CN111554975A - Solid electrolyte, preparation method thereof and lithium ion battery - Google Patents

Solid electrolyte, preparation method thereof and lithium ion battery Download PDF

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Publication number
CN111554975A
CN111554975A CN202010394307.XA CN202010394307A CN111554975A CN 111554975 A CN111554975 A CN 111554975A CN 202010394307 A CN202010394307 A CN 202010394307A CN 111554975 A CN111554975 A CN 111554975A
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Prior art keywords
electrolyte
solid
lithium
polymer
framework
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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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    • 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
    • H01M10/0564—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes the electrolyte being constituted of organic materials only
    • H01M10/0565—Polymeric materials, e.g. gel-type or solid-type
    • 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 solid electrolyte, a preparation method thereof and a lithium ion battery, wherein the solid electrolyte comprises a polymer electrolyte framework and a plastic crystal electrolyte at least filled in the polymer electrolyte framework; wherein the composition of the polymer electrolyte skeleton comprises a polymer and a lithium salt. The solid electrolyte has excellent conductivity and mechanical strength, and the cycle life of the lithium ion battery can be remarkably prolonged after the solid electrolyte is applied to the lithium ion battery.

Description

Solid electrolyte, preparation method thereof and lithium ion battery
Technical Field
The invention relates to an electrolyte, in particular to a solid electrolyte, a preparation method thereof and a lithium ion battery, and belongs to the technical field of lithium ion 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. The good mechanical property of the solid electrolyte can effectively inhibit the growth in the lithium metal negative electrode, greatly reduces the short circuit risk caused by the penetration of dendrites, and enables the metal lithium to be possible to be used as the negative electrode material of the lithium ion battery, thereby effectively improving the energy density of the lithium ion battery.
However, the problem of the interface between the solid electrolyte and the electrode is a difficult problem for limiting the development of the solid battery, and due to the characteristics of solid/solid rigid interface contact between the electrode and the solid electrolyte, particularly the interface resistance between positive electrode material particles is large, the compatibility is poor, the effective transmission of conductive carriers is seriously influenced, and finally the performance of the solid battery cannot be fully exerted. Therefore, how to improve the interface problem and increase the ionic conductivity becomes the focus of research in the field of solid-state batteries at present.
The plastic crystal electrolyte is a novel electrolyte material with plasticity, although the plastic electrolyte material is solid in appearance, the plastic crystal electrolyte has certain characteristics of liquid molecules, the lithium salt can be effectively dissociated by the high polarity and the high diffusivity of the plastic crystal material, the ionic conductivity and the electrochemical stability are ensured, and the plastic crystal electrolyte has the safety of a solid electrolyte and the contact property of a liquid electrolyte, so the plastic crystal electrolyte is a very potential electrolyte material. However, the plastic crystal electrolyte material has the problems of poor mechanical strength and poor formability, the mechanical strength of the plastic crystal electrolyte with a too thin thickness is too poor, and the plastic crystal electrolyte with a too thick thickness can not meet the requirement of the energy density of the battery.
Therefore, it is desirable to provide a solid electrolyte having both excellent conductivity and mechanical strength to improve the overall performance of the battery.
Disclosure of Invention
The invention provides a solid electrolyte which has excellent conductivity and mechanical strength by improving the structure of the solid electrolyte, and can obviously prolong the cycle life of a lithium ion battery after being applied to the lithium ion battery.
The invention also provides a preparation method of the solid electrolyte, which improves the polymerization environment of the plastic crystal electrolyte by introducing a 3D printing technology, so that the solid electrolyte with obviously improved conductivity and mechanical strength can be obtained.
The invention also provides a lithium ion battery which comprises the solid electrolyte, so that the cycle performance and the safety performance of the lithium ion battery are obviously improved.
The invention provides a solid electrolyte, which comprises a polymer electrolyte framework and a plastic crystal electrolyte at least filled in the polymer electrolyte framework;
wherein the composition of the polymer electrolyte skeleton comprises a polymer and a lithium salt.
The solid electrolyte as described above, wherein the mass ratio of the polymer electrolyte skeleton to the plastocrystalline electrolyte is (1: 4) - (4: 1).
The solid electrolyte as described above, wherein the polymer electrolyte skeleton comprises, in mass percent: 50-90% of polymer, 5-40% of lithium salt, 0-10% of nano ceramic filler and 0-5% of toughening compatilizer.
The solid electrolyte as described above, wherein the solid electrolyte is prepared by a method comprising:
volatilizing a solvent in a solution at least containing the polymer and lithium salt, preparing a wire from the obtained solid to obtain a wire material, and performing 3D printing by taking the wire material as a raw material to obtain the polymer electrolyte framework; soaking the polymer electrolyte into a precursor solution of plastic crystal electrolyte and heating to obtain the solid electrolyte;
the precursor solution comprises a monomer, an electrolyte and an initiator.
The solid electrolyte as described above, wherein the mass of the monomer is 20 to 60% of the mass of the precursor solution, the mass of the electrolyte is 40 to 80% of the mass of the precursor solution, and the mass of the initiator is 0.1 to 2% of the mass of the monomer.
The solid electrolyte as described above, wherein the polymer 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, polyvinyl acetate, and/or,
the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulphonylimide, lithium bistrifluorosulphonylimide, lithium dioxalate borate, lithium difluorooxalato borate, lithium trifluoromethanesulfonate and lithium bis (trifluoromethylsulphonyl) imide, and/or,
the nano ceramic filler is at least one selected from alumina, silica, titanium dioxide, zinc oxide and zirconia.
