CN116404246A - Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof - Google Patents
Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof Download PDFInfo
- Publication number
- CN116404246A CN116404246A CN202310479208.5A CN202310479208A CN116404246A CN 116404246 A CN116404246 A CN 116404246A CN 202310479208 A CN202310479208 A CN 202310479208A CN 116404246 A CN116404246 A CN 116404246A
- Authority
- CN
- China
- Prior art keywords
- titanium carbide
- self
- solid electrolyte
- polymer solid
- assembled
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 90
- 229920000642 polymer Polymers 0.000 title claims abstract description 86
- 239000007784 solid electrolyte Substances 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000002356 single layer Substances 0.000 claims abstract description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011701 zinc Substances 0.000 claims abstract description 13
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 238000005530 etching Methods 0.000 claims abstract description 6
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 62
- 239000000243 solution Substances 0.000 claims description 21
- 239000011259 mixed solution Substances 0.000 claims description 18
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 16
- 229910052744 lithium Inorganic materials 0.000 claims description 16
- 239000003792 electrolyte Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims description 11
- 229910001416 lithium ion Inorganic materials 0.000 claims description 11
- 229910003002 lithium salt Inorganic materials 0.000 claims description 11
- 159000000002 lithium salts Chemical class 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000003825 pressing Methods 0.000 claims description 5
- 239000010936 titanium Substances 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 4
- 239000010409 thin film Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 3
- 229910000951 Aluminide Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 20
- 239000000945 filler Substances 0.000 abstract description 7
- 239000002131 composite material Substances 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 4
- 239000000758 substrate Substances 0.000 abstract description 3
- 230000002441 reversible effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 150000002500 ions Chemical class 0.000 description 8
- GELKBWJHTRAYNV-UHFFFAOYSA-K lithium iron phosphate Chemical group [Li+].[Fe+2].[O-]P([O-])([O-])=O GELKBWJHTRAYNV-UHFFFAOYSA-K 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 230000001351 cycling effect Effects 0.000 description 5
- 239000010408 film Substances 0.000 description 5
- 229910001251 solid state electrolyte alloy Inorganic materials 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000004146 energy storage Methods 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical group [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000000996 additive effect Effects 0.000 description 2
- 239000001768 carboxy methyl cellulose Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 239000011244 liquid electrolyte Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000006245 Carbon black Super-P Substances 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 239000011231 conductive filler Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000012983 electrochemical energy storage Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- UNASZPQZIFZUSI-UHFFFAOYSA-N methylidyneniobium Chemical compound [Nb]#C UNASZPQZIFZUSI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Images
Classifications
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/056—Accumulators with non-aqueous electrolyte characterised by the materials used as electrolytes, e.g. mixed inorganic/organic electrolytes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0068—Solid electrolytes inorganic
-
- 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
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0065—Solid electrolytes
- H01M2300/0082—Organic polymers
-
- 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
-
- 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
- H01M2300/0088—Composites
- H01M2300/0091—Composites in the form of mixtures
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Dispersion Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Physics & Mathematics (AREA)
- Conductive Materials (AREA)
- Primary Cells (AREA)
Abstract
The invention relates to a self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof, which adopts PEO polymer as a base material, obtains single-layer titanium carbide (MXene) through standard etching stripping, mixes the obtained titanium carbide and PEO, prepares gel by self-assembly on a zinc sheet, and finally freeze-dries to obtain the PEO polymer solid electrolyte of self-assembled titanium carbide filler. Compared with the prior art, the stacking-free titanium carbide sheet obtained by the invention is uniformly dispersed in the PEO substrate by self-assembly, can obtain the high-performance composite polymer solid electrolyte in one step, and has the advantages of low cost, simple process, mild condition, high reversible capacity, very good cycle stability and the like.
Description
Technical Field
The invention relates to the technical field of electrochemistry, in particular to a self-assembled titanium carbide doped polymer solid electrolyte, and preparation and application thereof.
Background
With the development and progress of the automotive industry, the problem of human sustainable development faces a great challenge. Combustion of non-renewable fuels can release various exhaust gases, leading to various problems. Therefore, it is particularly important to find renewable and sustainable resource energy storage devices. The chargeable and dischargeable battery is economical, environment-friendly, high in power and long in service life, and compared with non-renewable energy sources, the chargeable and dischargeable battery achieves continuous utilization of energy sources. Particularly, the lithium ion battery has the advantages of high energy density, no memory effect, low maintenance cost, low self-discharge effect and the like, and is one of the most promising electrochemical energy storage battery technologies at present. And becomes one of the most important chargeable and dischargeable cells.
