CN110890546A - High-conductivity liquid metal-coated low-temperature-resistant energy storage material and preparation method thereof - Google Patents
High-conductivity liquid metal-coated low-temperature-resistant energy storage material and preparation method thereof Download PDFInfo
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- 238000004146 energy storage Methods 0.000 title claims abstract description 40
- 239000011232 storage material Substances 0.000 title claims abstract description 40
- 229910001338 liquidmetal Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000001291 vacuum drying Methods 0.000 claims abstract description 29
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- 239000000203 mixture Substances 0.000 claims abstract description 22
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- 239000000843 powder Substances 0.000 claims abstract description 17
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000007788 liquid Substances 0.000 claims abstract description 12
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- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000002033 PVDF binder Substances 0.000 claims abstract description 10
- 239000006230 acetylene black Substances 0.000 claims abstract description 10
- 239000013543 active substance Substances 0.000 claims abstract description 10
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 10
- 239000007787 solid Substances 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 239000011889 copper foil Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 claims description 4
- 239000011149 active material Substances 0.000 claims description 4
- 239000003599 detergent Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 239000007773 negative electrode material Substances 0.000 claims description 4
- 229960001948 caffeine Drugs 0.000 claims 1
- RYYVLZVUVIJVGH-UHFFFAOYSA-N trimethylxanthine Natural products CN1C(=O)N(C)C(=O)C2=C1N=CN2C RYYVLZVUVIJVGH-UHFFFAOYSA-N 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 5
- 239000002253 acid Substances 0.000 abstract description 4
- 238000005530 etching Methods 0.000 abstract description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 2
- 239000000523 sample Substances 0.000 abstract 4
- 239000000243 solution Substances 0.000 description 17
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
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- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910000846 In alloy Inorganic materials 0.000 description 1
- 229910013872 LiPF Inorganic materials 0.000 description 1
- 101150058243 Lipf gene Proteins 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- JHKXZYLNVJRAAJ-WDSKDSINSA-N Met-Ala Chemical compound CSCC[C@H](N)C(=O)N[C@@H](C)C(O)=O JHKXZYLNVJRAAJ-WDSKDSINSA-N 0.000 description 1
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- 230000003247 decreasing effect Effects 0.000 description 1
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- 238000000921 elemental analysis Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
- H01M4/386—Silicon or alloys based on silicon
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/624—Electric conductive fillers
- H01M4/626—Metals
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- 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
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- Y02E60/10—Energy storage using batteries
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Abstract
The invention relates to the technical field of preparation of energy storage materials of lithium ion batteries, in particular to a high-conductivity liquid metal-coated low-temperature-resistant energy storage material and a preparation method thereof, wherein the high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared by the following steps: adding Ti3AlC2 black powder into a hydrofluoric acid solution to obtain a first mixture; centrifuging, washing and vacuum drying the first mixture to obtain a sample MX; adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing and vacuum drying to obtain a sample MX-LM; mixing the MX-LM sample, acetylene black and polyvinylidene fluoride, adding N-methyl pyrrolidone serving as a solvent, stirring, uniformly coating a layer of active substance, and performing vacuum drying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material. The preparation method is simple, and the product has high porosity by acid etching of the layered material, can realize effective increase of ionic conductivity at low temperature, and has low temperature resistance.
Description
Technical Field
The invention relates to the technical field of preparation of energy storage materials of lithium ion batteries, in particular to a high-conductivity liquid metal-coated low-temperature-resistant energy storage material and a preparation method thereof.