The solid electrolyte as described above, wherein the monomer is at least one selected from the group consisting of triethylene glycol diacrylate, trimethylolpropane trimethacrylate, 2-phenoxyethyl acrylate, polyethylene glycol methacrylate, t-butyl acrylamide, and/or,
the initiator is selected from one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and benzoyl peroxide.
The invention also provides a preparation method of the solid electrolyte, which comprises the following steps:
volatilizing a solvent in a solution at least containing the polymer and lithium salt, and then preparing silk from the obtained solid substance to obtain a silk material;
3D printing is carried out by taking the wire as a raw material to obtain the polymer electrolyte framework;
soaking the polymer electrolyte framework in a precursor solution of plastic crystal electrolyte and heating to obtain the solid electrolyte; the precursor solution comprises a monomer, an electrolyte and an initiator.
The preparation method of the solid electrolyte comprises the steps of heating for 3-20h at 50-90 ℃.
The invention also provides a lithium ion battery, and the electrolyte of the lithium ion battery is the solid electrolyte.
The solid electrolyte comprises a polymer electrolyte framework and a plastic crystal electrolyte at least filled in the polymer electrolyte framework, wherein the polymer electrolyte framework comprises a polymer and a lithium salt. Wherein, the polymer electrolyte framework provides a powerful support for the plastic crystal electrolyte, thereby ensuring the strength of the plastic crystal electrolyte in the application process. Therefore, the solid electrolyte effectively utilizes the conductivity and electrochemical stability of the plastic crystal electrolyte on the premise of excellent mechanical strength. Furthermore, the polymer electrolyte framework also has certain ion conducting characteristics. Therefore, the solid electrolyte of the present invention can exhibit excellent electrical conductivity as well as mechanical strength.
The preparation method of the solid electrolyte utilizes the 3D printing technology to obtain the electro-polymer electrolyte framework which has enough mechanical strength and provides an in-situ polymerization place for the plastic crystal electrolyte, thereby obtaining the solid electrolyte with excellent conductivity and mechanical strength.
The lithium ion battery provided by the invention comprises the solid electrolyte, so that the lithium ion battery has excellent cycle performance and safety performance.
Drawings
FIG. 1 is a schematic structural view of a polymer electrolyte matrix according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a further embodiment of the polymer electrolyte skeleton of the present invention;
FIG. 3 is a schematic structural diagram of an embodiment of a solid electrolyte according to the present invention;
FIG. 4 is a schematic structural view of a solid electrolyte according to still another embodiment of the present invention;
fig. 5 is an ac impedance diagram of the solid electrolyte of example 7.
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 invention provides a solid electrolyte, which comprises a polymer electrolyte framework and a plastic crystal electrolyte filled in the polymer electrolyte framework; wherein the composition of the polymer electrolyte skeleton comprises a polymer and a lithium salt.
The polymer electrolyte in the solid electrolyte of the present invention means a structure having a composition including a polymer and a lithium salt, having a three-dimensional structure, having a receiving space, and having a certain supporting function, and the present invention does not limit parameters such as a specific shape, size, structure, porosity, and the like of the polymer electrolyte as long as the above definition is satisfied. For example, a regular network or an irregular network.
Fig. 1 is a schematic structural view of an embodiment of the polymer electrolyte skeleton according to the present invention, and as shown in fig. 1, the polymer electrolyte skeleton in fig. 1 is a regular network structure formed by intersecting a plurality of columnar structures.
Fig. 2 is a schematic structural view of another embodiment of the polymer electrolyte skeleton according to the present invention, and as shown in fig. 2, the polymer electrolyte skeleton in fig. 2 is an irregular network structure formed by intersecting a plurality of irregular structures.
In the specific implementation process of the invention, the preparation of the polymer electrolyte framework can be realized by using a 3D printing technology.
The solid electrolyte comprises a polymer electrolyte framework and a plastic crystal electrolyte filled at least in the pores of the polymer electrolyte framework. It is understood that the solid electrolyte of the present invention may include a plastic crystal electrolyte coated on the surface of the polymer electrolyte skeleton, in addition to the plastic crystal electrolyte filled in the pores of the polymer electrolyte skeleton.
Fig. 3 is a schematic structural diagram of an embodiment of the solid-state electrolyte of the present invention, and as shown in fig. 3, the solid-state electrolyte in fig. 3 includes the polymer electrolyte skeleton 1 shown in fig. 1 and the plastic-crystal electrolyte 2 wrapping the entire polymer electrolyte skeleton, wherein a portion of the plastic-crystal electrolyte is filled in the pores of the polymer electrolyte skeleton 1.
Fig. 4 is a schematic structural diagram of another embodiment of the solid-state electrolyte of the present invention, and as shown in fig. 4, the solid-state electrolyte in fig. 4 includes the polymer electrolyte skeleton 1 shown in fig. 2 and the plastic-crystal electrolyte 2 wrapping the entire polymer electrolyte skeleton, wherein a portion of the plastic-crystal electrolyte is filled in the pores of the polymer electrolyte skeleton 1.
According to the technical scheme provided by the invention, after the solid electrolyte is applied to the lithium ion battery, the growth of lithium dendrite can be effectively inhibited, and the cycle performance and the safety performance of the lithium ion battery are improved. The reason is that the structure of the solid electrolyte is designed, the plastic crystal electrolyte and the polymer electrolyte framework are compounded, wherein the polymer electrolyte framework not only has ion conductivity, but also has good contact wettability with the surface of an electrode and can effectively reduce the interface impedance, and more importantly, the polymer electrolyte framework provides strong adhesion for the plastic crystal electrolyte with excellent ionic conductivity and electrochemical stability, so that the defects of poor mechanical strength and poor formability of the plastic crystal electrolyte are overcome. Therefore, the solid electrolyte has excellent conductivity and mechanical strength, can inhibit the growth of lithium dendrites in the long-term circulation process of the lithium ion battery, reduces the short-circuit probability, and improves the circulation performance and the safety performance of the lithium ion battery.
In order to further ensure that the polymer electrolyte framework can strongly support the plastic crystal electrolyte, ensure that parameters such as flexibility, mechanical property and ion conductivity of the electrolyte meet most requirements, ensure that the solid electrolyte has better comprehensive performance, and control the mass ratio of the polymer electrolyte framework to the plastic crystal electrolyte to be (1: 4) - (4: 1).
In order to further improve the mechanical strength of the polymer electrolyte matrix, the polymer electrolyte matrix of the present invention may further include an auxiliary agent, such as a nano ceramic filler and a toughening compatibilizer, in addition to the above lithium salt and the polymer.
Specifically, the polymer electrolyte framework comprises the following components in percentage by mass: 50-90% of polymer, 5-40% of lithium salt, 0-10% of nano ceramic filler and 0-5% of toughening compatilizer.
The mass content of the nano ceramic filler and the toughening compatilizer in the polymer electrolyte framework can be selected according to the requirement on the mechanical property of the polymer electrolyte framework.
The solid electrolyte of the present invention is prepared by a method comprising the following processes:
volatilizing a solvent in a solution at least containing the polymer and lithium salt, preparing a wire from the obtained solid to obtain a wire material, and performing 3D printing by taking the wire material as a raw material to obtain the polymer electrolyte framework; soaking the polymer electrolyte framework in a precursor solution of plastic crystal electrolyte and heating to obtain the solid electrolyte; the precursor solution comprises a monomer, an electrolyte and an initiator.
In practice, the material for 3D printing may be prepared first. Specifically, raw materials (at least comprising lithium salt and polymer) forming a polymer electrolyte framework are mixed with an organic solvent, the mixture is stirred to enable the raw materials to be fully contacted and mixed to form a homogeneous solution, then the solvent in the mixed system is volatilized, and the obtained solid is subjected to wire making, so that the wire for 3D printing is obtained. And (3) carrying out 3D printing on the silk material serving as a raw material according to preset printing data to obtain the polymer electrolyte framework. And then, soaking the polymer electrolyte framework in a precursor solution containing a monomer, an electrolyte and an initiator and used for preparing a plastic crystal electrolyte, heating to initiate a polymerization reaction, wherein in the polymerization reaction, the plastic crystal electrolyte is attached to the polymer electrolyte framework and gradually expanded and filled in pores of the polymer electrolyte framework, even wraps the whole polymer electrolyte framework, and finally the solid electrolyte is obtained.
The invention is used for preparing the precursor solution of the plastic crystal electrolyte, the mass of a monomer is 20-60% of the mass of the precursor solution, the mass of an initiator is 0.1-2% of the mass of the monomer, and the mass of an electrolyte is 40-80% of the mass of the precursor solution.
In the raw materials for forming the polymer electrolyte framework, the polymer 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, and/or,
the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulphonylimide, lithium bistrifluorosulphonylimide, lithium dioxalate borate, lithium difluorooxalato borate, lithium trifluoromethanesulfonate and lithium bis (trifluoromethylsulphonyl) imide, and/or,
the nano ceramic filler is at least one of alumina, silica, titanium dioxide, zinc oxide and zirconia.
In the precursor solution for preparing the plastic crystal electrolyte, the monomer is at least one selected from triethylene glycol diacrylate, trimethylolpropane trimethacrylate, 2-phenoxyethyl acrylate, polyethylene glycol methacrylate and tert-butyl acrylamide, and/or,
the initiator is selected from one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and benzoyl peroxide.
Further, the electrolyte in the precursor solution may be 1M LiPF6/EC-DEC、1M LiPF6EC-DMC, or other commercially available electrolytes.
In a second aspect, the present invention provides a method for preparing the solid electrolyte of the first aspect, comprising the steps of:
volatilizing a solvent in a solution at least containing the polymer and lithium salt, and then preparing silk from the obtained solid substance to obtain a silk material;
3D printing is carried out by taking the wire as a raw material to obtain the polymer electrolyte framework;
soaking the polymer electrolyte framework in a precursor solution of plastic crystal electrolyte and heating to obtain a solid electrolyte; the precursor solution comprises a monomer, an electrolyte and an initiator.
The types of the raw materials, the compositions of the raw materials and the like in the preparation method are the same as those described above, and the details are not repeated herein.
Before performing 3D printing, raw materials including at least a lithium salt and a polymer for constituting a polymer electrolyte skeleton are mixed and stirred with an organic solvent, such as one or more of Acetonitrile (ACN), N-methylpyrrolidone (NMP), Dimethylformamide (DMF), Dimethylsulfoxide (DMSO), acetone, dichloromethane, chloroform, xylene, and Tetrahydrofuran (THF). In the stirring process, the homogeneity degree of the raw materials in the solvent can be increased by controlling the stirring temperature, the stirring speed and the stirring time, specifically, the stirring temperature can be 25-150 ℃, the stirring speed can be 300-1000rpm, and the stirring time can be 3-24 h. Wherein the stirring temperature may be further determined according to the boiling point of the solvent.