The polymer solid electrolyte is a novel electrolyte material, can be used in energy storage equipment such as lithium ion batteries and the like, and has good ion transmission performance, high chemical stability and excellent safety performance. Compared with the traditional liquid electrolyte, the polymer solid electrolyte can solve the problems of inflammability, volatilization, leakage and the like of the liquid electrolyte under the action of high temperature or external pressure, thereby improving the safety performance of the energy storage device.
Polymer solid state electrolytes are typically composed of an ion conducting polymer matrix and a lithium ion plasma, the optimization of their structure and performance being critical to the fabrication of high performance batteries. The polymer matrix may be made of various materials, such as polyethylene oxide (PEO), polyacrylonitrile (PAN), etc., and the ion transmission performance of the polymer matrix may be improved by different chemical modification, doping or crosslinking methods. Meanwhile, in order to improve lithium ion conductivity and chemical stability of the solid electrolyte, it is often necessary to add additives such as lithium salts, inorganic oxides, and the like.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the self-assembled titanium carbide doped polymer solid electrolyte, and the preparation and application thereof.
The aim of the invention can be achieved by the following technical scheme:
the preparation method of the self-assembled titanium carbide doped polymer solid electrolyte comprises the following specific steps:
s1, preparing single-layer titanium carbide (MXene);
s2, preparing PEO polymer solution;
s3, adding the single-layer titanium carbide obtained in the step S1 into the PEO polymer solution obtained in the step S2, and performing ultrasonic treatment to obtain a mixed solution A;
and S4, freeze-drying and pressing the mixed solution A obtained in the step S3 to obtain the self-assembled titanium carbide doped polymer solid electrolyte.
In step S1, the titanium carbide aluminide powder is etched and peeled off to obtain a two-dimensional single-layer titanium carbide (MXene).
The specific steps of the etching are as follows: adding LiF into concentrated hydrochloric acid, dissolving LiF, and adding Ti 3 AiC 2 And stirring to obtain a mixed solution C, wherein the etching principle is that Al in the raw materials is removed by strong acid.
The stirring temperature is 30 to 40 ℃, preferably 35 ℃.
The concentration of the concentrated hydrochloric acid is 8 to 10mol.
Further to the above, liF: ti (Ti) 3 AiC 2 : concentrated hydrochloric acid=1 to 2g: 1-2 g:30ml.
The specific steps of the stripping are as follows: and washing the mixed solution C, centrifuging, and performing ultrasonic treatment to obtain the two-dimensional single-layer titanium carbide (MXene).
The washing mode is as follows: washing with deionized water for 6-7 times.
The above further, the centrifugal speed is 4000-6000rpm, preferably 5000rpm, and the centrifugal time is 10-50min, preferably 30min.
The ultrasonic temperature is between-10 ℃ and 10 ℃, and the ultrasonic time is between 0.5h and 1.5h.
Further, in step S2, polyethylene oxide (PEO) is stirred uniformly in deionized water, and then lithium salt is added, and the PEO polymer solution is obtained after complete dissolution.
The lithium salt is lithium bis (trifluoromethylsulfonyl) imide (LiTFSi), and polyethylene oxide (PEO) is a substrate of a polymer solid electrolyte, and mainly serves as a substrate, and after the lithium salt is added, the decomposition of the lithium salt can be promoted, so that lithium ions can be transported.
The above further, the polyethylene oxide is in a powder form.
Further to the above, the number average molecular weight of the polyethylene oxide is 600000 ～ 100000.
The polyethylene oxide concentration in the PEO polymer solution is 85% to 95%, preferably 90%.
The mass ratio of the lithium salt to the polyethylene oxide is 1 to 1.5:10.
the stirring time is 12 to 24 hours.
Further, in step S3, the mass ratio of the single-layer titanium carbide to the polyethylene oxide in the PEO polymer solution is 1-2:10.
Further, in step S3, the single-layer titanium carbide obtained in step S1 is added to the PEO polymer solution obtained in step S2, magnetically stirred and sonicated to obtain a mixed solution a.