Background
Extreme temperatures can interfere with the normal operation of the power system battery to a large extent. Particularly in alpine regions, the extremely low temperature easily causes the power supply capacity to drop, the battery material to age, the capacity attenuation is serious, the charging and discharging curve is not matched with the design curve, the output power drops and other consequences, and instability is brought to the use of power supply equipment and the failure rate is increased. At present, more than 1 million power transmission and transformation monitoring devices are installed in high latitude areas in China, the real-time access rate of the power transmission and transformation monitoring devices is 87.88%, and the real-time access rate of the power transformation online monitoring devices is 98.76%; the real-time access rate of the power transmission on-line monitoring device is 62.92%. The failure of the power transmission and transformation monitoring device is averagely over 2000 times per year, and the failure is eliminated for thousands of times. Power failure is one of the main reasons for the failure of power transmission monitoring devices, which are distributed in unmanned areas such as high cold areas, high temperature areas and the like, and are affected by the environment, and the power supply is prone to failure (23% of failures are caused by power failure), so that the on-line monitoring equipment cannot normally operate and cannot upload on-line monitoring data.
Disclosure of Invention
The invention provides a high-conductivity liquid metal-coated low-temperature-resistant energy storage material and a preparation method thereof, overcomes the defects of the prior art, and can effectively solve the problems of low ionic conductivity and low capacitance in high and cold area climate.
One of the technical schemes of the invention is realized by the following measures: a high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared by the following method: in a first step, the desired amount of Ti3AlC2Adding the black powder into a hydrofluoric acid solution with the mass fraction of 20 wt% and uniformly mixing to obtain a first mixture, wherein 0.5g to 3.5g of Ti is added into every 10mL to 50mL of the hydrofluoric acid solution3AlC2Black powder; secondly, stirring the first mixture at room temperature for 12 to 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 11 to 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then carrying out vacuum drying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
The following is a further optimization or/and improvement of one of the above-mentioned technical solutions of the invention:
in the second step, the third step and the fourth step, the temperature of vacuum drying is 58 ℃ to 62 ℃, and the vacuum drying time is 10 hours to 12 hours.
And when the first solid substance and the second solid substance are washed, the detergent is deionized water or absolute ethyl alcohol, and the washing times are 1 to 3.
In the third step, the ultrasonic treatment time is 1.5 to 2.5 hours.
In the fourth step, the active material is graphite or silicon carbon negative electrode material.
The second technical scheme of the invention is realized by the following measures: a preparation method of a high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared according to the following steps: firstly, adding required amount of Ti3AlC2 black powder into hydrofluoric acid solution with the mass fraction of 20 wt% and uniformly mixing to obtain a first mixture, wherein 0.5g to 3.5g of Ti3AlC2 black powder is added into every 10mL to 50mL of hydrofluoric acid solution; secondly, stirring the first mixture at room temperature for 12 to 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 11 to 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then carrying out vacuum drying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
The following is further optimization or/and improvement of the second technical scheme of the invention:
in the second step, the third step and the fourth step, the temperature of vacuum drying is 58 ℃ to 62 ℃, and the vacuum drying time is 10 hours to 12 hours.
And when the first solid substance and the second solid substance are washed, the detergent is deionized water or absolute ethyl alcohol, and the washing times are 1 to 3.
In the third step, the ultrasonic treatment time is 1.5 to 2.5 hours.
In the fourth step, the active material is graphite or silicon carbon negative electrode material.
The preparation method is simple, and the product has high porosity by acid etching of the layered material, can realize effective increase of ionic conductivity at low temperature, and has low temperature resistance.
Drawings
FIG. 1 is an SEM image before and after blending of MX and LM under different magnifications in the invention.
FIG. 2 is a mapping diagram of the element analysis of MX and LM blends in the present invention.
FIG. 3 is a graph of the rate performance of the MX-LM/PP/Li cell of the present invention under different current test conditions.
FIG. 4 shows that the MX-LM/PP/Li cell of the present invention is in 1Ag state-1Cycle 1000 plots under current test conditions.
FIG. 5 is a graph of the cyclic capacity at different temperatures according to the present invention.
Fig. 6 is a graph comparing the capacity of the battery against low temperatures using different binders according to the present invention.
