CN111952673B - High-performance all-solid-state lithium battery and preparation method thereof - Google Patents
High-performance all-solid-state lithium battery and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a high-performance all-solid-state lithium battery and a preparation method thereof, wherein the method comprises the following steps: uniformly mixing a carbon nitride precursor and a fluorine source in parts by weight, and then carrying out heat treatment to obtain fluorine-doped carbon nitride powder A; then mixing and stirring the powder A, lithium salt, a polymer matrix and an organic solvent to obtain a mixed solution B, carrying out film forming treatment on the mixed solution B, and drying to obtain a fluorine-doped carbon nitride-polymer composite solid electrolyte; and assembling the positive plate, the fluorine-doped carbon nitride-polymer composite solid electrolyte and the negative electrode material together in a hot pressing mode, and packaging by using a battery shell to form the all-solid-state lithium battery. The battery preparation method realizes the unification of ionic conductivity, thermal stability, electrochemical stability and mechanical property, and the preparation process of the composite anode material and the assembly process of the all-solid-state battery obviously improve the interface performance of the electrode/solid-state electrolyte.
Description
Technical Field
The invention belongs to the technical field of all-solid-state lithium batteries, and particularly relates to a high-performance all-solid-state lithium battery and a preparation method thereof.
Background
The lithium ion battery plays an important role in the fields of large-scale power storage of portable energy storage devices, electric automobiles and power stations and the like due to the advantages of high working voltage, long cycle life, environmental friendliness, no memory effect and the like. However, the existing energy density and poor safety of lithium ion batteries have not been able to meet practical requirements. The all-solid-state lithium battery adopts solid electrolyte to replace liquid electrolyte which is inflammable, easy to leak and easy to react with high-reactivity lithium metal, and can effectively solve the problems.
At present, the development of all-solid-state lithium batteries still has a plurality of problems. The solid electrolyte is a key material for realizing high energy density, high safety performance and high cycle stability of the lithium battery, and is widely concerned by domestic and foreign scientific research institutions, battery enterprises and automobile enterprises, but the currently researched inorganic solid electrolyte and polymer solid electrolyte generally have short performance and cannot meet the requirement of large-scale commercial application. The cycle performance and rate performance of the all-solid-state lithium battery are limited by the lower room-temperature ionic conductivity, poorer mechanical property and solid electrolyte/electrode interface performance of the solid electrolyte. Therefore, it is urgently needed to provide an all-solid-state lithium battery having good cycle performance and rate capability and a preparation method thereof.
Disclosure of Invention
In order to solve the problem of insufficient interfacial properties of solid electrolytes in the prior art, the invention aims to provide a high-performance all-solid-state lithium battery and a preparation method thereof.
In order to achieve the purpose, the invention adopts the following technical means:
a preparation method of a high-performance all-solid-state lithium battery comprises the following steps:
uniformly mixing 10 parts of carbon nitride precursor and 1-5 parts of fluorine source by weight, and then carrying out heat treatment, and keeping the temperature at 450-600 ℃ for 2-5 hours to obtain fluorine-doped carbon nitride powder A; then mixing and stirring 0.02-0.5 part of powder A, 0.1-1 part of lithium salt, 2 parts of polymer matrix and an organic solvent to obtain a mixed solution B, carrying out film forming treatment on the mixed solution B, and drying to obtain a fluorine-doped carbon nitride-polymer composite solid electrolyte;
grinding and mixing the positive active substance and the conductive agent to obtain powder C, stirring and mixing the powder C, the binder and the N-methyl pyrrolidone to obtain positive slurry D, coating the positive slurry D on an aluminum foil, and drying in vacuum to obtain a positive plate;
and assembling the positive plate, the fluorine-doped carbon nitride-polymer composite solid electrolyte and the negative electrode material together in a hot pressing mode, and packaging by using a battery shell to form the all-solid-state lithium battery.
Optionally, the uniformly mixing is mixing in an ethanol aqueous solution and drying, grinding or ball milling.