Subsequently, the mixed solution is subjected to heat treatment to volatilize the solvent therein to obtain a solid. In order to further ensure the solid content of the solid, the solid can be subjected to vacuum drying treatment after the solvent is volatilized. Wherein 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.
In order to facilitate 3D printing, the solid matter needs to be subjected to silk making treatment. For example, the solid matter may be pulverized and fed into an extruder to be blended and drawn by a drawing machine to form a uniform-sized strand. In order to ensure that the polymer electrolyte framework is well macroscopically formed and has no air holes and crack defects, the wire with the diameter of 0.2-0.8 mm can be obtained by controlling the parameters of the wire making process. Illustratively, the filament discharging speed can be 5-30cm/min, and the filament making temperature can be 80-235 ℃.
And after the wire making treatment is finished, performing 3D printing on the obtained wire material serving as a raw material according to preset printing data to obtain the polymer electrolyte framework. The 3D printing of the present invention may specifically be a fused deposition technique, and the preset print data may be obtained by performing three-dimensional modeling using software such as 3D max, Maya, CAD, and the like, and it can be understood that the preset print data is different according to the difference in size, shape, structure, porosity, and pore diameter of the polymer electrolyte skeleton.
And finally, soaking the printed polymer electrolyte framework in a precursor solution of plastic crystal electrolyte and heating, wherein the plastic crystal electrolyte is continuously synthesized by taking the polymer electrolyte framework as an implantation space and an attachment point, has an enlarged volume, is gradually filled in pores of the polymer electrolyte framework, and even wraps the whole polymer electrolyte framework, so as to obtain the solid electrolyte.
In a third aspect, the present invention provides a lithium ion battery comprising the solid electrolyte of the first 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, it is possible to suppress the growth of lithium dendrites during long-term use, and has excellent cycle performance as well as safety performance.
Hereinafter, the solid electrolyte and the lithium ion battery according to the present invention will be described in detail by way of specific examples.
Example 1
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 23.6g of polylactic acid (PLA, Mw about 60000), 7.3g of lithium bistrifluoromethylsulfonimide (LiTFSI) and 2.8g of Silica (SiO)2) The mixture is placed in a beaker, dissolved in a certain amount of chloroform and uniformly stirred at the rotating speed of 500rpm for 3 hours at the temperature of 35 ℃ until a homogeneous solution is formed;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 50 ℃ for 12 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 161 ℃, the traction is carried out by a tractor at the speed of 10cm/min, the diameter of the extruded wires is 0.40mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using 3D max software to obtain printing data, performing 3D printing by using wires as raw materials by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing;
4. uniformly stirring 4.4g of triethylene glycol diacrylate (TEGDA), 16g of commercially available lithium ion electrolyte and 0.02g of Azobisisoheptonitrile (ABVN) at the rotating speed of 400rpm for 5 hours to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 50 ℃ for 12h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 3;
5. the lithium ion battery of the embodiment is manufactured by using the solid electrolyte of the embodiment, and a positive plate and a metal lithium negative plate which are coated by lithium cobaltate, acetylene black and PVDF, and adopting the existing lamination process.
Example 2
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. uniformly mixing 18g of polycaprolactone (PCL, the Mw of which is about 80000), 7.8g of polyethylene oxide (PEO, the Mw of which is about 100W), 8.5g of lithium difluorooxalato borate (LiDFOB) and 0.2g of epoxy type toughening compatilizer, putting the mixture into a beaker, dissolving the mixture into a certain amount of ACN, and uniformly stirring the mixture at the temperature of 50 ℃ and the rotating speed of 1000rpm for 3 hours to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 59 ℃ for 18h, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 78 ℃, the traction is carried out by a traction machine at the speed of 22cm/min, the diameter of the extruded wires is 0.80mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using 3D max software to obtain printing data, performing 3D printing by using wires as raw materials by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing;
4. 6.1g of trimethylolpropane trimethacrylate (TMPTMA) and 23.5g of LiPF6The solution is prepared by uniformly stirring EC/DEC electrolyte and 0.018g of Azobisisobutyronitrile (AIBN) for 6 hours at the rotating speed of 300rpm to form precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 55 ℃ for 8h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment, wherein the mass ratio of the polymer electrolyte framework to the plastic crystal electrolyte is 2.4: 1;
5. the solid electrolyte of the present example was used in combination with LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.6Mn0.2O2The Super-P and CMC are coated into a positive plate, and the graphite negative plate is manufactured into the lithium ion battery of the embodiment by adopting the existing winding process.
Example 3
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. uniformly mixing 11.9g of acrylonitrile-butadiene-styrene (ABS) plastic and 4.1g of lithium bis (oxalato) borate (LiBOB), putting the mixture into a beaker, dissolving the mixture into a certain amount of dichloromethane, and uniformly stirring the mixture at 25 ℃ at the rotating speed of 800rpm for 6 hours to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 50 ℃ for 10 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 225 ℃, the traction is carried out by a traction machine at the speed of 30cm/min, the diameter of the extruded wires is 0.70mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using Maya software to obtain printing data, performing 3D printing by using wires as raw materials by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 2, and weighing;
4. uniformly stirring 5.2g of 2-phenoxyethyl acrylate (EGPEA), 15.8g of commercially available lithium ion electrolyte and 0.023g of Azobisisobutyronitrile (AIBN) at the rotating speed of 300rpm for 14 hours to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 70 ℃ for 6h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 1.5 of a solid electrolyte;
5. the lithium ion battery of the embodiment is manufactured by using the solid electrolyte of the embodiment, and a positive plate and a metallic lithium negative plate which are coated by lithium iron phosphate, PVDF and CNT, and adopting the existing lamination process.