Detailed Description
The present invention is not limited by the following examples, and specific embodiments may be determined according to the technical solutions and practical situations of the present invention. The various chemical reagents and chemical articles mentioned in the invention are all the chemical reagents and chemical articles which are well known and commonly used in the prior art, unless otherwise specified; the percentages in the invention are mass percentages unless otherwise specified; the solution in the present invention is an aqueous solution in which the solvent is water, for example, a hydrochloric acid solution is an aqueous hydrochloric acid solution, unless otherwise specified; the normal temperature and room temperature in the present invention generally mean a temperature of 15 ℃ to 25 ℃, and are generally defined as 25 ℃.
The invention is further described below with reference to the following examples:
example 1: the high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared by the following method: in a first step, the desired amount of Ti3AlC2Adding the black powder into a hydrofluoric acid solution with the mass fraction of 20 wt%, and uniformly mixing to obtain a first mixture, wherein 0.5g to 3.5g of Ti3AlC2 black powder is added into every 10mL to 50mL of the hydrofluoric acid solution; secondly, stirring the first mixture at room temperature for 12 to 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding solvent N-methyl pyrrolidone, stirring for 11-12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then carrying out vacuumDrying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
According to the invention, the layered material is etched by acid, so that the obtained high-conductivity liquid metal-coated low-temperature-resistant energy storage material has high porosity, the reaction active area is increased, the overall ionic conductivity is increased at low temperature, and the low-temperature-resistant energy storage material has low-temperature resistance, can effectively solve the key bottleneck restricting the capacity exertion limitation of the lithium battery under the low-temperature condition, and has wide application prospect in the application field of large-scale low-temperature region power supplies.
In the present invention, the liquid LM metal is a conventional liquid gallium indium alloy known in the art.
Example 2: the high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared by the following method: in a first step, the desired amount of Ti3AlC2Adding the black powder into a hydrofluoric acid solution with the mass fraction of 20 wt%, and uniformly mixing to obtain a first mixture, wherein 0.5g or 3.5g of Ti3AlC2 black powder is added into 10mL or 50mL of the hydrofluoric acid solution; secondly, stirring the first mixture at room temperature for 12 hours or 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 11 hours or 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then drying in vacuum to obtain the high-conductivity liquid metal coated low-temperature-resistant energy storage material.
Example 3: as optimization of the above embodiment, in the second step, the third step and the fourth step, the temperature of vacuum drying is 58 ℃ to 62 ℃, and the vacuum drying time is 10 hours to 12 hours.
Example 4: as an optimization of the above embodiment, the washing agents of the first solid substance and the second solid substance are deionized water or absolute ethyl alcohol, and the number of washing times is 1 to 3.
Example 5: as an optimization of the above examples, in the third step, the sonication time is from 1.5 hours to 2.5 hours.
Example 6: the preparation method of the high-conductivity liquid metal-coated low-temperature-resistant energy storage material comprises the following steps: in a first step, the desired amount of Ti3AlC2Adding the black powder into a hydrofluoric acid solution with the mass fraction of 20 wt%, and uniformly mixing to obtain a first mixture, wherein 0.5g to 3.5g of Ti3AlC2 black powder is added into every 10mL to 50mL of the hydrofluoric acid solution; secondly, stirring the first mixture at room temperature for 12 to 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 11 to 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then carrying out vacuum drying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
Example 7: the high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared by the following method: in the first step, 0.5g of Ti is added3AlC2Adding the black powder into 10mL of 20 wt% hydrofluoric acid solution, and uniformly mixing to obtain a first mixture; secondly, stirring the first mixture at room temperature for 12 hours, centrifuging, washing the obtained first solid substance with deionized water for three times, and drying in vacuum at 60 ℃ for 12 hours to obtain a sample MX; thirdly, adding a sample MX into liquid LM metal, performing ultrasonic treatment for 2 hours, centrifuging, washing the obtained second solid substance with deionized water for three times, and performing vacuum drying at 60 ℃ for 12 hours to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then drying in vacuum at 60 ℃ for 12 hours to obtain the high-conductivity liquid metal coated low-resistance metalA thermal energy storage material.