Optionally, the carbon nitride precursor is at least one of melamine, cyanamide, dicyandiamide and urea;
the fluorine source is at least one of sodium fluoride and vinyl fluoride.
Optionally, the lithium salt is at least one of lithium bistrifluoromethylsulfonyl imide, lithium perchlorate, lithium bis-oxalate borate, lithium difluoro-oxalate borate, lithium trifluoromethanesulfonate and lithium bis-fluorosulfonyl imide;
the polymer matrix is at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polypropylene carbonate, polyurethane, polyvinyl chloride, polypropylene oxide, polyvinylidene chloride, polyphosphazine and polysiloxane;
the organic solvent is at least one of dimethylacetamide, acetonitrile, N-dimethylformamide, acetone and N-methylpyrrolidone.
Optionally, the positive electrode active material is at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, high nickel ternary material NCM523, NCM622, NCM811 and NCA;
the conductive agent is at least one of Super P, Ketjen black, acetylene black, conductive graphite, carbon nanotubes, vapor grown carbon fibers and graphene.
Optionally, the proportion of the binder formed by mixing the positive electrode active material, the conductive agent, the polymer and the lithium salt is (6-8): 1: 1.
optionally, the binder is formed by mixing a polymer and a lithium salt, wherein the lithium salt accounts for 10-40 wt% of the polymer by mass, and the solid content of the binder is 3-10 wt%.
A high-performance all-solid-state lithium battery comprises a positive plate, a solid electrolyte and a negative electrode material which are packaged in a battery shell, wherein the solid electrolyte is a fluorine-doped carbon nitride-polymer composite solid electrolyte, and the positive plate, the fluorine-doped carbon nitride-polymer composite solid electrolyte and the negative electrode material are assembled in a hot-pressing mode.
Optionally, the preparation process of the solid electrolyte is as follows:
uniformly mixing 10 parts of carbon nitride precursor and 1-5 parts of fluorine source by weight, and then carrying out heat treatment, and keeping the temperature at 450-600 ℃ for 2-5 hours to obtain fluorine-doped carbon nitride powder A; and then mixing and stirring 0.02-0.5 part of the powder A, 0.1-1 part of lithium salt, 2 parts of the polymer matrix and an organic solvent to obtain a mixed solution B, performing film forming treatment on the mixed solution B, and drying to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Optionally, the negative electrode material is a lithium sheet or a lithium foil, and the battery case is a button battery case or an aluminum plastic film.
Compared with the prior art, the invention has the following advantages:
the preparation method comprises the steps of preparation of a solid electrolyte, preparation of a composite anode material, assembly of an all-solid-state lithium battery and the like, wherein the solid electrolyte firstly introduces fluorine-doped carbon nitride with a porous structure as an inorganic filler to be compounded with a polymer matrix, the fluorine-doped carbon nitride has light weight, low cost, good stability and simple preparation process, an anion receptor rich in the surface of the fluorine-doped carbon nitride can promote the dissociation of lithium salt, and the porous structure provides a potential transmission channel for lithium ions, so that the solid electrolyte has good electrochemical performance, mechanical performance, heat resistance and processability; the composite positive electrode material is composed of a binder formed by mixing a polymer and a lithium salt, a positive active substance and a conductive agent, and provides close ionic contact for the positive active substance, promotes good permeation of electrolyte among positive particles, and obviously improves the utilization rate of the positive electrode material and the interfacial property of a positive electrode/solid electrolyte; the assembly of the all-solid battery improves the contact of the electrode/solid electrolyte interface by introducing a hot pressing process during the assembly of the battery. The invention can synchronously improve the electrochemical performance, the mechanical performance and the heat resistance of the solid electrolyte and optimize the interface performance of the electrode/the solid electrolyte, thereby comprehensively improving the performances such as the cycle performance, the rate performance and the like of the all-solid-state lithium battery.
The novel solid electrolyte prepared by introducing the fluorine-doped carbon nitride with the porous structure as the inorganic filler in the product realizes the unification of ionic conductivity, thermal stability, electrochemical stability and mechanical property, the preparation process of the composite anode material and the assembly process of the all-solid-state battery obviously improve the interface property of the electrode/the solid electrolyte, and a novel method is provided for preparing the all-solid-state lithium battery with good cycle performance and rate capability.