Example 4
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 17.2g of thermoplastic polyurethane (TPU, Mw of around 70000), 5.8g of lithium perchlorate (LiClO)4) Uniformly mixing, placing in a beaker, dissolving in a certain amount of DMF, and uniformly stirring at the rotation speed of 550rpm at 75 ℃ for 7h to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 115 ℃ for 15 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 162 ℃, the traction is carried out by a traction machine at the speed of 12cm/min, the diameter of the extruded wires is 0.40mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using CAD software to obtain printing data, performing 3D printing by using a wire material as a raw material by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 2, and weighing the framework;
4. uniformly stirring 9.6g of polyethylene glycol methacrylate (PEGMA), 27.3g of commercially available lithium ion electrolyte and 0.015g of Azobisisoheptonitrile (ABVN) at 900rpm for 3h to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 60 ℃ for 20h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 3.2 of a solid electrolyte;
5. the solid electrolyte of the present example was used in combination with LiNi0.8Co0.15Al0.05O2The lithium ion battery of the present embodiment is manufactured by using the conventional winding process for the positive electrode sheet and the lithium indium alloy negative electrode sheet coated with ketjen black and SA.
Example 5
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 19.3g of acrylonitrile-butadiene-styrene (ABS), 2.5g of polyvinyl acetate (PVAc, Mw about 100000), and 8g of lithium hexafluorophosphate (LiPF)6) And cyclic acid anhydride typeUniformly mixing 0.12g of toughening compatilizer, putting the mixture into a beaker, dissolving the mixture into a certain amount of acetone, and uniformly stirring the mixture at 40 ℃ for 5 hours at the rotating speed of 850rpm to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 50 ℃ for 6 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, 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 wires is 0.4mm, wire materials with uniform size are formed, and the wire materials are coiled;
3. performing three-dimensional modeling by using 3D max software to obtain printing data, performing 3D printing by using wires as raw materials by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing;
4. 7.6g of t-butylacrylamide and 19.1g of LiPF6The solution is uniformly stirred for 1h at the rotation speed of 600rpm by 0.046g of Benzoyl Peroxide (BPO) and EC/DMC electrolyte to form precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 80 ℃ for 9h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 2;
5. the lithium ion battery of the embodiment is manufactured by using the solid electrolyte of the embodiment, and a positive plate and a metal lithium alloy negative plate which are coated by lithium cobaltate, PVDF and graphene, and adopting the existing lamination process.
Example 6
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 2.3g of polyethylene oxide (PEO, Mw about 5000000), 17.6g of polylactic acid (PLA), 5.9g of lithium bis (fluorosulfonyl) imide (LiFSI), 4.1g of Al2O3Mixing with 0.08g of cyclic anhydride type toughening compatibilizer uniformly, placing the mixture into a beaker, dissolving the mixture into a certain amount of chloroform, and uniformly stirring the mixture at 35 ℃ for 10 hours at the rotating speed of 900rpm to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 52 ℃ for 15 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 136 ℃, the traction is carried out by a traction machine at the speed of 24cm/min, the diameter of the extruded wires is 0.65mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using CAD software to obtain printing data, performing 3D printing by using a wire material as a raw material by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 2, and weighing the framework;
4. uniformly stirring 5.4g of trimethylolpropane trimethacrylate (TMPTMA), 12.3g of commercially available lithium ion electrolyte and 0.002g of Azobisisoheptonitrile (ABVN) at the rotating speed of 500rpm for 2 hours to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 65 ℃ for 20h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1.4: 1;
5. the lithium ion battery of the embodiment is manufactured by using the solid electrolyte of the embodiment, lithium iron phosphate, a positive plate of Super-P, PVDF and a graphite negative plate through the conventional winding process.
Example 7
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 16.9g of polylactic acid (PLA), 2.8g of polyvinyl acetate (PVAc, Mw about 500000) and 4.1g of lithium trifluoromethanesulfonate (LiCF)3SO3) Uniformly mixing, placing in a beaker, dissolving in a certain amount of dichloromethane, and uniformly stirring at the rotation speed of 750rpm for 4h at the temperature of 30 ℃ to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at the temperature of 35 ℃ for 19 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 144 ℃, the traction is carried out by a traction machine at the speed of 7cm/min, the diameter of the extruded wires is 0.35mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using CAD software to obtain printing data, performing 3D printing by using a wire material as a raw material by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing the framework;
4. 5.0g of triethylene glycol diacrylate (TEGDA) and 18.1g of LiPF6The solution is prepared by uniformly stirring EC/DEC electrolyte and 0.016g of Azobisisobutyronitrile (AIBN) for 3 hours at the rotating speed of 1000rpm to form precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 70 ℃ for 18h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 3.5 of a solid electrolyte;
5. the solid electrolyte of the present example was used in combination with LiNi0.8Co0.1Mn0.1O2The lithium ion battery of the embodiment is manufactured by adopting the existing lamination process for the positive plate and the silicon-carbon negative plate which are assembled by the Super-P and the PVDF.
Example 8
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 11.4g of Polycaprolactone (PCL), 1g of polyvinyl chloride (PVC, Mw about 55000) and 3.5g of lithium bis (trifluoromethylsulfonyl) imide LiN (CF)3SO2)2Mixing with 0.05g oxazoline toughening compatibilizer uniformly, placing into a beaker, dissolving in a certain amount of THF, heating in a water bath at 65 ℃, and uniformly stirring at the rotating speed of 650rpm for 4h to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 58 ℃ for 24 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 96 ℃, the traction is carried out by a traction machine at the speed of 15cm/min, the diameter of the extruded wires is 0.55mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using Maya software to obtain printing data, performing 3D printing by using wires as raw materials by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing;
4. uniformly stirring 6.9g of 2-phenoxyethyl acrylate (EGPEA), 20g of commercially available lithium ion electrolyte and 0.06g of dimethyl Azodiisobutyrate (AIBME) at the rotating speed of 450rpm for 5 hours to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 90 ℃ for 8h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 1.9 of a solid electrolyte;
5. the solid electrolyte of the present example was used in combination with LiNi0.3Co0.3Mn0.3O2And the positive plate and the metal lithium negative plate which are assembled by AB and PVDF are manufactured into the solid-state lithium ion battery by adopting the existing winding process.
Example 9
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 14.4g of thermoplastic polyurethane (TPU, Mw of around 70000), 4.6g of vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP, Mw of around 500000), 5.5g of lithium bistrifluoromethylsulfonyl imide (LiTFSI) and 1.6g of titanium dioxide (TiO)2) The components are uniformly mixed and then are placed in a beaker, then are dissolved in a certain amount of NMP, are heated in a water bath at 70 ℃, and are uniformly stirred for 8 hours at the rotating speed of 700rpm until a homogeneous solution is formed;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 150 ℃ for 14h, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending to prepare wires, wherein the silk preparation temperature is 167 ℃, drawing at the speed of 24cm/min by a drawing machine, the diameter of the extruded wires is 0.6mm, forming wires with uniform size, and coiling the wires;
3. performing three-dimensional modeling by using 3D max software to obtain printing data, performing 3D printing by using wires as raw materials by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 2, and weighing the framework;
4. 7.5g of 2-phenoxyethyl acrylate (EGPEA) and 27.4g of LiPF6EC/DMC electrolyte, 0.02g Azodiisobutyronitrile (AIBN) and 900rpm speed stirring evenly for 4 hours, precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 70 ℃ for 5 hours for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 2.5 of a solid electrolyte;
5. the solid electrolyte of the embodiment is matched with lithium cobaltate, CNT and CMC to assemble a positive plate and a graphite negative plate, and the solid lithium ion battery is manufactured by adopting the existing lamination process.
Example 10
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. uniformly mixing 9.2g of acrylonitrile-butadiene-styrene (ABS) plastic and 3.8g of lithium difluorooxalato borate (LiDFOB), putting the mixture into a beaker, dissolving the mixture in a certain amount of DMF, heating the mixture in a water bath at 55 ℃, and uniformly stirring the mixture for 15 hours at the rotating speed of 800rpm to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 120 ℃ for 16h, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing silk, wherein the silk preparation temperature is 227 ℃, the silk preparation temperature is dragged by a tractor at a speed of 15cm/min, the diameter of the extruded silk is 0.25mm, the silk with uniform size is formed, and the silk is coiled;
3. performing three-dimensional modeling by using CAD software to obtain printing data, performing 3D printing by using a wire material as a raw material by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing the framework;
4. uniformly stirring 5.8g of 2-phenoxyethyl acrylate (EGPEA), 22g of commercially available lithium ion electrolyte and 0.13g of Benzoyl Peroxide (BPO) at the rotating speed of 600rpm for 5 hours to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 80 ℃ for 13h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 2: 1.3 of a solid electrolyte;
5. the solid electrolyte of the present example was used in combination with LiNi0.6Co0.2Mn0.2O2The positive plate and the metal lithium negative electrode which are assembled by the CNT and the PVDF adopt the existing lamination process to manufacture the lithium ion battery of the embodiment.
Example 11
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. 16.9g of polylactic acid (PLA), 2.8g of polyvinyl acetate (PVAc, Mw about 500000) and 4.1g of lithium trifluoromethanesulfonate (LiCF)3SO3) Uniformly mixing, placing in a beaker, dissolving in a certain amount of dichloromethane, and uniformly stirring at the rotation speed of 750rpm for 4h at the temperature of 30 ℃ to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at the temperature of 35 ℃ for 19 hours, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing wires, wherein the wire preparation temperature is 144 ℃, the traction is carried out by a traction machine at the speed of 7cm/min, the diameter of the extruded wires is 0.35mm, wires with uniform size are formed, and the wires are coiled;
3. performing three-dimensional modeling by using CAD software to obtain printing data, performing 3D printing by using a wire material as a raw material by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing the framework;
4. 5.0g of triethylene glycol diacrylate (TEGDA) and 18.1g of LiPF6The solution is prepared by uniformly stirring EC/DEC electrolyte and 0.016g of Azobisisobutyronitrile (AIBN) for 3 hours at the rotating speed of 1000rpm to form precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 70 ℃ for 18h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte of the embodiment with a mass ratio of 1: 6;
5. the solid electrolyte of the present example was used in combination with LiNi0.8Co0.1Mn0.1O2The lithium ion battery of the embodiment is manufactured by adopting the existing lamination process for the positive plate and the silicon-carbon negative plate which are assembled by the Super-P and the PVDF.