Example 8: the high-conductivity liquid metal-coated low-temperature-resistant energy storage material is prepared by the following method: step one, adding 3.5g of Ti3AlC2 black powder into 50mL of hydrofluoric acid solution with the mass fraction of 20 wt% and uniformly mixing to obtain a first mixture; secondly, stirring the first mixture at room temperature for 48 hours, centrifuging, washing the obtained first solid substance with deionized water for three times, and performing vacuum drying at 60 ℃ for 12 hours to obtain a sample MX; thirdly, adding a sample MX into liquid LM metal, performing ultrasonic treatment for 2 hours, centrifuging, washing the obtained second solid substance with deionized water for three times, and performing vacuum drying at 60 ℃ for 12 hours to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then drying in vacuum at 60 ℃ for 12 hours to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
In examples 7 and 8 of the present invention, the electron microscope observation is performed on the sample MX, and the result is shown in FIG. 1-a and FIG. 1-b, wherein FIG. 1-a is an SEM image of the sample MX at 1 μm, and FIG. 1-b is an SEM image of the sample MX at 10 μm; it can be seen from FIGS. 1-a and 1-b that MX has a typical layered structure.
In examples 7 and 8 of the invention, the result of electron microscope observation of the sample MX-LM is shown in FIGS. 1-c and 1-d, wherein FIG. 1-c is an SEM image of the sample MX-LM at 1 μm, and FIG. 1-d is an SEM image of the sample MX-LM at 5 μm; it can be seen from FIGS. 1-c and 1-d that MX-LM has a typical layered structure.
In examples 7 and 8 of the present invention, elemental analysis is performed on a sample MX-LM, and the results are shown in FIG. 2-a, FIG. 2-b, FIG. 2-c, and FIG. 2-d, wherein FIG. 2-a is an SEM image of the sample MX-LM at 1 μm, FIG. 2-b is an analysis photograph of element Ga, FIG. 2-c is an analysis photograph of element Ti, FIG. 2-d is an elemental energy spectrum of MX-LM, and it can be seen from FIG. 2-a, FIG. 2-b, FIG. 2-c, and FIG. 2-d that the elemental composition of the product MX-LM includes all elements of the raw material. Thus, it can be demonstrated that LM is fully incorporated into the layered result, forming a composite structure, which provides the possibility for subsequent electrochemical performance.
According to the high-conductivity liquid metal-coated low-temperature-resistant energy storage material obtained in the embodiment 7 and the embodiment 8 of the invention, a 14mm cutter is used for cutting the high-conductivity liquid metal-coated low-temperature-resistant energy storage material into a circular pole piece, the circular pole piece is assembled in an Ar atmosphere glove box to obtain a button battery, namely an MX-LM diaphragm/Li battery, and LiPF is used6As the electrolyte, MX-LM separator/Li cell specification 2025, binder WAR 268. The electrochemical performance test and the low temperature resistance test of the MX-LM membrane/Li battery are carried out, and the results are respectively shown in fig. 3, fig. 4 and fig. 5, wherein fig. 3 is a multiplying power performance diagram of the MX-LM membrane/Li battery under different current test conditions, and fig. 4 is a 1Ag performance diagram of the MX-LM/membrane/Li battery-1The cycle under current test conditions is shown in 1000 cycles, fig. 5 is a graph of the cycle capacity at different temperatures, and fig. 6 is a graph of the resistance of different binder batteries to low temperatures.
As can be seen from fig. 3 and 4, the high-conductivity liquid metal-coated low-temperature-resistant energy storage material can maintain good cycle performance at high current density;
FIG. 5 shows that the change of the cyclic capacity curve at different temperatures is greatly improved after modification;
the parameters of the MX-LM membrane/Li battery using SBR and WAR268 as binders are tested, the results are shown in FIG. 6, and FIG. 6 shows that the low-temperature capacity of the composite electrode is greatly improved by using the binder WRA268 compared with the capacity of the SBR battery.
In conclusion, the preparation method is simple, and the product has high porosity by acid etching of the layered material, can realize effective increase of ionic conductivity at low temperature and has low temperature resistance.