Detailed Description
The invention relates to a preparation method of a high-performance all-solid-state lithium battery, which comprises the following steps:
s1, preparing a solid electrolyte: uniformly mixing 10 parts of carbon nitride precursor and 1-5 parts of fluorine source by weight, and then carrying out heat treatment by using a muffle furnace, heating for 2 hours to 450-600 ℃, and keeping the temperature for 2-5 hours to obtain fluorine-doped carbon nitride powder A. And then mixing 0.02-0.5 part of the powder A, 0.1-1 part of lithium salt, 2 parts of the polymer matrix and an organic solvent in a certain sequence, continuously stirring and mixing for 6-24 hours at room temperature to obtain a mixed solution B, carrying out film forming treatment on the mixed solution B, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
S2, preparing a composite anode material: grinding and mixing the positive active substance and the conductive agent according to a certain proportion to obtain powder C, then stirring and mixing the powder C, a binder formed by mixing a polymer and a lithium salt and N-methyl pyrrolidone for 12 hours to obtain positive slurry D, coating the positive slurry D on an aluminum foil, drying in vacuum to obtain a positive plate, and cutting by a slicer for subsequent use.
S3, assembling the all-solid-state lithium battery: and (4) assembling the positive plate prepared in the step (S2), the fluorine-doped carbon nitride-polymer composite solid electrolyte prepared in the step (S1) and the negative electrode material together in a hot pressing mode, and packaging by using a battery shell to form the all-solid-state lithium battery.
Preferably, the carbon nitride precursor in step S1 is one, two or more mixtures of melamine, cyanamide, dicyanodiamide and urea in any ratio; the fluorine source is one, two or a mixture of more than two of sodium fluoride and vinyl fluoride in any proportion; the uniform mixing mode is mixing in ethanol water solution and drying, grinding or ball milling; the lithium salt is one or a mixture of two or more than two of bistrifluoromethylsulfonyl imide lithium, lithium perchlorate, lithium bis oxalate borate, lithium difluoro oxalate borate, lithium trifluoromethanesulfonate and lithium bis fluoro sulfonyl imide in any proportion; the polymer matrix is one or a mixture of two or more of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polypropylene carbonate, polyurethane, polyvinyl chloride, polypropylene oxide, polyvinylidene chloride, polyphosphazine and polysiloxane in any proportion; the organic solvent is one, two or a mixture of more than two of dimethylacetamide, acetonitrile, N-dimethylformamide, acetone and N-methylpyrrolidone in any proportion;
wherein, the mixing in a certain sequence is that the fluorine-doped carbon nitride powder, the salt, the polymer matrix and the organic solvent are simultaneously ultrasonically mixed; or the fluorine-doped carbon nitride powder is firstly mixed with the organic solvent by ultrasound, and then the salt and the polymer matrix are added; or firstly ultrasonically mixing salt and a polymer matrix with an organic solvent, and then adding fluorine-doped carbon nitride powder; or firstly, respectively ultrasonically mixing the salt, the polymer matrix and the fluorine-doped carbon nitride powder with the organic solvent, and then mixing and stirring; the film forming treatment mode is a pouring method or a coating method;
the positive active material in step S2 is one or a mixture of two or more of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, high nickel ternary material NCM523, NCM622, NCM811, and NCA in any ratio; the conductive agent is one or a mixture of two or more of Super P, Ketjen black, acetylene black, conductive graphite, carbon nanotubes, vapor grown carbon fibers and graphene in any proportion; the proportion of a binder formed by mixing the positive electrode active material, the conductive agent, the polymer and the lithium salt is (6-8): 1: 1; one or a mixture of two or more of acetylene black, conductive graphite, carbon nanotubes, vapor grown carbon fibers and graphene in any proportion; the lithium salt accounts for 10-40 wt% of the polymer, and the solid content of the binder is 3-10 wt%;
the invention also provides a high-performance all-solid-state lithium battery which comprises a positive plate, a solid electrolyte and a negative electrode material, wherein the positive plate, the solid electrolyte and the negative electrode material are packaged in a battery shell, the solid electrolyte is a fluorine-doped carbon nitride-polymer composite solid electrolyte, and the positive plate, the fluorine-doped carbon nitride-polymer composite solid electrolyte and the negative electrode material are assembled in a hot pressing mode. The cathode material is lithium sheet or lithium foil, and the battery shell is button battery shell or aluminum plastic film.
