CN111952674A - Fluorine-doped carbon nitride-polymer composite solid electrolyte and preparation method and application thereof - Google Patents
Fluorine-doped carbon nitride-polymer composite solid electrolyte and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a fluorine-doped carbon nitride-polymer composite solid electrolyte and a preparation method and application thereof, wherein the method comprises the following steps: uniformly mixing 20 parts of carbon nitride precursor and 1-10 parts of fluorine source by weight to obtain mixed powder A; heating the mixed powder A to 450-600 ℃ for heat treatment, and preserving heat for 2-5 hours to obtain fluorine-doped carbon nitride powder B; sequentially mixing 0.02-0.6 part of powder B, 0.2-1 part of salt, 2 parts of polymer matrix and an organic solvent, and stirring to obtain a mixed solution C; and (3) performing film forming treatment on the mixed solution C, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte. The prepared fluorine-doped carbon nitride improves the ionic conductivity, ionic mobility and electrochemical stability window of the composite solid electrolyte, and simultaneously can stabilize the distribution of ions, reduce the deposition energy barrier and obviously improve the comprehensive performance of the composite solid electrolyte.
Description
Technical Field
The invention belongs to the technical field of solid lithium and sodium batteries, and particularly relates to a fluorine-doped carbon nitride-polymer composite solid electrolyte and a preparation method and application thereof.
Background
With the increasing demand of energy for social development, the problems of environmental pollution and sustainable development become more and more serious, and the strategy of energy transformation mainly based on new energy becomes a global consensus. Meanwhile, the accidents of fire and explosion caused by overcharge of the battery, mechanical impact and internal short circuit frequently occur, so that relatively serious property loss and casualties are caused. Therefore, attention is increasingly paid to all-solid-state batteries having better safety, higher energy density, and longer cycle life.
The solid electrolyte may be classified into an inorganic electrolyte and a solid polymer electrolyte. Inorganic electrolytes have high thermal stability and are not easy to burn and explode, but often have high lattice energy and poor processability; the Solid Polymer Electrolyte (SPE) has the advantages of light weight, low cost, easy film forming and processing, high flexibility and contribution to miniaturization of electronic products. Currently, polyethylene oxide (PEO), Polyacrylonitrile (PAN), polymethyl methacrylate (PMMA), polyvinylidene fluoride (PVDF), and the like are often used as matrix materials for SPEs. However, the problems of low room temperature ionic conductivity, high temperature instability, large interface resistance, insufficient mechanical properties, incapability of inhibiting the penetration of lithium dendrites and the like of SPE become bottlenecks which restrict the development of SPE. Researchers often use blending or copolymerization methods to reduce the crystallinity of SPE to improve the ionic conductivity, such as Klongkan et al introducing polyethylene glycol and dioctyl phthalate into PEO to reduce SPE crystallinity, which can increase the ionic conductivity by two orders of magnitude. However, the mechanical properties of SPE are significantly reduced due to blending modification of small molecular plasticizers or low molecular weight polymers, and it is difficult to meet the requirements of practical applications. The use of inorganic fillers in combination with a polymer matrix is another approach to improving SPE performance,inorganic fillers such as SiO2、Al2O3、BaTiO3And fast ion conductors and the like are widely applied to modification of SPE, but some key scientific problems still exist to be solved.
The carbon nitride has excellent thermal stability and chemical stability, light weight, various synthesis methods and modification strategies, environmental friendliness and high mechanical strength (the shear modulus can be as high as 21.6 GPa). And the polarity and semiconductor characteristics of the carbon nitride itself help to adjust the spatial and interfacial distribution of ionic charges in the solid polymer electrolyte. The carbon nitride is used as the inorganic filler of the SPE to prepare the SPE with coordinated and unified room temperature ionic conductivity, thermal stability, electrochemical stability and mechanical property, and has obvious scientific significance and application value. However, currently, there are few researches and reports on the preparation of SPE by compounding carbon nitride as an inorganic filler with a polymer matrix, and the application of fluorine-doped carbon nitride in solid electrolytes has not been reported yet.
Disclosure of Invention
In order to solve the problem of insufficient interfacial properties of the solid electrolyte in the prior art, the invention aims to provide a fluorine-doped carbon nitride-polymer composite solid electrolyte, and a preparation method and application thereof. The invention takes the fluorine-doped carbon nitride with porous structure as the inorganic filler of the composite solid electrolyte for the first time. The method has the advantages that the prepared fluorine-doped carbon nitride is of a porous structure, and a network structure for efficient transmission is constructed for ions in the polymer; f groups are introduced into the fluorine-doped carbon nitride, so that the Lewis acid-base interaction with salt is enhanced, the salt dissociation is promoted, the ion conductivity, the ion mobility and the electrochemical stability window of the composite solid electrolyte are improved, the distribution of ions can be stabilized, the deposition energy barrier is reduced, and the comprehensive performance of the composite solid electrolyte is obviously improved.
In order to achieve the purpose, the invention adopts the following technical means:
a preparation method of a fluorine-doped carbon nitride-polymer composite solid electrolyte comprises the following steps:
uniformly mixing 20 parts of carbon nitride precursor and 1-10 parts of fluorine source by weight to obtain mixed powder A;
heating the mixed powder A to 450-600 ℃ for heat treatment, and preserving heat for 2-5 hours to obtain fluorine-doped carbon nitride powder B;
sequentially mixing 0.02-0.6 part of powder B, 0.2-1 part of salt, 2 parts of polymer matrix and an organic solvent, and stirring to obtain a mixed solution C;
and (3) performing film forming treatment on the mixed solution C, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Optionally, 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.
Optionally, the uniformly mixing means mixing in an ethanol aqueous solution and drying, grinding or ball milling.
Optionally, the 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; or at least one of sodium perchlorate, sodium bistrifluoromethanesulfonylimide, sodium trifluoromethanesulfonylimide and sodium bisfluorosulfonylimide.
Optionally, 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.
Optionally, the organic solvent is at least one of dimethylacetamide, acetonitrile, N-dimethylformamide, acetone, and N-methylpyrrolidone.
Optionally, the sequential mixing is simultaneous ultrasonic mixing of the fluorine-doped carbon nitride powder, the salt, the polymer matrix and the organic solvent; 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 the salt, the polymer matrix and the fluorine-doped carbon nitride powder are respectively ultrasonically mixed with the organic solvent, and then are mixed and stirred.
Optionally, the film forming treatment mode is a pouring method or a coating method.
The fluorine-doped carbon nitride-polymer composite solid electrolyte is prepared by the preparation method.
The application of the fluorine-doped carbon nitride-polymer composite solid electrolyte in a solid battery is characterized in that the composite solid electrolyte is prepared by the preparation method; the solid-state battery is a solid-state lithium ion battery or a solid-state sodium ion battery.
Compared with the prior art, the invention has the following advantages:
firstly, performing heat treatment on a carbon nitride precursor and a fluorine source which are uniformly mixed in an ethanol water solution in a muffle furnace to obtain fluorine-doped carbon nitride; then ultrasonically mixing and stirring the fluorine-doped carbon nitride, the salt, the polymer matrix and the organic solvent in a certain sequence to obtain a uniform mixed solution; and finally, forming a film from the mixed solution and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte. The fluorine-doped carbon nitride-polymer composite solid electrolyte with good comprehensive performance and dispersibility is prepared by adopting the fluorine-doped carbon nitride as the inorganic filler of the composite solid electrolyte for the first time. The porous structure of the fluorine-doped carbon nitride in the product provides a transmission network for the efficient transmission of ions in a polymer, the introduction of the fluorine-doped carbon nitride increases the dissociation degree of salt, improves the ionic conductivity, ionic mobility and electrochemical stability window of the composite solid electrolyte, and simultaneously can stabilize the distribution of ions and reduce the deposition energy barrier, thereby providing new possibility for the development of all-solid-state lithium and sodium batteries with good cycle stability, safety and multiplying power charge and discharge performance. The carbon nitride has excellent thermal stability and chemical stability, light weight, various synthesis methods and modification strategies, environmental friendliness and high mechanical strength (the shear modulus can be as high as 21.6 GPa). And the polarity and semiconductor characteristics of the carbon nitride itself help to adjust the spatial and interfacial distribution of ionic charges in the solid polymer electrolyte. The carbon nitride is used as the inorganic filler of the SPE to prepare the SPE with coordinated and unified room temperature ionic conductivity, thermal stability, electrochemical stability and mechanical property, and has obvious scientific significance and application value. However, currently, there are few researches and reports on the preparation of SPE by compounding carbon nitride as an inorganic filler with a polymer matrix, and the application of fluorine-doped carbon nitride in solid electrolytes has not been reported yet.