The time of the magnetic stirring is 12-24 hours.
The ultrasonic time is 10 to 15 hours.
In step S4, the mixed solution A obtained in step S3 is coated on a zinc sheet for a certain time, and then the self-assembled titanium carbide doped polymer solid electrolyte is obtained after freeze-drying and pressing.
The zinc sheet is a polished smooth zinc sheet.
The mixed solution a obtained in step S3 is further held on the zinc sheet for 1 to 3 hours.
The invention also provides a self-assembled titanium carbide doped polymer solid electrolyte, which is prepared by adopting the preparation method of the self-assembled titanium carbide doped polymer solid electrolyte.
Further, the self-assembled titanium carbide doped polymer solid electrolyte is a thin film with a flat surface as a whole, and a two-dimensional single layer of titanium carbide is uniformly dispersed in the thin film.
In addition, the invention also provides a lithium ion battery, which comprises the self-assembled titanium carbide doped polymer solid electrolyte.
Further, the lithium ion battery is a lithium symmetrical battery or a button type full battery, the positive electrode and the negative electrode of the lithium symmetrical battery are all pure lithium sheets, the positive electrode of the button type full battery is lithium iron phosphate, and the negative electrode of the button type full battery is a pure lithium sheet.
The principle of the invention is as follows:
titanium carbide (MXene) is a potential filler that can be used in polymer solid state electrolytes. When filled into PEO solid state electrolytes, titanium carbide, because of its high electrical conductivity, can be used as an additive to enhance the ion transport properties of polymer solid state electrolytes and thus enhance the performance characteristics of batteries. In addition, titanium carbide has high chemical stability, can effectively prevent the decomposition and oxidation of electrolyte, improve the stability and durability of electrolyte. However, on the other hand, the amount of titanium carbide added needs to be controlled, and too high an amount of titanium carbide added causes an increase in viscosity of the electrolyte, affecting charge and discharge efficiency of the battery. The dispersibility of titanium carbide is not easily controlled, resulting in a decrease in uniformity and stability of the electrolyte. The addition of two-dimensional titanium carbide as a filler to PEO solid state electrolytes is therefore primarily needed to address the above issues. Therefore, due to the intrinsic two-dimensional nano layered structure, good hydrophilicity, excellent conductivity and mechanical property of the MXene, the Mxene-based material is widely used for electrode material compounding in the fields of energy storage and conversion, and has wide application prospects in various fields such as lithium ion batteries, supercapacitors, photo (electro) catalyst electrodes and the like.
According to the invention, by adding the single-layer titanium carbide (MXene), the composite polymer solid electrolyte material obtained after self-assembly can improve the originally insufficient cycling stability and increase the ionic conductivity so as to have better electrochemical performance.
Compared with niobium carbide nano-sheets, the single-layer titanium carbide has better mechanical properties, the mechanical strength of the battery can be improved, PEO polymer solid electrolyte is generally fragile and easy to break, and the mechanical strength of the electrolyte can be improved by filling the single-layer titanium carbide into the PEO solid electrolyte, so that the durability and the reliability of the battery are improved.
The single-layer titanium carbide has good thermal stability, can protect PEO polymer solid electrolyte in the battery, prevent the PEO polymer solid electrolyte from being decomposed due to high temperature, and prolong the service life of the battery; and the thermal runaway of the battery can be effectively restrained, the spontaneous combustion and explosion risks of the battery are reduced, and the safety performance of the battery is improved.
According to the invention, the preparation of the solid electrolyte is directly carried out on the zinc sheet, so that a film with a flat surface and uniform dispersion can be obtained in one step; in the preparation of the solid electrolyte film, the dispersing of the MXene is directly induced by zinc ions in the zinc plate, so that the performance degradation caused by stacking of MXene sheets can be directly avoided from the source, the functional groups on the surface of the MXene which are dispersed by the zinc ions are induced to better promote the decomposition of lithium salt so as to improve the performance, and an additive is not required to be added in the later stage to improve the uniform dispersing of the MXene filler.