The technical solution of the present invention will be described in detail with reference to specific examples, which are not intended to limit the present invention.
Example 1:
s1, preparing a solid electrolyte: mixing 10 parts of urea and 1 part of fluoroethylene in an ethanol water solution, drying, performing heat treatment by using a muffle furnace, heating to 450 ℃ for 2 hours, and keeping the temperature for 2 hours to obtain fluorine-doped carbon nitride powder A. And then ultrasonically mixing 0.02 part of the powder A, 0.1 part of lithium perchlorate, 2 parts of polypropylene carbonate and N, N-dimethylformamide, continuously stirring and mixing for 6 hours at room temperature to obtain a mixed solution B, pouring the mixed solution B to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
S2, preparing a composite anode material: grinding and mixing lithium iron phosphate and Super P according to a certain proportion to obtain powder C, then stirring and mixing the powder C, a binder formed by mixing polypropylene carbonate and lithium perchlorate and N-methyl pyrrolidone for 12 hours to obtain anode slurry D, wherein the ratio of the binder formed by mixing the lithium iron phosphate, the Super P, the polypropylene carbonate and the lithium perchlorate is 6: 1: 1, lithium perchlorate accounts for 10 wt% of the polypropylene carbonate, and the solid content of the binder is 3 wt%; and coating the positive electrode slurry D on an aluminum foil and performing vacuum drying to obtain a positive electrode plate, and cutting by using a slicing machine for subsequent use.
S3, assembling the all-solid-state lithium battery: and (4) assembling the positive plate prepared in the step (S2), the fluorine-doped carbon nitride-polymer composite solid electrolyte prepared in the step (S1) and the lithium foil together in a hot pressing mode, and packaging by using an aluminum plastic film to form the all-solid-state lithium battery.
Example 2:
s1, preparing a solid electrolyte: according to the weight portion, 10 portions of dicyanodiamine and 5 portions of sodium fluoride are ball-milled and uniformly mixed, then are subjected to heat treatment by a muffle furnace, the temperature is increased for 2 hours to 600 ℃, and the temperature is kept for 5 hours, so that fluorine-doped carbon nitride powder A is obtained. And then ultrasonically mixing 0.5 part of the powder A with N-methylpyrrolidone, adding 1 part of lithium trifluoromethanesulfonate and 2 parts of polyvinylidene fluoride, continuously stirring and mixing for 24 hours at room temperature to obtain a mixed solution B, coating the mixed solution B to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
S2, preparing a composite anode material: grinding and mixing NCM811 and acetylene black according to a certain proportion to obtain powder C, then stirring and mixing the powder C, a binder formed by mixing polypropylene carbonate and lithium perchlorate and N-methyl pyrrolidone for 12 hours to obtain anode slurry D, wherein the proportion of the binder formed by mixing lithium iron phosphate, Super P, polyvinylidene fluoride and lithium trifluoromethanesulfonate is 8: 1: 1, lithium trifluoromethanesulfonate accounts for 40 wt% of polyvinylidene fluoride, and the solid content of the binder is 10 wt%; and coating the positive electrode slurry D on an aluminum foil and performing vacuum drying to obtain a positive electrode plate, and cutting by using a slicing machine for subsequent use.
S3, assembling the all-solid-state lithium battery: and (4) assembling the positive plate obtained in the step (S2), the fluorine-doped carbon nitride-polymer composite solid electrolyte obtained in the step (S1) and the lithium plate together in a hot pressing mode, and packaging by using a button cell case to form the all-solid-state lithium battery.