Drawings
FIG. 1 is a transmission electron micrograph of fluorine-doped carbon nitride prepared according to the present invention;
FIG. 2 is an optical photograph of a fluorine-doped carbon nitride-polymer composite solid electrolyte prepared according to the present invention after being bent, twisted and re-expanded;
fig. 3 is an optical photograph of the solid electrolyte prepared in comparative example 1;
fig. 4 is an optical photograph of the solid electrolyte prepared in comparative example 2;
FIG. 5 is impedance spectra at room temperature of example 3, comparative example 1 and comparative example 2 in the present invention;
FIG. 6 is a linear sweep voltammogram at room temperature for example 3, comparative example 1, and comparative example 2 of the present invention.
Detailed Description
The invention relates to a preparation method of a fluorine-doped carbon nitride-polymer composite solid electrolyte, which comprises the following steps:
1) uniformly mixing 20 parts of carbon nitride precursor and 1-10 parts of fluorine source by weight to obtain mixed powder A;
2) placing the mixed powder A in a crucible and performing heat treatment in a muffle furnace, heating the mixed powder A for 2 hours to 450-600 ℃, and preserving the heat for 2-5 hours to obtain fluorine-doped carbon nitride powder B;
3) mixing 0.02-0.6 part of powder B, 0.2-1 part of salt, 2 parts of polymer matrix and an organic solvent in a certain sequence, and continuously stirring and mixing at room temperature for 6-24 hours to obtain a mixed solution C;
4) and (3) performing film forming treatment on the mixed solution C, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Preferably, 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; the uniform mixing mode is mixing in an ethanol water solution, drying, grinding or ball milling;
preferably, the 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; or at least one of sodium perchlorate, sodium bistrifluoromethylsulfonyl imide, sodium trifluoromethanesulfonylimide and sodium bisfluorosulfonylimide; 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;
wherein the mixing in a certain sequence is to simultaneously ultrasonically mix the fluorine-doped carbon nitride powder, the salt, the polymer matrix and the organic solvent; 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 fluorine-doped carbon nitride-polymer composite solid electrolyte can be applied as a solid electrolyte in a solid battery, and can be a solid lithium ion battery or a solid sodium ion battery.
The technical solutions of the present invention will be described in detail below with reference to specific examples and drawings, but the present invention is not limited to the examples.
Example 1:
1) uniformly mixing 20 parts of dicyanodiamine and 1 part of vinyl fluoride in an ethanol water solution by weight, and drying to obtain mixed powder A;
2) placing the mixed powder A in a crucible and performing heat treatment in a muffle furnace, heating the mixed powder A to 450 ℃ for 2 hours, and keeping the temperature for 2 hours to obtain fluorine-doped carbon nitride powder B;
3) simultaneously ultrasonically mixing 0.02 part of powder B, 0.2 part of sodium perchlorate, 2 parts of polyacrylonitrile and N-methyl pyrrolidone, and continuously stirring and mixing at room temperature for 6 hours to obtain a mixed solution C;
4) and pouring the mixed solution C to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Example 2:
1) according to the parts by weight, 20 parts of urea and 10 parts of vinyl fluoride are uniformly mixed by ball milling to obtain mixed powder A;
2) placing the mixed powder A in a crucible and performing heat treatment in a muffle furnace, heating the mixed powder A to 600 ℃ for 2 hours, and keeping the temperature for 5 hours to obtain fluorine-doped carbon nitride powder B;
3) firstly, ultrasonically mixing 1 part of lithium bis (oxalato) borate, 2 parts of polymethyl methacrylate and N, N-dimethylformamide, then adding 0.6 part of powder B, and continuously stirring and mixing for 24 hours at room temperature to obtain a mixed solution C;
4) and coating the mixed solution C to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Example 3:
1) according to the parts by weight, 20 parts of melamine and 5 parts of sodium fluoride are ground, uniformly mixed and dried to obtain mixed powder A;
2) placing the mixed powder A in a crucible and performing heat treatment in a muffle furnace, heating the mixed powder A to 525 ℃ for 2 hours, and preserving the heat for 3.5 hours to obtain fluorine-doped carbon nitride powder B;
3) firstly, ultrasonically mixing 0.3 part of powder B with dimethylacetamide, then adding 0.6 part of lithium bis (trifluoromethyl) sulfonyl imide and 2 parts of polyvinylidene fluoride-hexafluoropropylene, and continuously stirring and mixing for 24 hours at room temperature to obtain a mixed solution C;