Compared with the prior art, the invention has the following beneficial effects:
1. the gel prepared by self-assembling the single-layer titanium carbide and PEO on a zinc sheet after mixing, and finally freeze-drying to obtain the PEO polymer solid electrolyte of the self-assembled titanium carbide filler, so that the method is simple and convenient;
2. the invention takes two-dimensional titanium carbide as filler, and has the advantages of designability of raw materials and wide application;
3. the self-assembled composite polymer solid electrolyte material prepared by the method of the invention has the advantages that in the solid electrolyte material, MXene is added as a filler, so that the electrochemical performance of the solid electrolyte material can be obviously improved, and the ion conductivity and the mechanical strength of the solid electrolyte are improved;
4. PEO (polyethylene oxide) is a common solid electrolyte material, which has higher ionic conductivity at room temperature, but lower mechanical strength, and is easy to cause mechanical failure, and when MXene is added into PEO, the mechanical strength can be increased, and meanwhile, a large number of polymer chains can be grafted on oxide functional groups on the surface of MXene, so that the compatibility of the MXene and the PEO is increased, and the conductivity and stability of the electrode material are improved;
5. MXene as conductive filler can promote ion transmission in PEO material, increase ion migration number and ion diffusion coefficient, and enhance functional group (-OH, etc.) on MXene-based material surface and anion (TFSI) in lithium salt - ) To promote Li + Migration in polyethylene oxide (PEO) matrix to improve the output power and cycling stability of the cell;
6. in the working environment of 60 ℃, the ion conductivity of the self-assembled titanium carbide doped polymer solid electrolyte is as high as 2.62x10 -4 S/cm -1 Under the charge-discharge flow of 0.3C, the full battery capacity of the lithium iron phosphate/lithium sheet can reach 158 mAh.g -1 Can maintain an overpotential of 26mv at a charge-discharge current of 0.1mA for more than 300 hours, thus self-assemblingThe titanium carbide doped polymer solid electrolyte has wide application prospect in the field of lithium ion batteries, and provides good experimental data and theoretical support for the research and application of MXene and inorganic materials in the electrochemical field.
Drawings
FIG. 1 is a schematic diagram of a self-assembled titanium carbide doped polymer solid electrolyte dry film material obtained in example 1;
FIG. 2 is a cross-sectional view of the self-assembled titanium carbide doped polymer solid electrolyte material of example 1;
FIG. 3 is an SEM image of the solid electrolyte surface of the pure PEO polymer obtained in comparative example 1;
FIG. 4 is an SEM image of the surface of a self-assembled titanium carbide doped polymer solid electrolyte material obtained in example 1;
FIG. 5 is a schematic diagram showing the results of testing the ionic conductivity of the self-assembled titanium carbide doped polymer solid electrolyte material obtained in example 1 in a working environment of 30-60 ℃;
FIG. 6 is a graph showing the cycling performance of the solid state electrolyte of the simple mixing of titanium carbide/PEO obtained in comparative example 2 and the self-assembled titanium carbide doped polymer solid state electrolyte obtained in example 1 as a lithium symmetric battery electrolyte;
fig. 7 is a graph showing the cycling performance of the pure PEO polymer solid electrolyte obtained in comparative example 1, the titanium carbide/PEO simple mixed solid electrolyte obtained in comparative example 2, and the self-assembled titanium carbide doped polymer solid electrolyte material obtained in example 1 as lithium iron phosphate/lithium tablet full cell electrolyte.
Detailed Description
The invention will now be described in detail with reference to the drawings and specific examples.
Example 1
The embodiment provides a preparation method of self-assembled titanium carbide doped polymer solid electrolyte, which comprises the following specific steps:
firstly, preparing single-layer titanium carbide:
(1) Preparing 60ml of 10mol HCL solution;
(2) 3g LiF was added to the HCL solution and stirred for 10min until all dissolved;
(3) 3g of Ti 3 AiC 2 Slowly adding the solution, and etching for 72 hours;
(4) And (3) washing the solution obtained in the step (3) with deionized water for 6-7 times, centrifuging at a rotation speed of 5000rmp for 30min, adding water into the obtained sample, and putting the sample into a plastic bottle for ice bath ultrasonic treatment for 1h to obtain two-dimensional single-layer titanium carbide (MXene).
Second step, preparing PEO polymer solution:
600mg of polyethylene oxide (PEO) was mixed and stirred in deionized water for 12 hours, then 60mg of LiTFSi was added, and ultrasonic treatment was performed to sufficiently dissolve it, thereby obtaining a PEO polymer solution, wherein the concentration of polyethylene oxide in the PEO polymer solution was 90%.