Example 3:
s1, preparing a solid electrolyte: according to the weight portion, 10 portions of urea and 3 portions of vinyl fluoride are ground and uniformly mixed, then a muffle furnace is used for carrying out heat treatment, the temperature is increased to 525 ℃ for 2 hours, and the temperature is kept for 3.5 hours, so that fluorine-doped carbon nitride powder A is obtained. And then ultrasonically mixing 0.26 part of the powder A with dimethylacetamide, adding 0.55 part of lithium bis (fluorosulfonyl) imide and 2 parts of polymethyl methacrylate, continuously stirring and mixing for 12 hours at room temperature to obtain a mixed solution B, pouring the mixed solution B to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
S2, preparing a composite anode material: grinding and mixing lithium iron phosphate and ketjen black according to a certain proportion to obtain powder C, then stirring and mixing the powder C, a binder formed by mixing polymethyl methacrylate and lithium bis (fluorosulfonyl) imide and N-methyl pyrrolidone for 12 hours to obtain a positive electrode slurry D, wherein the ratio of the binder formed by mixing the lithium iron phosphate, the ketjen black, the polymethyl methacrylate and the lithium bis (fluorosulfonyl) imide is 7: 1: 1, the lithium bis (fluorosulfonyl) imide accounts for 25 wt% of the polymethyl methacrylate, and the solid content of the binder is 6.5 wt%; and coating the positive electrode slurry D on an aluminum foil and performing vacuum drying to obtain a positive electrode plate, and cutting by using a slicing machine for subsequent use.
S3, assembling the all-solid-state lithium battery: and (4) assembling the positive plate prepared in the step (S2), the fluorine-doped carbon nitride-polymer composite solid electrolyte prepared in the step (S1) and the lithium foil together in a hot pressing mode, and packaging by using an aluminum plastic film to form the all-solid-state lithium battery.
Example 4:
s1, preparing a solid electrolyte: according to the weight portion, 10 portions of melamine and 2 portions of sodium fluoride are ball-milled and evenly mixed, then are subjected to heat treatment by a muffle furnace, the temperature is increased for 2 hours to 550 ℃, and the temperature is kept for 3 hours, so that fluorine-doped carbon nitride powder A is obtained. Then, 0.35 part of lithium bistrifluoromethylsulfonyl imide, 2 parts of polyethylene oxide and 0.15 part of fluorine-doped carbon nitride powder A are respectively ultrasonically mixed with acetonitrile, then the mixture is mixed and stirred, the mixture is continuously stirred and mixed for 9 hours at room temperature to obtain a mixed solution B, the mixed solution B is coated to form a film, and the film is dried in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
S2, preparing a composite anode material: grinding and mixing NCM811 and Super P according to a certain proportion to obtain powder C, then stirring and mixing the powder C, a binder formed by mixing polyethylene oxide and lithium bis (trifluoromethyl) sulfonyl imide and N-methyl pyrrolidone for 12 hours to obtain positive electrode slurry D, wherein the proportion of the binder formed by mixing the NCM811, the Super P, the polyethylene oxide and the lithium bis (trifluoromethyl) sulfonyl imide is 6.5: 1: 1, the lithium bistrifluoromethylsulfonyl imide accounts for 17.5 wt% of the polyethylene oxide, and the solid content of the binder is 5 wt%. And coating the positive electrode slurry D on an aluminum foil and performing vacuum drying to obtain a positive electrode plate, and cutting by using a slicing machine for subsequent use.
S3, assembling the all-solid-state lithium battery: and (4) assembling the positive plate obtained in the step (S2), the fluorine-doped carbon nitride-polymer composite solid electrolyte obtained in the step (S1) and the lithium plate together in a hot pressing mode, and packaging by using a button cell case to form the all-solid-state lithium battery.