4) and coating the mixed solution C to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Example 4:
1) uniformly mixing 20 parts of urea and 7.5 parts of sodium fluoride in an ethanol aqueous solution in parts by weight, and drying to obtain mixed powder A;
2) placing the mixed powder A in a crucible and performing heat treatment in a muffle furnace, heating the mixed powder A to 560 ℃ for 2 hours, and keeping the temperature for 4.25 hours to obtain fluorine-doped carbon nitride powder B;
3) respectively ultrasonically mixing 0.45 part of powder B, 0.8 part of sodium bistrifluoromethylsulfonyl imide and 2 parts of polyethylene oxide with acetonitrile, and then continuously stirring and mixing for 19.5 hours at room temperature to obtain a mixed solution C;
4) and pouring the mixed solution C to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
Example 5:
1) according to the weight parts, 20 parts of cyanamide and 2.5 parts of vinyl fluoride are ball-milled and uniformly mixed to obtain mixed powder A;
2) placing the mixed powder A in a crucible and performing heat treatment in a muffle furnace, heating the mixed powder A to 495 ℃ for 2 hours, and keeping the temperature for 2.75 hours to obtain fluorine-doped carbon nitride powder B;
3) simultaneously ultrasonically mixing 0.15 part of powder B, 0.4 part of lithium trifluoromethanesulfonate, 2 parts of polyvinylidene fluoride and N-methylpyrrolidone, and continuously stirring and mixing for 10.5 hours at room temperature to obtain a mixed solution C;
4) and pouring the mixed solution C to form a film, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
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 data of performance of fluorine doped carbon nitride-polymer composite solid electrolytes prepared under different conditions of examples
As can be seen from example 3, comparative example 1 and comparative example 2, with reference to fig. 1 to 6, the addition of fluorine-doped carbon nitride can greatly improve the comprehensive properties of the solid electrolyte, such as ionic conductivity, electrochemical stability window, lithium ion migration number, and the like. And the performance is superior to that of carbon nitride which is not doped by fluorine.
In summary, the invention discloses a preparation method of a fluorine-doped carbon nitride-polymer composite solid electrolyte. Firstly, performing heat treatment on a carbon nitride precursor and a fluorine source which are uniformly mixed in an ethanol water solution in a muffle furnace to obtain fluorine-doped carbon nitride; then ultrasonically mixing and stirring the fluorine-doped carbon nitride, the salt, the polymer matrix and the organic solvent in a certain sequence to obtain a uniform mixed solution; and finally, forming a film from the mixed solution and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte. The fluorine-doped carbon nitride-polymer composite solid electrolyte with good comprehensive performance and dispersibility is prepared by adopting the fluorine-doped carbon nitride as the inorganic filler of the composite solid electrolyte for the first time. The porous structure of the fluorine-doped carbon nitride in the product provides a transmission network for the efficient transmission of ions in a polymer, the introduction of the fluorine-doped carbon nitride increases the dissociation degree of salt, improves the ionic conductivity, ionic mobility and electrochemical stability window of the composite solid electrolyte, and simultaneously can stabilize the distribution of ions and reduce the deposition energy barrier, thereby providing new possibility for the development of all-solid-state lithium and sodium batteries with good cycle stability, safety and multiplying power charge and discharge performance.
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 (10)
1. A preparation method of fluorine-doped carbon nitride-polymer composite solid electrolyte is characterized by comprising the following steps: the method comprises the following steps:
uniformly mixing 20 parts of carbon nitride precursor and 1-10 parts of fluorine source by weight to obtain mixed powder A;
heating the mixed powder A to 450-600 ℃ for heat treatment, and preserving heat for 2-5 hours to obtain fluorine-doped carbon nitride powder B;
sequentially mixing 0.02-0.6 part of powder B, 0.2-1 part of salt, 2 parts of polymer matrix and an organic solvent, and stirring to obtain a mixed solution C;
and (3) performing film forming treatment on the mixed solution C, and drying in vacuum to obtain the fluorine-doped carbon nitride-polymer composite solid electrolyte.