The technical characteristics form an embodiment of the invention, which has strong adaptability and implementation effect, and unnecessary technical characteristics can be increased or decreased according to actual needs to meet the requirements of different situations.
Claims (10)
1. A high-conductivity liquid metal-coated low-temperature-resistant energy storage material is characterized by being prepared according to the following method: first, theIn one step, the required amount of Ti3AlC2Adding the black powder into a hydrofluoric acid solution with the mass fraction of 20 wt% and uniformly mixing to obtain a first mixture, wherein 0.5g to 3.5g of Ti3AlC2 black powder is added into every 10mL to 50mL of the hydrofluoric acid solution; secondly, stirring the first mixture at room temperature for 12 to 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; and fourthly, mixing the MX-LM sample, the acetylene black and the polyvinylidene fluoride according to the ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 11 to 12 hours, uniformly coating a layer of active substance on the copper foil by using a 100-micrometer scraper, and then carrying out vacuum drying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
2. The high-conductivity liquid metal-coated low-temperature-resistant energy storage material as claimed in claim 1, wherein the temperature of vacuum drying in the second step, the third step and the fourth step is 58 ℃ to 62 ℃ and the time of vacuum drying is 10 hours to 12 hours.
3. The high-conductivity liquid metal-coated low-temperature-resistant energy storage material as claimed in claim 1 or 2, wherein the detergent used for washing the first solid substance and the second solid substance is deionized water or absolute ethyl alcohol, and the number of washing times is 1 to 3.
4. The high-conductivity liquid metal coated low-temperature-resistant energy storage material according to claim 1, 2 or 3, wherein in the third step, the ultrasonic time is 1.5 hours to 2.5 hours.
5. The high-conductivity liquid metal coated low-temperature-resistant energy storage material as claimed in claim 1, 2, 3 or 4, wherein in the fourth step, the active material is graphite or silicon carbon negative electrode material.
6. A preparation method of a high-conductivity liquid metal-coated low-temperature-resistant energy storage material is characterized by comprising the following steps: firstly, adding required amount of Ti3AlC2 black powder into hydrofluoric acid solution with the mass fraction of 20 wt% and uniformly mixing to obtain a first mixture, wherein 0.5g to 3.5g of Ti3AlC2 black powder is added into every 10mL to 50mL of hydrofluoric acid solution; secondly, stirring the first mixture at room temperature for 12 to 48 hours, centrifuging, washing the obtained first solid matter, and drying in vacuum to obtain a sample MX; thirdly, adding the sample MX into liquid LM metal, performing ultrasonic treatment, centrifuging, washing the obtained second solid substance, and performing vacuum drying to obtain a sample MX-LM; fourthly, mixing MX-LM, acetylene black and polyvinylidene fluoride according to a ratio of 8:1:1, adding a solvent N-methyl pyrrolidone, stirring for 11 to 12 hours, uniformly coating a layer of active substance on a copper foil by using a 100um scraper, and then carrying out vacuum drying to obtain the high-conductivity liquid metal-coated low-temperature-resistant energy storage material.
7. The high-conductivity liquid metal-coated low-temperature-resistant energy storage material as claimed in claim 6, wherein the temperature of vacuum drying in the second step, the third step and the fourth step is 58 ℃ to 62 ℃ and the time of vacuum drying is 10 hours to 12 hours.
8. The high-conductivity liquid metal-coated low-temperature-resistant energy storage material as claimed in claim 6 or 7, wherein the detergent used for washing the first solid substance and the second solid substance is deionized water or absolute ethyl alcohol, and the number of washing times is 1 to 3.
9. The high-conductivity liquid metal coated low-temperature-resistant energy storage material according to claim 6, 7 or 8, wherein in the third step, the ultrasonic time is 1.5 hours to 2.5 hours.
10. The high-conductivity liquid metal coated low-temperature-resistant energy storage material as claimed in claim 6, 7, 8 or 9, wherein in the fourth step, the active material is graphite or silicon carbon negative electrode material.
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