Example 5:
s1, preparing a solid electrolyte: according to the weight portion, 10 portions of melamine and 4 portions of vinyl fluoride are ball-milled and evenly mixed, then are subjected to heat treatment by a muffle furnace, the temperature is increased to 550 ℃ for 2 hours, and the temperature is kept for 4 hours, so that fluorine-doped carbon nitride powder A is obtained. And then ultrasonically mixing 0.35 part of powder A, 0.75 part of lithium bis (trifluoromethyl) sulfonyl imide and 2 parts of polymer polyvinylidene fluoride-hexafluoropropylene with acetone, continuously stirring and mixing for 18 hours at room temperature to obtain a mixed solution B, coating the mixed solution B to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
S2, preparing a composite anode material: grinding and mixing NCM811 and Super P according to a certain proportion to obtain powder C, then stirring and mixing the powder C, a binder formed by mixing polyethylene oxide and lithium bis (trifluoromethyl) sulfonyl imide and N-methyl pyrrolidone for 12 hours to obtain positive electrode slurry D, wherein the ratio of the binder formed by mixing NCM811, Super P, polyethylene oxide and lithium bis (trifluoromethyl) sulfonyl imide is 7.5: 1: 1, the lithium bistrifluoromethylsulfonyl imide accounts for 32.5 wt% of the polyethylene oxide, and the solid content of the binder is 7.5 wt%. And coating the positive electrode slurry D on an aluminum foil and performing vacuum drying to obtain a positive electrode plate, and cutting by using a slicing machine for subsequent use.
S3, assembling the all-solid-state lithium battery: and (4) assembling the positive plate obtained in the step (S2), the fluorine-doped carbon nitride-polymer composite solid electrolyte obtained in the step (S1) and the lithium plate together in a hot pressing mode, and packaging by using a button cell case to form the all-solid-state lithium battery.
Comparative example 1:
the other parameters of this comparative example and example 3 were the same, except that the fluorine-doped carbon nitride powder was not added in the preparation of the solid electrolyte.
Comparative example 2:
the other parameters of this comparative example and example 3 were the same, except that sodium fluoride as a fluorine source was not added in the preparation of carbon nitride, that is, carbon nitride powder was added instead of fluorine-doped carbon nitride powder in the preparation of a composite solid electrolyte.
TABLE 1 all solid-state lithium batteries prepared under different example conditions
As can be seen from example 3, comparative example 1, and comparative example 2, the cycle performance and rate performance of the all-solid-state lithium battery can be significantly improved by using the fluorine-doped carbon nitride-polymer composite solid electrolyte as the electrolyte of the all-solid-state lithium battery.
In summary, the invention discloses a preparation method of a high-performance all-solid-state lithium battery, which comprises the steps of preparation of a solid electrolyte, preparation of a composite cathode material, assembly of the all-solid-state lithium battery and the like. The solid electrolyte is a composite solid electrolyte prepared by compounding fluorine-doped carbon nitride with a porous structure and a polymer matrix, the fluorine-doped carbon nitride is light in weight, low in cost, good in stability and simple in preparation process, an anion receptor rich in the surface of the composite solid electrolyte can promote the dissociation of lithium salt, and the porous structure provides a potential transmission channel for lithium ions, so that the composite solid electrolyte has good electrochemical performance, mechanical performance, heat resistance and processability. The composite positive electrode material comprises a binder formed by mixing a polymer and a lithium salt, a positive active substance and a conductive agent, provides close ionic contact for positive electrode particles, promotes good permeation of electrolyte among the positive electrode particles, and obviously improves the utilization rate of the positive electrode material and the interfacial property of a positive electrode/solid electrolyte. The assembly of the all-solid-state battery comprises the assembly of the all-solid-state button lithium battery and the assembly of the all-solid-state soft package lithium battery, and a hot pressing process is introduced in the battery assembly process to improve the contact of an electrode/solid electrolyte interface. The invention aims to synchronously improve the electrochemical performance, the mechanical performance and the heat resistance of the solid electrolyte and optimize the interface performance of the electrode/the solid electrolyte, thereby improving the performances of the all-solid-state lithium battery, such as the cycle performance, the rate performance and the like.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. A preparation method of a high-performance all-solid-state lithium battery is characterized by comprising the following steps:
uniformly mixing 10 parts of carbon nitride precursor and 1-5 parts of fluorine source by weight, and then carrying out heat treatment, and keeping the temperature at 450-600 ℃ for 2-5 hours to obtain fluorine-doped carbon nitride powder A; then mixing and stirring 0.02-0.5 part of powder A, 0.1-1 part of lithium salt, 2 parts of polymer matrix and an organic solvent to obtain a mixed solution B, carrying out film forming treatment on the mixed solution B, and drying to obtain a fluorine-doped carbon nitride-polymer composite solid electrolyte;
grinding and mixing the positive active substance and the conductive agent to obtain powder C, stirring and mixing the powder C, the binder and the N-methyl pyrrolidone to obtain positive slurry D, coating the positive slurry D on an aluminum foil, and drying in vacuum to obtain a positive plate;
and assembling the positive plate, the fluorine-doped carbon nitride-polymer composite solid electrolyte and the negative electrode material together in a hot pressing mode, and packaging by using a battery shell to form the all-solid-state lithium battery.
