obtained according to the following preparation method:
1. placing 20.4g of polypropylene 100(PP, Mw of about 250000) in a beaker, dissolving in a certain amount of xylene, heating and stirring at 150 ℃, and uniformly stirring at 500rpm for 6h to form a homogeneous solution;
2. adding 7.5g of lithium difluoro (oxalato) borate (LiDFOB) and 2.9g of imidazole ionic liquid into the homogeneous solution, and continuing to stir for 3 hours uniformly;
3. continuously adding 3.1g of ceramic magnesium oxide powder (MgO) into the system, and stirring for 2 hours until the mixture is uniformly dispersed;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 90 ℃ for 16h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 192 ℃, drawing the wire by a tractor at the speed of 11cm/min, the diameter of the extruded wire material is 0.50mm, forming the wire material with uniform size, and coiling the wire material for later use.
Example 11
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polylactic acid): 60.75 percent
Ceramic particles (calcium oxide): 17.06 percent
Lithium salt (lithium bistrifluoromethylsulfonyl imide): 16.72 percent
The balance is added with an auxiliary agent (pyridine ionic liquid).
The wire of this example was obtained according to the following preparation method:
1. placing 17.8g of polylactic acid (PLA, Mw about 60000) in a beaker, dissolving in a certain amount of chloroform, and uniformly stirring at 25 ℃ and 600rpm for 3h to form a homogeneous solution;
2. adding 4.9g of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and 1.6g of pyridine ionic liquid into the homogeneous solution, and continuing to stir for 2 hours uniformly;
3. continuously adding 5g of ceramic powder calcium oxide (CaO) into the system, and stirring for 6 hours until the mixture is uniformly dispersed;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 40 ℃ for 12h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 156 ℃, the traction is carried out by a traction machine at the speed of 8cm/min, the diameter of the extruded wire material is 0.80mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 12
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polycaprolactone, polyvinyl chloride): 58.16 percent
Ceramic particles (silicon nitride): 12.28 percent
Lithium salt (lithium perchlorate): 16.31 percent
Addition of auxiliaries (LiPF)6EC/DEC forming electrolyte): 12.86 percent
The balance of toughening compatilizer (oxazoline toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 11.4g of polycaprolactone (PCL, with Mw of about 80000), 18.9g of polyvinyl chloride (PVC, with Mw of about 55000) and 0.2g of oxazoline toughening compatibilizer in a beaker for sufficient mechanical mixing, then dissolving in a certain amount of Tetrahydrofuran (THF), heating in a water bath at 65 ℃, and uniformly stirring at 650rpm for 4h to form a homogeneous solution;
2. to the homogeneous solution was added 8.5g of lithium perchlorate (LiClO)4) And 6.7g of LiPF6Continuing to stir the electrolyte formed by the EC/DEC for 3 hours uniformly;
3. 6.4g of ceramic powder silicon nitride (Si) was further added to the system3N4) Stirring for 6h until the dispersion is uniform;
4. fully volatilizing the solvent to obtain a solid matter, drying the solid matter in vacuum at 58 ℃ for 28h, and shearing and grinding the solid matter to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 96 ℃, the traction is carried out by a traction machine at the speed of 15cm/min, the diameter of the extruded wire material is 0.55mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 13
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polylactic acid, polyvinyl acetate): 61.37 percent
Ceramic particles (copper oxide): 9.35 percent
Lithium salt (lithium bis (fluorosulfonyl) imide): 16.51 percent
The balance is added with an auxiliary agent (pyridine ionic liquid).