Example 12
The preparation method of the lithium ion battery of the embodiment comprises the following steps:
1. uniformly mixing 9.2g of acrylonitrile-butadiene-styrene (ABS) plastic and 3.8g of lithium difluorooxalato borate (LiDFOB), putting the mixture into a beaker, dissolving the mixture in a certain amount of DMF, heating the mixture in a water bath at 55 ℃, and uniformly stirring the mixture for 15 hours at the rotating speed of 800rpm to form a homogeneous solution;
2. heating the homogeneous solution to fully volatilize the solvent to obtain a blocky solid, drying the blocky solid in vacuum at 120 ℃ for 16h, and shearing and grinding the blocky solid;
feeding the ground particles into a screw extruder, blending and preparing silk, wherein the silk preparation temperature is 227 ℃, the silk preparation temperature is dragged by a tractor at a speed of 15cm/min, the diameter of the extruded silk is 0.25mm, the silk with uniform size is formed, and the silk is coiled;
3. performing three-dimensional modeling by using CAD software to obtain printing data, performing 3D printing by using a wire material as a raw material by using a fused deposition technology to obtain a polymer electrolyte framework shown in figure 1, and weighing the framework;
4. uniformly stirring 5.8g of 2-phenoxyethyl acrylate (EGPEA), 22g of commercially available lithium ion electrolyte and 0.13g of Benzoyl Peroxide (BPO) at the rotating speed of 600rpm for 5 hours to form a precursor solution;
soaking the polymer electrolyte framework in the precursor solution, heating at 80 ℃ for 13h for in-situ polymerization, and cutting according to a required shape after curing to obtain the polymer electrolyte framework and the plastic crystal electrolyte with the mass ratio of 4.3: 1;
5. the solid electrolyte of the present example was used in combination with LiNi0.6Co0.2Mn0.2O2The positive plate and the metal lithium negative electrode which are assembled by the CNT and the PVDF adopt the existing lamination process to manufacture the lithium ion battery of the embodiment.
Comparative example 1
Compared with the preparation method of the lithium ion battery of the comparative example 1, the preparation method does not contain the step of preparing the polymer electrolyte framework, and comprises the following specific steps:
1. coating the precursor solution in the example 1 on a glass plate, heating at 50 ℃ for 12h for in-situ polymerization, and cutting according to a required shape after curing to obtain the solid electrolyte of the comparative example;
2. the lithium ion battery of the comparative example is manufactured by adopting the existing lamination process to manufacture the positive plate and the metal lithium negative plate which are coated by matching the solid electrolyte of the comparative example with lithium cobaltate, acetylene black and PVDF.
Comparative example 2
Compared with the preparation method of the lithium ion battery of the comparative example 2, the preparation method does not contain the step of preparing the polymer electrolyte framework, and comprises the following specific steps:
1. coating the precursor solution in the example 2 on a glass plate, heating at 55 ℃ for 8h for in-situ polymerization, and cutting according to a required shape after curing to obtain the solid electrolyte of the comparative example;
2. the solid electrolyte of the comparative example was used in combination with LiNi0.5Co0.3Mn0.2O2、LiNi0.6Co0.6Mn0.2O2The positive plate and the graphite negative plate coated by the Super-P and the CMC are manufactured into the lithium ion battery of the comparative example by adopting the existing winding process.
Comparative example 3
Compared with example 3, the preparation method of the lithium ion battery of the comparative example does not contain the step of preparing the polymer electrolyte framework, and comprises the following specific steps:
1. coating the precursor solution in the example 3 on a glass plate, heating at 70 ℃ for 6h for in-situ polymerization, and cutting according to a required shape after curing to obtain the solid electrolyte of the comparative example;
2. the lithium ion battery of the comparative example is manufactured by using the solid electrolyte of the comparative example, and adopting the existing lamination process to manufacture the positive plate and the metal lithium negative plate which are coated by matching lithium iron phosphate, PVDF and CNT.
Comparative example 4
Compared with the preparation method of the lithium ion battery of the comparative example 4, the preparation method does not contain the step of preparing the polymer electrolyte framework, and comprises the following specific steps:
1. coating the precursor solution in the example 4 on a glass plate, heating at 60 ℃ for 20h for in-situ polymerization, and cutting according to the required shape after curing to obtain the solid electrolyte of the comparative example;
2. the solid electrolyte of the comparative example was used in combination with LiNi0.8Co0.15Al0.05O2The lithium ion battery of the comparative example is manufactured by adopting the existing winding process for the positive plate and the lithium indium alloy negative plate which are coated by Ketjen black and SA.
Comparative example 5
Compared with the preparation method of the lithium ion battery of the comparative example 5, the preparation method does not contain the step of preparing the polymer electrolyte framework, and comprises the following specific steps:
1. coating the precursor solution in the example 5 on a glass plate, heating at 80 ℃ for 9h for in-situ polymerization, and cutting according to a required shape after curing to obtain the solid electrolyte of the comparative example;
2. the lithium ion battery of the comparative example is manufactured by using the solid electrolyte of the comparative example, and a positive plate and a metal lithium alloy negative plate which are coated by lithium cobaltate, PVDF and graphene and adopting the existing lamination process.
Test examples
1. The room temperature (25 ℃ C.) impedance of the solid electrolytes of examples 1 to 10 and comparative examples 1 to 5 was measured in the following manner
The test is carried out by adopting an electrochemical workstation of Shanghai Chenghua CHI600E, stainless steel symmetrical electrodes are arranged on two sides of the electrolyte, the amplitude is set to be 10mV, and the frequency range is 0.1 HZ-1 MHZ.
Fig. 5 is an ac impedance diagram of the solid electrolyte of example 7. As shown in fig. 5, the all-solid electrolyte of example 7 has excellent conductivity. The ac impedance plots of the solid electrolytes of examples 1 to 6 and 8 to 10 are similar to fig. 5. Therefore, the all-solid-state electrolyte of the present invention has excellent conductivity.