2. The method of claim 1, wherein: the uniform mixing is mixing in ethanol water solution and drying, grinding or ball milling.
3. The method of claim 1, wherein: the carbon nitride precursor is at least one of melamine, cyanamide, dicyanodiamide and urea;
the fluorine source is at least one of sodium fluoride and vinyl fluoride.
4. The method of claim 1, wherein: the lithium salt is at least one of lithium bistrifluoromethylsulfonyl imide, lithium perchlorate, lithium bistrifluoromethyl oxalate borate, lithium difluorooxalate borate, lithium trifluoromethanesulfonate and lithium bistrifluorosulfonyl imide;
the polymer matrix is at least one of polyvinylidene fluoride, polyvinylidene fluoride-hexafluoropropylene, polyethylene oxide, polyacrylonitrile, polymethyl methacrylate, polypropylene carbonate, polyurethane, polyvinyl chloride, polypropylene oxide, polyvinylidene chloride, polyphosphazine and polysiloxane;
the organic solvent is at least one of dimethylacetamide, acetonitrile, N-dimethylformamide, acetone and N-methylpyrrolidone.
5. The method of claim 1, wherein: the positive active material is at least one of lithium cobaltate, lithium manganate, lithium nickelate, lithium iron phosphate, high-nickel ternary materials NCM523, NCM622, NCM811 and NCA;
the conductive agent is at least one of Super P, Ketjen black, acetylene black, conductive graphite, carbon nanotubes, vapor grown carbon fibers and graphene.
6. The method of claim 1, wherein: the proportion of a binder formed by mixing the positive active material, the conductive agent, the polymer and the lithium salt is (6-8): 1: 1.
7. the method of claim 1, wherein: the binder is formed by mixing a polymer and lithium salt, wherein the lithium salt accounts for 10-40 wt% of the polymer, and the solid content of the binder is 3-10 wt%.
8. A high-performance all-solid-state lithium battery is characterized in that: the composite type solid electrolyte battery comprises a positive plate, a solid electrolyte and a negative electrode material which are packaged in a battery shell, wherein the solid electrolyte is a fluorine-doped carbon nitride-polymer composite type solid electrolyte, and the positive plate, the fluorine-doped carbon nitride-polymer composite type solid electrolyte and the negative electrode material are assembled in a hot pressing mode;
the preparation process of the solid electrolyte comprises the following steps:
uniformly mixing 10 parts of carbon nitride precursor and 1-5 parts of fluorine source by weight, and then carrying out heat treatment, and keeping the temperature at 450-600 ℃ for 2-5 hours to obtain fluorine-doped carbon nitride powder A; and then mixing and stirring 0.02-0.5 part of the powder A, 0.1-1 part of lithium salt, 2 parts of the polymer matrix and an organic solvent to obtain a mixed solution B, performing film forming treatment on the mixed solution B, and drying to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
9. A lithium battery as claimed in claim 8, characterized in that: the negative electrode material is a lithium sheet or a lithium foil, and the battery shell is a button battery shell or an aluminum plastic film.
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