2. 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.
3. The method of claim 1, wherein: the uniform mixing refers to mixing in an ethanol aqueous solution and drying, grinding or ball milling.
4. The method of claim 1, wherein: the salt is at least one of lithium bis (trifluoromethyl) sulfonyl imide, lithium perchlorate, lithium bis (oxalate) borate, lithium difluoro (oxalate) borate, lithium trifluoro (methyl) sulfonate and lithium bis (fluoro) sulfonyl imide; or at least one of sodium perchlorate, sodium bistrifluoromethanesulfonylimide, sodium trifluoromethanesulfonylimide and sodium bisfluorosulfonylimide.
5. The method of claim 1, wherein: 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.
6. The method of claim 1, wherein: the organic solvent is at least one of dimethylacetamide, acetonitrile, N-dimethylformamide, acetone and N-methylpyrrolidone.
7. The method of claim 1, wherein: the sequential mixing 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 the salt, the polymer matrix and the fluorine-doped carbon nitride powder are respectively ultrasonically mixed with the organic solvent, and then are mixed and stirred.
8. The method of claim 1, wherein: the film forming treatment mode is a pouring method or a coating method.
9. A fluorine-doped carbon nitride-polymer composite solid electrolyte is characterized in that: prepared by the preparation method of any one of claims 1 to 8.
10. The application of the fluorine-doped carbon nitride-polymer composite solid electrolyte in the solid battery is characterized in that: the composite solid electrolyte is prepared by the preparation method of any one of claims 1 to 8; the solid-state battery is a solid-state lithium ion battery or a solid-state sodium ion battery.
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Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116435A1 (en) * | 2006-03-30 | 2007-10-18 | Fujitsu Limited | Solid electrolyte composition and polymer fuel cell |
| CN104659338A (en) * | 2015-03-17 | 2015-05-27 | 东莞市迈科科技有限公司 | Preparation method of positive electrode material of lithium sulfur battery |
| CN104772160A (en) * | 2015-04-17 | 2015-07-15 | 北京师范大学 | Carbon nitride photocatalytic activity nano fiber membrane and preparation method thereof |
| CN105874642A (en) * | 2013-12-27 | 2016-08-17 | 索尼公司 | Battery, electrolyte, battery pack, electronic device, electric vehicle, electricity-storage device, and power system |
| CN108198691A (en) * | 2017-12-25 | 2018-06-22 | 阜阳师范学院 | Nitrogenize the preparation method and dye-sensitized solar cells of carbon derivative and redox graphene compound |
| US20190020027A1 (en) * | 2017-07-14 | 2019-01-17 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode active material containing carbon, boron, and calcium, and nitrogen or phosphorus, and battery |
| CN109378522A (en) * | 2018-10-22 | 2019-02-22 | 北京科技大学 | A kind of sodium zirconium silicon phosphorus method for preparing composite solid electrolyte |
| CN109755640A (en) * | 2019-03-13 | 2019-05-14 | 西安交通大学 | A kind of preparation method of composite solid polymer electrolyte |
| CN109802173A (en) * | 2019-01-24 | 2019-05-24 | 北京化工大学 | A kind of three-phase organic/inorganic plural gel state polymer dielectric and preparation method thereof |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
| US20190190005A1 (en) * | 2017-12-18 | 2019-06-20 | Samsung Electronics Co., Ltd. | Negative electrode for metal battery, metal battery comprising the same, and method of preparing the negative electrode for metal battery |
| CN110389162A (en) * | 2019-07-23 | 2019-10-29 | 合肥工业大学 | Gold doping carbonitride composite material and preparation method, the detection method of methyl mercury |
| US10594322B2 (en) * | 2017-07-11 | 2020-03-17 | iCometrue Company Ltd. | Logic drive based on standard commodity FPGA IC chips using non-volatile memory cells |