2. The tensile strengths of the solid electrolytes of examples 1 to 10 and comparative examples 1 to 5 were measured in the following manner
The testing is carried out by adopting an electronic tensile machine with the detection precision of 0.1N, and the tensile speed is as follows: (100. + -.1) mm/min, stretch spacing: (100 ± 5) mm, sample width: (15. + -. 0.1) mm.
3. The cycle life of the lithium ion batteries of examples 1 to 10 and comparative examples 1 to 5 was measured in the following manner
And (3) testing the cycle performance of the lithium ion battery by adopting Wuhan blue light test equipment under the test condition that constant-current charging and discharging tests are carried out at room temperature at 0.1 ℃.
4. The short-circuit rates of the lithium ion batteries of examples 1 to 10 and comparative examples 1 to 5 were measured using a multimeter
TABLE 1
Figure BDA0002487040550000191
Figure BDA0002487040550000201
From table 1, it can be seen that: the solid electrolyte of the present invention has both excellent electrical conductivity and mechanical strength. Therefore, the lithium ion battery comprising the solid electrolyte can inhibit the growth of lithium dendrites, and has good cycle performance and safety 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. The solid electrolyte is characterized by comprising a polymer electrolyte framework and a plastic crystal electrolyte filled in the polymer electrolyte framework;
wherein the composition of the polymer electrolyte skeleton comprises a polymer and a lithium salt.
2. The solid electrolyte of claim 1, wherein the mass ratio of the polymer electrolyte backbone to the plastocrystalline electrolyte is (1: 4) - (4: 1).
3. The solid-state electrolyte of claim 1 or 2, wherein the polymer electrolyte skeleton comprises, in mass percent: 50-90% of polymer, 5-40% of lithium salt, 0-10% of nano ceramic filler and 0-5% of toughening compatilizer.
4. The solid electrolyte of claim 3, wherein the solid electrolyte is prepared by a method comprising:
volatilizing a solvent in a solution at least containing the polymer and lithium salt, preparing a wire from the obtained solid to obtain a wire material, and performing 3D printing by taking the wire material as a raw material to obtain the polymer electrolyte framework; soaking the polymer electrolyte into a precursor solution of plastic crystal electrolyte and heating to obtain the solid electrolyte;
the precursor solution comprises a monomer, an electrolyte and an initiator.
5. Solid-state electrolyte according to claim 4, characterized in that the mass of the monomer is 20-60% of the mass of the precursor solution, the mass of the electrolyte is 40-80% of the mass of the precursor solution, and the mass of the initiator is 0.1-2% of the mass of the monomer.
6. The solid-state electrolyte according to any one of claims 3 to 5, wherein the polymer is selected from at least one of acrylonitrile-butadiene-styrene plastic, polyethylene oxide, polylactic acid, polyvinyl chloride, polyvinyl alcohol, polyacrylonitrile, polypropylene, polycarbonate, polycaprolactone, vinylidene fluoride-hexafluoropropylene copolymer, thermoplastic polyurethane, polymethyl methacrylate, polyvinyl acetate, and/or,
the lithium salt is selected from at least one of lithium hexafluorophosphate, lithium tetrafluoroborate, lithium perchlorate, lithium bistrifluoromethylsulphonylimide, lithium bistrifluorosulphonylimide, lithium dioxalate borate, lithium difluorooxalato borate, lithium trifluoromethanesulfonate and lithium bis (trifluoromethylsulphonyl) imide, and/or,
the nano ceramic filler is at least one selected from alumina, silica, titanium dioxide, zinc oxide and zirconia.
7. The solid-state electrolyte according to claim 4 or 5, wherein the monomer is selected from at least one of triethylene glycol diacrylate, trimethylolpropane trimethacrylate, 2-phenoxyethyl acrylate, polyethylene glycol methacrylate, t-butyl acrylamide, and/or,
the initiator is selected from one of azobisisobutyronitrile, azobisisoheptonitrile, dimethyl azobisisobutyrate and benzoyl peroxide.
8. A method for producing a solid electrolyte according to any one of claims 1 to 7, comprising the steps of:
volatilizing a solvent in a solution at least containing the polymer and lithium salt, and then preparing silk from the obtained solid substance to obtain a silk material;
3D printing is carried out by taking the wire as a raw material to obtain the polymer electrolyte framework;
soaking the polymer electrolyte framework in a precursor solution of plastic crystal electrolyte and heating to obtain the solid electrolyte; the precursor solution comprises a monomer, an electrolyte and an initiator.
9. The method for preparing a solid electrolyte according to claim 8, wherein the heating temperature is 50 to 90 ℃ and the heating time is 3 to 20 hours.
10. A lithium ion battery, characterized in that the electrolyte of the lithium ion battery is the solid-state electrolyte according to any one of claims 1 to 7.
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CN112993384A (en) * 2021-01-21 2021-06-18 上海工程技术大学 In-situ polymerized ZnO composite solid polymer electrolyte and preparation method thereof
CN113571764A (en) * 2021-07-14 2021-10-29 北京理工大学 Composite solid electrolyte membrane and preparation method thereof
CN113571764B (en) * 2021-07-14 2022-09-02 北京理工大学 Composite solid electrolyte membrane and preparation method thereof
CN113895051A (en) * 2021-10-08 2022-01-07 北京化工大学 Preparation method of high-load-bearing polymer functional composite material based on 3D printing technology
CN114300741A (en) * 2021-12-27 2022-04-08 合肥国轩高科动力能源有限公司 Raw material composition for preparing thermosetting PAN (polyacrylonitrile) -based composite solid electrolyte membrane, preparation method and application

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Application publication date: 20200818