Thirdly, preparing the surfactant modified MXene/polymer solid electrolyte:
adding 60mg of two-dimensional single-layer titanium carbide obtained in the first step into the PEO polymer solution obtained in the second step, magnetically stirring for 12h, performing ultrasonic treatment for 10h to obtain a mixed solution A, coating the mixed solution A on a zinc sheet for 3 h, and performing freeze-drying and pressing to obtain the self-assembled titanium carbide doped polymer solid electrolyte, wherein a physical diagram and a morphology diagram are shown in figures 1 and 2.
Example 2
This example is substantially the same as example 1 except that in this example, in the third step, the amount of titanium carbide added to the two-dimensional monolayer was 70mg.
Example 3
This example is substantially the same as example 1 except that in this example, in the third step, the amount of titanium carbide added to the two-dimensional monolayer was 80mg.
Performance test:
the self-assembled titanium carbide doped polymer solid electrolyte obtained in example 1 was used as a lithium battery solid electrolyte for lithium symmetric batteries and button type full batteries.
The symmetrical battery uses two pure lithium sheets as a pair of electrodes,
the full battery was prepared by mixing lithium iron phosphate, carbon black (Super-P), sodium carboxymethylcellulose (CMC) in a weight ratio of 7:2:1, and then uniformly coating the mixture on a pure aluminum foil (99.6%) by a coating method, and using a pure lithium sheet as a negative electrode.
The cycle performance test and the electrochemical test are carried out by using the lithium symmetrical battery and the button type full battery, the cycle performance graph and the multiplying power performance graph are shown in fig. 6 and 7, and the cycle performance and the stability after the self-assembled titanium carbide doped polymer solid electrolyte is added can be seen to be improved.
Comparative example 1
The present comparative example uses pure PEO polymer solid state electrolyte.
Comparative example 2
This comparative example was substantially the same as example 1 except that in the third step, 60mg of two-dimensional monolayer titanium carbide obtained in the first step was added to the PEO polymer solution obtained in the second step to be sonicated, to obtain a mixed solution A, and the mixed solution A was dropped on a mold to be dried, to obtain a solid electrolyte of titanium carbide/PEO simple mixing.
Analysis of results:
FIG. 1 is a schematic representation of the self-assembled titanium carbide doped polymer solid electrolyte dried film material obtained in example 1, from which the dried composite film is evident;
FIG. 2 is a cross-sectional view of the self-assembled titanium carbide doped polymer solid electrolyte material of example 1, from which it can be seen that the uniform dispersion of the thickness and cross-section of the thin film and the zinc ions participate in the self-assembly;
FIG. 3 is an SEM image of the surface of a solid electrolyte of a pure PEO polymer obtained in comparative example 1, from which voids and irregularities of the surface are evident;
fig. 4 is an SEM image of the surface of the self-assembled titanium carbide doped polymer solid electrolyte material obtained in example 1, from which it is apparent that the surface is very flat.
FIG. 5 shows the ionic conductivity of the self-assembled titanium carbide doped polymer solid electrolyte material obtained in example 1 in a working environment of 30-60 ℃ by testing, and it can be seen that the ionic conductivity is significantly increased with increasing temperature, and the ionic conductivity in a working environment of 60 ℃ is calculatedThe rate is 2.62x10 -4 S/cm -1 ；
FIG. 6 is a graph showing the cycling performance of the solid state electrolyte of the simple mixing of titanium carbide/PEO obtained in comparative example 2 and the self-assembled titanium carbide doped polymer solid state electrolyte obtained in example 1 as a lithium symmetric battery electrolyte, showing a significant reduction in overpotential after self-assembling MXene.
FIG. 7 is a graph showing the cycle performance of the pure PEO polymer solid electrolyte obtained in comparative example 1, the solid electrolyte of simple mixing of titanium carbide/PEO obtained in comparative example 2, and the self-assembled titanium carbide doped polymer solid electrolyte material obtained in example 1 as a lithium iron phosphate/lithium tablet full cell electrolyte, showing that the capacity is significantly improved after the self-assembled titanium carbide doped polymer solid electrolyte obtained in example 1 is subjected to a charge-discharge flow of 0.3C, and the capacity of the lithium iron phosphate/lithium tablet full cell can reach 158 mAh.g -1 The over-potential of 26mv can be kept for more than 300 hours under the charge-discharge current of 0.1mA, so that the self-assembled titanium carbide doped polymer solid electrolyte has wide application prospect in the field of lithium ion batteries, and provides good experimental data and theoretical support for research and application of MXene and inorganic materials in the electrochemical field.