The wire of this example was obtained according to the following preparation method:
1. placing 16.9g of polylactic acid (PLA, Mw is about 60000) and 2.8g of polyvinyl acetate (PVAc, Mw is about 100000) in a beaker, fully and mechanically mixing, then dissolving in a certain amount of dichloromethane, stirring at 25 ℃, and uniformly stirring at 750rpm for 15 hours to form a homogeneous solution;
2. adding 5.3g of lithium bis (fluorosulfonyl) imide (LiFSI) and 4.1g of pyridine ionic liquid into the homogeneous solution, and continuing to stir for 2 hours uniformly;
3. adding 3g of ceramic powder copper oxide (CuO) into the system, and stirring for 5 hours until the mixture is uniformly dispersed;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 35 ℃ for 20h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 144 ℃, the traction is carried out by a traction machine at the speed of 7cm/min, the diameter of the extruded wire material is 0.35mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 14
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polyethylene oxide, polylactic acid): 58.82 percent
Ceramic particle (β -Al)2O3)：16.22％
Lithium salt (lithium dioxalate borate): 15.26 percent
Addition of auxiliaries (LiPF)6EC/DMC-forming electrolyte): 9.22 percent
The balance of toughening compatilizer (cyclic anhydride type toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 1.9g of polyethylene oxide (PEO, Mw is about 1000000), 16.6g of polylactic acid (PLA, Mw is about 60000) and 0.15g of cyclic anhydride type toughening compatibilizer into a beaker for sufficient mechanical mixing, then dissolving into a certain amount of chloroform, stirring at 40 ℃, and uniformly stirring at 900rpm for 10 hours to form a homogeneous solution;
2. to the homogeneous solution were added 4.8g of lithium bis (oxalato) borate (LiBOB) and 2.9g of LiPF6Continuing to stir the electrolyte formed by the EC/DMC for 3 hours uniformly;
3. 5.1g of ceramic powder β -Al was further added to the system2O3Stirring for 4h until the dispersion is uniform;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 52 ℃ for 15h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 136 ℃, the traction is carried out by a traction machine at the speed of 24cm/min, the diameter of the extruded wire material is 0.65mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 15
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (acrylonitrile-butadiene-styrene plastic, polycarbonate): 68.43 percent
Ceramic particles (titanium dioxide): 10.30 percent
Lithium salt (lithium bis (fluorosulfonyl) imide): 14.35 percent
Adding an auxiliary agent (imidazole ionic liquid): 6.62 percent
The balance of toughening compatilizer (cyclic anhydride type toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 15g of acrylonitrile-butadiene-styrene (ABS), 3.6g of polycarbonate (PC, Mw is about 45000) and 0.08g of cyclic anhydride type toughening compatilizer in a beaker for full mechanical mixing, then dissolving in a certain amount of dichloromethane, stirring at 25 ℃, and uniformly stirring at 600rpm for 8h to form a homogeneous solution;
2. adding 3.9g of lithium bis (fluorosulfonyl) imide (LiFSI) and 1.8g of imidazole ionic liquid into the homogeneous solution, and continuing to stir for 2 hours uniformly;
3. 2.8g of ceramic powder titanium dioxide (TiO) was further added to the system2) Stirring for 4h until the dispersion is uniform;
4. fully volatilizing the solvent to obtain a solid matter, drying the solid matter in vacuum at 40 ℃ for 24 hours, and shearing and grinding the solid matter to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 225 ℃, the traction is carried out by a traction machine at the speed of 12cm/min, the diameter of the extruded wire material is 0.6mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Example 16
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (thermoplastic polyurethane, vinylidene fluoride-hexafluoropropylene copolymer, polycaprolactone): 61.17 percent
Ceramic particles (gamma-Al)2O3)：11.33％
Lithium salt (lithium bistrifluoromethylsulfonyl imide): 18.97 percent
Adding an auxiliary agent (imidazole ionic liquid): 7.65 percent
The balance of toughening compatilizer (epoxy toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. 4.3g of thermoplastic polyurethane (TPU, Mw of about 70000), 2.1g of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP, Mw of about 500000), 15.2g of polycaprolactone (PCL, Mw of about 80000) and 0.31g of epoxy toughening compatilizer are placed in a beaker for full mechanical mixing, then dissolved in a certain amount of DMF, heated in a water bath at 60 ℃, and uniformly stirred for 5 hours at the rotating speed of 700rpm to form a homogeneous solution;
2. adding 6.7g of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and 2.7g of imidazole ionic liquid into the homogeneous solution, and continuing to stir for 3 hours uniformly;
3. 4g of ceramic powder gamma-Al is continuously added into the system2O3Stirring for 8h until the dispersion is uniform;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 140 ℃ for 15h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and making the wire material, wherein the making temperature is 155 ℃, the traction is carried out by a traction machine at the speed of 9cm/min, the diameter of the extruded wire material is 0.3mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Comparative example 1
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polylactic acid): 50.81 percent
Ceramic particles (ceramic powder ZrO)2)：32.72％
Lithium salt (lithium bistrifluoromethylsulfonyl imide): 12.48 percent
The balance is added with an auxiliary agent (pyridine ionic liquid).
The wire of this example was obtained according to the following preparation method:
1. placing 23.6g of polylactic acid (PLA, Mw about 60000) in a beaker, dissolving in a certain amount of chloroform, and uniformly stirring at 35 ℃ and 500rpm for 3h to form a homogeneous solution;
2. adding 5.8g of lithium bis (trifluoromethyl) sulfonyl imide and 1.85g of pyridine ionic liquid into the homogeneous solution, and continuing to stir for 1 hour uniformly;
3. 15.2g of ceramic powder ZrO was further added to the system2Stirring for 3h until the dispersion is uniform;
4. fully volatilizing the solvent, carrying out vacuum drying on the obtained solid at 50 ℃ for 14h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the wire precursor into a screw extruder, blending and making wires, wherein the wire making temperature is 161 ℃, drawing the wires at the speed of 10cm/min by a tractor, the diameter of the extruded wires is 0.40mm, forming wires with uniform size, and coiling the wires for later use;
comparative example 2
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (polycaprolactone, polyethylene oxide): 60.14 percent
Ceramic particles (gamma-Al)2O3)：31.01％
Lithium salt (lithium difluorooxalato borate): 3.50 percent
Adding an auxiliary agent (imidazole ionic liquid): 4.89 percent
The balance of toughening compatilizer (epoxy toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 18g of polycaprolactone (PCL, the Mw of which is about 80000), 7.8g of polyethylene oxide (PEO, the Mw of which is about 500W) and 0.2g of epoxy toughening compatibilizer into a beaker for sufficient mechanical mixing, then dissolving into a certain amount of ACN, heating in a water bath at 52 ℃, and uniformly stirring at the rotating speed of 1000rpm for 4 hours to form a homogeneous solution;
2. adding 1.5g of lithium difluoro (oxalato) borate (LiDFOB) and 2.1g of imidazole ionic liquid into the homogeneous solution, and continuing to stir for 1 hour;
3. 13.3g of ceramic powder gamma-Al is continuously added into the system2O3Continuously stirring for 2h until the dispersion is uniform;
4. fully volatilizing the solvent, vacuum-drying the obtained solid at 58 ℃ for 18h, and shearing and grinding the solid to obtain a granular wire precursor;
5. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 78 ℃, the traction is carried out by a traction machine at the speed of 22cm/min, the diameter of the extruded wire material is 0.80mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Comparative example 3
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (thermoplastic polyurethane): 67.18 percent
Lithium salt (lithium perchlorate): 22.65 percent
The balance being additive (LiPF)6EC/DMC Forming electrolyte).
The wire of this example was obtained according to the following preparation method:
1. placing 17.2g of thermoplastic polyurethane (TPU, Mw of about 70000) in a beaker, then dissolving in a certain amount of DMF, heating in a water bath at 80 ℃, and uniformly stirring at the rotating speed of 550rpm for 7 hours to form a homogeneous solution;
2. to the homogeneous solution was added 5.8g of lithium perchlorate (LiClO)4) And 2.6g of LiPF6Continuing to stir the electrolyte formed by the EC/DMC for 2 hours uniformly;
3. fully volatilizing the solvent, vacuum-drying the obtained solid at 120 ℃ for 16h, and shearing and grinding the solid to obtain a granular wire precursor;
4. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 162 ℃, the traction is carried out by a traction machine at the speed of 12cm/min, the diameter of the extruded wire material is 0.40mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Comparative example 4
The wire of the embodiment comprises the following components in percentage by mass:
polymer electrolyte (acrylonitrile-butadiene-styrene plastic, polyvinyl acetate): 70.23 percent
Lithium salt (lithium hexafluorophosphate): 18.54 percent
Adding an auxiliary agent (pyrrole ionic liquid): 10.71 percent
The balance of toughening compatilizer (cyclic anhydride type toughening compatilizer).
The wire of this example was obtained according to the following preparation method:
1. placing 29.6g of acrylonitrile-butadiene-styrene (ABS), 4.5g of polyvinyl acetate (PVAc, Mw is about 100000) and 0.25g of cyclic anhydride type toughening compatibilizer into a beaker for sufficient mechanical mixing, then dissolving into a certain amount of acetone, stirring at 40 ℃, and uniformly stirring at 1000rpm for 5 hours to form a homogeneous solution;
2. to the homogeneous solution was added 9g of lithium hexafluorophosphate (LiPF)6) And 5.2g of pyrrole ionic liquid, and stirring uniformly for 2 hours;
3. fully volatilizing the solvent to obtain a solid matter, drying the solid matter for 6 hours in vacuum at 50 ℃, and shearing and grinding the solid matter to obtain a granular wire precursor;
4. feeding the precursor of the wire material into a screw extruder, blending and preparing the wire, wherein the wire preparing temperature is 205 ℃, the traction is carried out by a traction machine at the speed of 15cm/min, the diameter of the extruded wire material is 0.4mm, the wire material with uniform size is formed, and the wire material is coiled for standby.
Test example 1
The ionic conductivity and tensile strength properties of the wires of the above examples and comparative examples were measured and the results are shown in Table 1.
Wherein, the ionic conductivity is tested by adopting a thunder magnetic DDSJ-319L type conductivity meter;
the tensile strength is tested by an electronic tensile machine with the detection precision of 0.1N, the tensile speed is (100 +/-1) mm/min, and the tensile interval is (100 +/-5) mm.
TABLE 1
Ion conductivity (mS/cm) Tensile strengthStrength (MPa)
Example 1 0.32 10.65
Example 2 0.53 12.81
Example 3 0,49 14.37
Example 4 0.24 13.64
Example 5 0.38 9.44
Example 6 0,57 10.50
Example 7 0.27 7.89
Example 8 0.52 8.94
Example 9 0.29 11.24
Example 10 0.40 10.26
Example 11 0.22 15.63
Example 12 0.41 9.88
Example 13 0.33 12.06
Example 14 0.45 19.10
Example 15 0.28 13.92
Example 16 0.36 8.86
Comparative example 1 0.096 7.35
Comparative example 2 0.11 5.42
Comparative example 3 0.20 4.71
Comparative example 4 0.074 6.55
As can be seen from Table 1, the wire of the present invention facilitates printing of solid-state electrolytes for ion conducting properties as well as mechanical properties.
Test example 2
Using the wires of example 1 and comparative example 1 as raw materials, respectively, and performing fused deposition modeling printing according to preset printing data to obtain solid electrolytes A1 and a1 with the thickness of 100 μm; solid electrolytes A1 and a1 are respectively used to match LiNi0.5Co0.3Mn0.2O2(80 wt%), SP: KB (1:1) (10 wt%) and PVDF (10 wt%) to form a positive plate and a metallic lithium negative electrode, and button lithium ion batteries S1 and S1 are prepared.
Using the wires of example 2 and comparative example 2 as raw materials, respectively, and performing fused deposition modeling printing according to preset printing data to obtain solid electrolytes A2 and a2 with the thickness of 100 μm; winding soft package lithium ion batteries S2 and S2 are manufactured by respectively using solid electrolytes A2 and a2 and a positive plate and a metallic lithium negative electrode which are assembled by lithium cobaltate (95 wt%), SP (2.5 wt%) and PVDF (2.5 wt%).
Using the wires of example 3 and comparative example 3 as raw materials, respectively, and performing fused deposition modeling printing according to preset printing data to obtain solid electrolytes A3 and a3 with the thickness of 100 μm; solid electrolytes A3 and a3 are respectively used to match LiNi0.8Co0.1Mn0.2O1(80 wt%), SP-CNT (1:1) (10 wt%) and PVDF (10 wt%) were assembled into a positive plate and a metallic lithium negative electrode to make button lithium ion batteries S3 and S3.
Using the wires of example 4 and comparative example 4 as raw materials, respectively, and performing fused deposition modeling printing according to preset printing data to obtain solid electrolytes A4 and a4 with the thickness of 100 μm; the laminated soft package lithium ion batteries S4 and S4 are manufactured by respectively using solid electrolytes A4 and a4 and a positive plate and a metallic lithium negative electrode which are assembled by lithium iron phosphate (90 wt%), AB (5 wt%) and PVDF (5 wt%).
The lithium ion batteries S1, S2, S3, S4, S1, S2, S3 and S4 were subjected to constant current charging and discharging at room temperature at 0.1C by wuhan blue electric test equipment, and the capacity retention rate and the number of cycles (battery failure or short circuit, which indicates that charging and discharging cannot be performed normally) after 50 cycles are shown in table 2.
TABLE 2
Figure BDA0002487040690000211
Figure BDA0002487040690000221
As can be seen from Table 2, the lithium ion batteries comprising the solid electrolytes printed from the wire of the present invention have excellent cycle performance.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.

Claims (10)

1. A wire is characterized by comprising the following components in percentage by mass: 50-90% of polymer electrolyte, 1-30% of ceramic particles, 5-40% of lithium salt and 1-15% of additive.
2. The wire according to claim 1, further comprising 5% or less of a toughening compatibilizer in mass percentage.
3. A wire according to claim 1 or 2, wherein the diameter of the wire is 0.2-0.8 mm.
4. A wire according to any of claims 1 to 3, wherein the polymer electrolyte is at least one selected from acrylonitrile-butadiene-styrene plastics, polyethylene oxide, polylactic acid, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, thermoplastic polyurethane, polymethyl methacrylate, polyvinyl acetate.
5. A wire according to any one of claims 1 to 4, wherein said ceramic particles are selected from at least one of oxides, carbides and nitrides.
6. The wire according to claim 1, wherein the lithium salt is at least one selected from the group consisting of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulfonyl imide, lithium bistrifluorosulfonyl imide, lithium dioxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate and lithium bistrifluoromethylsulfonyl imide.
7. The wire according to claim 1, wherein the additive auxiliary agent is selected from an electrolyte and/or an ionic liquid.
8. The wire according to claim 2, wherein the toughening compatibilizer is at least one selected from the group consisting of a cyclic anhydride type toughening compatibilizer, an epoxy type toughening compatibilizer, and an oxazoline type toughening compatibilizer.
9. A solid electrolyte obtained by printing using the fused deposition modeling technique from the wire material according to any one of claims 1 to 8.
10. A lithium ion battery, characterized in that the electrolyte of the lithium ion battery is the solid-state electrolyte of claim 9.
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* Cited by examiner, † Cited by third party
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CN113067029A (en) * 2021-02-05 2021-07-02 中国地质大学（武汉） Gel electrolyte 3D printing paste and forming method thereof
CN115895218A (en) * 2022-12-30 2023-04-04 浙江大学台州研究院 Polycaprolactone magnesium ceramic composite 3D printing wire and preparation method thereof

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