| CN111048828A (en) * | 2018-10-12 | 2020-04-21 | 三星电子株式会社 | Composite electrolyte, lithium metal battery including the same, and method of preparing the composite electrolyte |
| US10680243B2 (en) * | 2017-07-19 | 2020-06-09 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode active material containing carbon and boron, and nitrogen or phosphorus, and battery including the same |
| CN111354972A (en) * | 2020-02-06 | 2020-06-30 | 华南理工大学 | Composite solid electrolyte material and preparation method and application thereof |
-
2020
- 2020-08-20 CN CN202010844626.6A patent/CN111952674B/en active Active
Patent Citations (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007116435A1 (en) * | 2006-03-30 | 2007-10-18 | Fujitsu Limited | Solid electrolyte composition and polymer fuel cell |
| CN105874642A (en) * | 2013-12-27 | 2016-08-17 | 索尼公司 | Battery, electrolyte, battery pack, electronic device, electric vehicle, electricity-storage device, and power system |
| CN104659338A (en) * | 2015-03-17 | 2015-05-27 | 东莞市迈科科技有限公司 | Preparation method of positive electrode material of lithium sulfur battery |
| CN104772160A (en) * | 2015-04-17 | 2015-07-15 | 北京师范大学 | Carbon nitride photocatalytic activity nano fiber membrane and preparation method thereof |
| US10594322B2 (en) * | 2017-07-11 | 2020-03-17 | iCometrue Company Ltd. | Logic drive based on standard commodity FPGA IC chips using non-volatile memory cells |
| US20190020027A1 (en) * | 2017-07-14 | 2019-01-17 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode active material containing carbon, boron, and calcium, and nitrogen or phosphorus, and battery |
| US10680243B2 (en) * | 2017-07-19 | 2020-06-09 | Panasonic Intellectual Property Management Co., Ltd. | Negative electrode active material containing carbon and boron, and nitrogen or phosphorus, and battery including the same |
| US20190190005A1 (en) * | 2017-12-18 | 2019-06-20 | Samsung Electronics Co., Ltd. | Negative electrode for metal battery, metal battery comprising the same, and method of preparing the negative electrode for metal battery |
| CN108198691A (en) * | 2017-12-25 | 2018-06-22 | 阜阳师范学院 | Nitrogenize the preparation method and dye-sensitized solar cells of carbon derivative and redox graphene compound |
| CN111048828A (en) * | 2018-10-12 | 2020-04-21 | 三星电子株式会社 | Composite electrolyte, lithium metal battery including the same, and method of preparing the composite electrolyte |
| CN109378522A (en) * | 2018-10-22 | 2019-02-22 | 北京科技大学 | A kind of sodium zirconium silicon phosphorus method for preparing composite solid electrolyte |
| CN109802173A (en) * | 2019-01-24 | 2019-05-24 | 北京化工大学 | A kind of three-phase organic/inorganic plural gel state polymer dielectric and preparation method thereof |
| CN109841817A (en) * | 2019-03-01 | 2019-06-04 | 同济大学 | For the modification lithium base composite negative pole material of solid state battery and its preparation and application |
| CN109755640A (en) * | 2019-03-13 | 2019-05-14 | 西安交通大学 | A kind of preparation method of composite solid polymer electrolyte |
| CN110389162A (en) * | 2019-07-23 | 2019-10-29 | 合肥工业大学 | Gold doping carbonitride composite material and preparation method, the detection method of methyl mercury |
| CN111354972A (en) * | 2020-02-06 | 2020-06-30 | 华南理工大学 | Composite solid electrolyte material and preparation method and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| KANG, SUHEE等: "Evaluation of dual layered photoanode for enhancement of visible-light-driven applications", 《RSC ADVANCES》 * |
| LI, XUE等: "One-dimension carbon self-doping g-C3N4 nanotubes: Synthesis and application in dye-sensitized solar cells", 《NANO RESEARCH 》 * |
| WANG, YANLIN等: "Ultrasensitive photoelectrochemical microRNA biosensor based on doxorubicin sensitized graphitic carbon nitride assisted by a target-activated enzyme-free DNA walker", 《CHEMICAL COMMUNICATIONS》 * |
| 汪勋 等: "一种高离子电导率复合聚合物电解质的简易热处理制备", 《中国科学:化学》 * |
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