The previous description of the embodiments is provided to facilitate a person of ordinary skill in the art in order to make and use the present invention. It will be apparent to those skilled in the art that various modifications can be readily made to these embodiments and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above-described embodiments, and those skilled in the art, based on the present disclosure, should make improvements and modifications without departing from the scope of the present invention.
Claims (10)
1. The preparation method of the self-assembled titanium carbide doped polymer solid electrolyte is characterized by comprising the following specific steps:
s1, preparing single-layer titanium carbide;
s2, preparing PEO polymer solution;
s3, adding the single-layer titanium carbide obtained in the step S1 into the PEO polymer solution obtained in the step S2, and performing ultrasonic treatment to obtain a mixed solution A;
and S4, freeze-drying and pressing the mixed solution A obtained in the step S3 to obtain the self-assembled titanium carbide doped polymer solid electrolyte.
2. The method for preparing the self-assembled titanium carbide doped polymer solid electrolyte according to claim 1, wherein in the step S1, the titanium carbide aluminide powder is etched and stripped to obtain the two-dimensional single-layer titanium carbide.
3. The method for preparing the self-assembled titanium carbide doped polymer solid electrolyte according to claim 2, wherein the specific steps of etching are as follows: adding LiF into concentrated hydrochloric acid, dissolving LiF, and adding Ti 3 AiC 2 Stirring to obtain a mixed solution C, wherein the etching principle is that Al in the raw materials is removed by strong acid;
the stirring temperature is 30-40 ℃, the concentration of the concentrated hydrochloric acid is 8-10 mol,
LiF：Ti 3 AiC 2 : concentrated hydrochloric acid=1 to 2g: 1-2 g:30ml;
the specific steps of the stripping are as follows: washing the mixed solution C, centrifuging, performing ultrasonic treatment to obtain two-dimensional single-layer titanium carbide,
the washing mode is as follows: washing with deionized water for 6-7 times,
the centrifugal speed is 4000-6000rpm, the centrifugal time is 10-50min,
the ultrasonic temperature is-10 ℃ to 10 ℃, and the ultrasonic time is 0.5h to 1.5h.
4. The method for preparing a self-assembled titanium carbide doped polymer solid electrolyte according to claim 1, wherein in step S2, polyethylene oxide is stirred uniformly in deionized water, and then lithium salt is added, and after sufficient dissolution, PEO polymer solution is obtained.
5. The method for preparing a self-assembled titanium carbide doped polymer solid electrolyte according to claim 4, wherein the lithium salt is lithium bistrifluoromethylsulfonylimide,
the polyethylene oxide is in the form of powder,
the number average molecular weight of the polyethylene oxide is 600000 ～ 100000,
the concentration of polyethylene oxide in the PEO polymer solution is 85% -95%,
the mass ratio of the lithium salt to the polyethylene oxide is 1-1.5: 10,
the stirring time is 12-24 hours.
6. The method for preparing a self-assembled titanium carbide doped polymer solid electrolyte according to claim 1, wherein in the step S3, the mass ratio of the single-layer titanium carbide to polyethylene oxide in the PEO polymer solution is 1-2:10;
in the step S3, adding the single-layer titanium carbide obtained in the step S1 into the PEO polymer solution obtained in the step S2, magnetically stirring and carrying out ultrasonic treatment to obtain a mixed solution A;
the magnetic stirring time is 12-24 h, and the ultrasonic time is 10-15 h.
7. The method for preparing the self-assembled titanium carbide doped polymer solid electrolyte according to claim 1, wherein in the step S4, the mixed solution A obtained in the step S3 is coated on a zinc sheet for a certain time, and the self-assembled titanium carbide doped polymer solid electrolyte is obtained after the freeze-drying and pressing,
the zinc sheet is a polished smooth zinc sheet, and the mixed solution A obtained in the step S3 is kept on the zinc sheet for 1-3 hours.
8. A self-assembled titanium carbide doped polymer solid electrolyte prepared by the method of any one of claims 1-7.
9. The self-assembled titanium carbide doped polymer solid electrolyte according to claim 8, wherein the self-assembled titanium carbide doped polymer solid electrolyte is a thin film having a flat surface throughout and wherein a two-dimensional monolayer of titanium carbide is uniformly dispersed therein.
10. A lithium ion battery comprising the self-assembled titanium carbide doped polymer solid state electrolyte of claim 8 or claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310479208.5A CN116404246A (en) | 2023-04-28 | 2023-04-28 | Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310479208.5A CN116404246A (en) | 2023-04-28 | 2023-04-28 | Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116404246A true CN116404246A (en) | 2023-07-07 |
Family
ID=87017984
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310479208.5A Pending CN116404246A (en) | 2023-04-28 | 2023-04-28 | Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116404246A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117174989A (en) * | 2023-09-04 | 2023-12-05 | 华北电力大学 | High-conductivity composite solid electrolyte with continuous interface and preparation method and application thereof |
-
2023
- 2023-04-28 CN CN202310479208.5A patent/CN116404246A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117174989A (en) * | 2023-09-04 | 2023-12-05 | 华北电力大学 | High-conductivity composite solid electrolyte with continuous interface and preparation method and application thereof |
| CN117174989B (en) * | 2023-09-04 | 2024-07-09 | 华北电力大学 | High-conductivity composite solid electrolyte with continuous interface and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Xu et al. | Gel polymer electrolyte based on PVDF-HFP matrix composited with rGO-PEG-NH2 for high-performance lithium ion battery | |
| US10826130B2 (en) | Negative active material and preparation method thereof and secondary battery | |
| CN110350196B (en) | Composite binder, silicon-based negative plate and preparation method thereof | |
| CN108682820B (en) | Silicon-carbon composite negative electrode material, negative electrode plate, preparation method of negative electrode plate and lithium ion battery | |
| CN109346767A (en) | A kind of solid polymer electrolyte and its application in lithium metal battery | |
| CN103633293A (en) | Lithium ion battery negative electrode piece using hard carbon and soft carbon as active materials and lithium ion battery | |
| CN102274965B (en) | Method for improving electrochemical performance of hydrogen storage alloy powder by utilizing electropolymerization polyaniline | |
| CN109728342A (en) | A kind of selfreparing composite solid electrolyte, quasi-solid electrolyte and lithium battery | |
| Yang et al. | Three-electrode flexible zinc-nickel battery with black phosphorus modified polymer electrolyte | |
| KR102334001B1 (en) | Silicon/polymer composite nanoparticles, anode for lithium secondary battery comprising the same, and method for manufacturing the silicon/polymer composite nanoparticles | |
| Chen et al. | Polymeric Binders Used in Lithium Ion Batteries: Actualities, Strategies and Trends | |
| CN115832412A (en) | Composite solid electrolyte and preparation method and application thereof | |
| CN116404246A (en) | Self-assembled titanium carbide doped polymer solid electrolyte and preparation and application thereof | |
| CN110931727A (en) | Preparation method of conductive polymer-coated silicon-based negative electrode material | |
| CN110911741A (en) | Carbon oxide sphere doped solid polymer electrolyte membrane and preparation method and application thereof | |
| CN112271324B (en) | High-voltage solid-state lithium battery and preparation method thereof | |
| CN110931850A (en) | Polysiloxane composite electrolyte, application thereof and preparation method thereof | |
| CN114094096B (en) | Method for forming protective polymer film on surface of sodium titanium phosphate negative electrode material, product and application thereof | |
| CN114204125B (en) | Preparation method of integrated solid-state lithium iron phosphate battery | |
| CN116014079A (en) | Lignin water-based composite battery binder and preparation method and application of silicon-based negative plate thereof | |
| CN101794908B (en) | Method for preparing solid electrolyte based on polyphosphazenes nanometer tube dope | |
| JP4054925B2 (en) | Lithium battery | |
| CN114361391B (en) | Polymer modified nano silicon negative electrode material and preparation method and application thereof | |
| CN116598581A (en) | Surfactant modified MXene/polymer solid electrolyte and preparation and application thereof | |
| CN114464879B (en) | Self-repairing block polymeric ionic liquid/polyethylene oxide composite solid electrolyte and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |