CN115832222A - Flexible sodium-ion battery cathode, preparation method thereof and flexible sodium-ion battery - Google Patents
Flexible sodium-ion battery cathode, preparation method thereof and flexible sodium-ion battery Download PDFInfo
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- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 80
- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 80
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000002238 carbon nanotube film Substances 0.000 claims abstract description 51
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 238000011065 in-situ storage Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 14
- 239000010406 cathode material Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 27
- 239000004952 Polyamide Substances 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- 229920002647 polyamide Polymers 0.000 claims description 18
- 239000002243 precursor Substances 0.000 claims description 16
- 229910052717 sulfur Inorganic materials 0.000 claims description 15
- 239000011593 sulfur Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 238000004806 packaging method and process Methods 0.000 claims description 11
- -1 polydimethylsiloxane Polymers 0.000 claims description 11
- 239000002994 raw material Substances 0.000 claims description 11
- 239000011149 active material Substances 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 238000005096 rolling process Methods 0.000 claims description 9
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- 239000003792 electrolyte Substances 0.000 claims description 8
- 239000004005 microsphere Substances 0.000 claims description 8
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 7
- 239000002002 slurry Substances 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002033 PVDF binder Substances 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000002073 nanorod Substances 0.000 claims description 6
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- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 5
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 5
- 239000011248 coating agent Substances 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 3
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000006835 compression Effects 0.000 claims description 2
- 238000007906 compression Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000007773 negative electrode material Substances 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 10
- 229910052799 carbon Inorganic materials 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 239000003431 cross linking reagent Substances 0.000 description 7
- 238000011161 development Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical group COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- 239000006258 conductive agent Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000007772 electrode material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 3
- 239000004312 hexamethylene tetramine Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
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- 150000002815 nickel Chemical class 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
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- 239000002245 particle Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
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- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
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Images
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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
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
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- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention provides a flexible sodium-ion battery cathode, a preparation method thereof and a flexible sodium-ion battery. The flexible sodium-ion battery cathode comprises a carbon nano tube film and a nickel sulfide cathode material growing on the carbon nano tube film in situ; wherein the mass of the nickel sulfide negative electrode material growing on the carbon nano tube film in situ is 0.3-1mg/cm 2 (ii) a The thickness of the carbon nano tube film is 1-5 mu m. The invention is formed by carbon nano-tubeThe film is used as a current collector, and a nickel sulfide negative electrode material is grown on the carbon nano tube film in situ by a one-step hydrothermal method to prepare a flexible sodium ion battery negative electrode; the flexible sodium-ion battery assembled by the prepared flexible sodium-ion battery cathode does not peel off in the circulation process, is stable in circulation, and has the advantages of high energy density, high rate capability and high safety performance.
Description
Technical Field
The invention belongs to the technical field of sodium ion batteries, and particularly relates to a flexible sodium ion battery cathode, a preparation method thereof and a flexible sodium ion battery.
Background
The energy problem is one of the most urgent problems in the development process of the economic science society at the present stage, and the development of novel high-energy-density secondary battery anode and cathode materials is the key point of the research in the energy storage field at present. At present, secondary batteries applied in large scale industry are mainly lithium ion batteries for realizing energy storage through intercalation reaction, however, with the increasing shortage of global lithium resources, the huge future demands on the lithium ion battery market are difficult to meet, and sodium ion batteries are batteries with similar charge and discharge mechanisms as lithium ion batteries, and because the sodium resources are far richer than the lithium resources, the sodium ion batteries have great research and development prospects; at present, sodium ion batteries are not put into large-scale production and application formally, and are mainly limited by the development of high-performance anode and cathode materials, and the electrochemical performance of the electrode material mainly depends on the sodium storage mechanism of the material.
In addition, with the rapid development of smart wearable devices, flexible electronic products, implantable medical devices, and other concepts, flexible energy storage technology is also receiving increasing attention. At present, under the condition that the flexibility problem of other components is gradually solved, the flexibility of the driving power becomes a key for restricting the development and application of flexible electronic devices. Therefore, development of low-cost, high-performance, light and thin secondary battery systems to drive development of flexible electronic devices is urgently needed.
The invention patent CN113036097A discloses a preparation method of a sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material, which comprises the following steps: firstly, respectively dissolving inorganic nickel salt and hexamethylenetetramine in a solvent to respectively obtain an inorganic nickel salt solution and a hexamethylenetetramine solution; then, uniformly mixing the inorganic nickel salt solution and the hexamethylenetetramine solution in a dropwise manner, and then standing and growing for 12-50h at the temperature of 80-160 ℃ to obtain a primary product containing the nickel-based metal organic framework template; after centrifugal separation, mixing the nickel sulfide with a sulfur source and an oxidant, and then carrying out pyrolysis reaction to prepare the sulfur vacancy nitrogen doped carbon coated nickel sulfide composite electrode material; however, the sodium ion battery negative electrode material has no flexibility, and a binder and a conductive agent are required to be added in the electrode preparation process, and the negative electrode prepared by coating the material on a metal current collector is easy to peel off in the circulation process after being bent for many times, so that the circulation performance is influenced, the requirement of the existing flexible device cannot be met, and the material has no competitiveness in the field of intelligent wearable equipment.
Therefore, it is very important to provide a flexible sodium ion battery having high energy density, high flexibility and excellent electrochemical performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a flexible sodium-ion battery cathode, a preparation method thereof and a flexible sodium-ion battery; according to the invention, the carbon nanotube film is used as a current collector, and the nickel sulfide negative electrode material growing on the carbon nanotube film in situ is used as the negative electrode of the flexible sodium-ion battery, so that a conductive agent and a binder are not required to be added, and the carbon nanotube film has light weight and large specific surface area, so that the mass energy density of the carbon nanotube film is improved; meanwhile, the nickel sulfide negative electrode material grows on the carbon nano tube film in situ, so that the adhesion force between the nickel sulfide negative electrode material and the carbon nano tube film is good, the phenomenon of powder falling and demoulding can not occur after the nickel sulfide negative electrode material is bent for multiple times, the flexible sodium ion battery assembled by the flexible sodium ion battery negative electrode prepared by the method can not generate the stripping phenomenon in the circulating process, the circulation is stable, and the flexible sodium ion battery has the advantages of high energy density, high rate capability and good safety performance.
In order to achieve the above object, a first aspect of the present invention provides a flexible sodium ion battery negative electrode, which adopts the following technical scheme:
a flexible sodium-ion battery negative electrode comprising: the cathode material comprises a carbon nano tube film and a nickel sulfide cathode material growing on the carbon nano tube film in situ;
wherein the mass of the nickel sulfide cathode material in-situ grown on the carbon nanotube film is 0.3-1mg/cm 2 (ratio ofE.g. 0.4mg/cm 2 、0.5mg/cm 2 、0.6mg/cm 2 、0.7mg/cm 2 、0.8mg/cm 2 、0.9mg/cm 2 、0.95mg/cm 2 )；
The carbon nanotube film has a thickness of 1 to 5 μm (e.g., 1.5 μm, 2 μm, 2,5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm).
In the above flexible sodium-ion battery negative electrode, as a preferred embodiment, the nickel sulfide negative electrode material has a micro-morphology of a secondary microsphere composed of a plurality of nanorods, the nanorods have a diameter of 10-30nm (such as 12nm, 15nm, 20nm, 22nm, 25nm, 28nm, 29 nm), and the secondary microsphere has a diameter of 1-200 μm (such as 5 μm, 10 μm, 20 μm, 50 μm, 100 μm, 150 μm, 180 μm).
The second aspect of the invention provides a preparation method of the flexible sodium-ion battery cathode, which comprises the following steps:
s1, dispersing a template agent, a nickel source and a sulfur source into an organic solvent for mixing treatment to obtain a precursor solution;
and S2, adding the carbon nanotube film into the precursor solution, carrying out hydrothermal reaction, and after the reaction is finished, sequentially carrying out filtering treatment, washing treatment, drying treatment and compression roller treatment to obtain the flexible sodium-ion battery cathode.
In the above preparation method, as a preferred embodiment, in step S1, the template is an amino-terminated hyperbranched polyamide;
preferably, the nickel source is selected from one or more of nickel acetate, nickel sulfate and nickel chloride;
preferably, the sulfur source is selected from one or more of sulfur powder, thiourea and sodium persulfate;
preferably, the molar ratio of the amino-terminated hyperbranched polyamide to the nickel element in the nickel source and the sulfur element in the sulfur source is (1-8): 1:3 (e.g. 2.
Adding a carbon nanotube film into a precursor solution, and utilizing the complexation between terminal amino groups in amino-terminated hyperbranched polyamide (AHP) and Ni ions to further assemble amino-terminated hyperbranched polyamide molecules into a super-molecular body with a hyperbranched flexible chain segment structure; then, growing a nickel sulfide negative electrode material with a secondary microsphere structure on the carbon nano tube film in situ through a hydrothermal reaction; due to the fact that the hyperbranched flexible chain segments are arranged inside the nickel sulfide negative electrode material and can provide elastic buffer areas for the electrodes, structure evolution in the circulating process is adapted, aggregation and volume expansion of nickel sulfide particles are reduced, excellent rate performance and long circulating stability of the material are achieved, in addition, due to the fact that the carbon nano tube film can provide elastic conductive grids and ion diffusion paths, sodium ion diffusion dynamics in the electrodes are enhanced, and meanwhile due to the fact that the carbon nano tube film is light in weight and large in specific surface area, mass energy density of the battery is improved.
In the above preparation method, as a preferred embodiment, in step S1, the preparation method of the amino-terminated hyperbranched polyamide comprises: dispersing diethylenetriamine and methyl acrylate as reaction raw materials in methanol, stirring and reacting for 10-15h (such as 11h, 12h, 13h and 14 h) at 0-10 ℃ (such as 2 ℃, 3 ℃,5 ℃, 7 ℃ and 9 ℃), then adding ethylenediamine, reacting for 0.5-2h (such as 0.8h, 1h, 1.5h and 1.8 h) at 60-80 ℃ (such as 62 ℃, 65 ℃, 70 ℃, 75 ℃ and 78 ℃), and reacting for 6-10h (such as 6.5h, 7h, 7.5h, 8h and 9 h) at 120-140 ℃ (such as 122 ℃, 125 ℃, 130 ℃, 135 ℃ and 138 ℃) in nitrogen atmosphere;
preferably, the molar ratio of the diethylenetriamine to the methyl acrylate and the ethylenediamine is 2.
Preferably, the volume ratio of the methanol to the diethylenetriamine is 1.
In the above production method, as a preferred embodiment, in step S1, the organic solvent is selected from methanol and/or ethanol;
preferably, the amount concentration of the template in the precursor solution is 0.05-0.5mol/L (e.g., 0.08mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4 mol/L).
In the above preparation method, as a preferred embodiment, in step S2, the temperature of the hydrothermal reaction is 160 to 200 ℃ (such as 165 ℃, 170 ℃, 175 ℃, 185 ℃, 180 ℃, 190 ℃) and the hydrothermal reaction time is 12 to 24 hours (such as 15 hours, 18 hours, 20 hours, 22 hours, 23 hours).
In the above preparation method, as a preferred embodiment, in step S2, the temperature of the drying treatment is 60 to 80 ℃ (such as 62 ℃, 65 ℃, 70 ℃, 75 ℃, 78 ℃) and the drying time is 6 to 20h (such as 7h, 10h, 12h, 15h, 18 h).
A third aspect of the invention provides a flexible sodium-ion battery comprising: the flexible sodium-ion battery comprises an electrode assembly, electrolyte and an outer packaging body, wherein the electrode assembly and the electrolyte are packaged by the outer packaging body to prepare the flexible sodium-ion battery; wherein the electrode assembly includes: the negative electrode is the flexible sodium-ion battery negative electrode or the flexible sodium-ion battery negative electrode prepared by the preparation method.
In the above flexible sodium-ion battery, as a preferred embodiment, the positive electrode includes: a positive current collector and active material layers attached to the front and back sides of the positive current collector; the active material layer comprises the following raw materials in percentage by mass: 90% -95% (such as 90.5%, 91%, 92%, 93%, 94%, 94.5%, 94.8%) of sodium vanadium phosphate, 3% -7% (such as 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%) of conductive carbon black (SP), 2% -5% (such as 2.2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 4.8%) of polyvinylidene fluoride (PVDF).
In the above flexible sodium-ion battery, as a preferred embodiment, the positive electrode current collector is a carbon nanotube thin film with a thickness of 1-5 μm (e.g., 1.5 μm, 2 μm, 2,5 μm, 3 μm, 3.5 μm, 4 μm, 4.5 μm);
preferably, the raw material of the active material layer is dispersed in N-methyl pyrrolidone (NMP) to prepare slurry, and then the slurry is coated and attached on the positive electrode current collector, and then dried and rolled to prepare the positive electrode;
preferably, the positive electrode obtained after the rolling treatment is compactedThe degree is 1.8-2.4g/cm 3 (e.g., 1.9 mg/cm) 2 、2mg/cm 2 、2.1mg/cm 2 、2.2mg/cm 2 、2.3mg/cm 2 、2.35mg/cm 2 、2.38mg/cm 2 )。
In the above flexible sodium ion battery, as a preferred embodiment, the ratio of N/P (negative electrode active material gram volume × negative electrode surface density × negative electrode active material content ratio ÷ (positive electrode active material gram volume × positive electrode surface density × positive electrode active material content ratio)) in the electrode assembly is 1.06 to 1.2:1 (such as 1.08.
In the above flexible sodium-ion battery, as a preferred embodiment, the material of the exterior body is polydimethylsiloxane.
Compared with the prior art, the invention has the following advantages:
(1) According to the invention, the carbon nanotube film is used as a current collector, and the nickel sulfide negative electrode material growing on the carbon nanotube film in situ is used as the negative electrode of the flexible sodium-ion battery, so that a conductive agent and a binder are not required to be added, and the carbon nanotube film has light weight and large specific surface area, so that the mass energy density is improved; meanwhile, the nickel sulfide cathode material has good binding power with the carbon nanotube film, and the phenomenon of powder falling and demoulding can not occur after multiple times of bending.
(2) The flexible sodium-ion battery assembled by the prepared flexible sodium-ion battery cathode does not peel off in the circulation process, is stable in circulation, and has the advantages of high energy density, high rate capability and high safety performance.
(3) The invention further assembles amino-terminated hyperbranched polyamide molecules into a super molecular body with a hyperbranched flexible chain segment structure by utilizing the complexation of the terminal amino group in the amino-terminated hyperbranched polyamide (AHP) and Ni ions; then, growing a nickel sulfide negative electrode material with a secondary microsphere structure on the carbon nano tube film in situ through a hydrothermal reaction; due to the fact that the hyperbranched flexible chain segments are arranged inside the nickel sulfide negative electrode material and can provide an elastic buffer area for the electrode, structure evolution in the circulating process is adapted, aggregation and volume expansion of nickel sulfide particles are relieved, and excellent rate performance and long-cycle stability of the material are achieved.
Drawings
Fig. 1 is a schematic structural view of a flexible sodium ion battery manufactured according to the present invention;
fig. 2 is an XRD pattern of nickel sulfide cathode material in the cathode of the flexible sodium-ion battery prepared in example 1 of the present invention;
fig. 3 is an SEM image of the negative electrode of the flexible sodium-ion battery according to example 1 of the present invention;
fig. 4 is a diagram of a flexible sodium-ion battery prepared in example 1 of the present invention.
Description of reference numerals: 1. an electrode assembly; 11. a diaphragm; 12. a negative electrode; 121. carbon nanotube film, 122, nickel sulfide negative electrode material; 13. a positive electrode; 131. a positive current collector; 132. an active material layer; 2. and an outer packaging body.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitation of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, the terms "longitudinal", "lateral", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings, which are for convenience of description of the present invention only and do not require that the present invention must be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present invention. The terms "connected," "connected," and "disposed" as used herein are intended to be broadly construed, and may include, for example, fixed and removable connections; can be directly connected or indirectly connected through intermediate components; the connection may be a wired electrical connection, a wireless electrical connection, or a wireless communication signal connection, and a person skilled in the art can understand the specific meaning of the above terms according to specific situations.
The embodiments of the present invention are implemented on the premise of the technical scheme of the present invention, and detailed embodiments and processes are given, but the scope of the present invention is not limited to the following embodiments, and the following embodiments do not indicate process parameters of specific conditions, and generally follow conventional conditions.
The endpoints of the ranges and any values disclosed in the present application are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
In the present invention, all numerical values relating to amounts of components are "parts by weight" throughout, unless otherwise specified and/or indicated. The process parameters for the following examples, without specifying the particular conditions, are generally in accordance with conventional conditions. The starting materials described in the following examples are all commercially available from the public. The preparation method of the carbon nanotube film used in the embodiment of the invention refers to the preparation method of the hydrophilic carbon nanotube film disclosed in patent CN108584917A of the invention, and the carbon nanotube film is cut to the available size for standby application according to the use requirement; the preparation method of the amino-terminated hyperbranched polyamide used in the specific embodiment of the invention comprises the following steps: adding 0.12mol of diethylenetriamine and 0.12mol of methyl acrylate into 60mL of methanol, stirring and reacting for 12h at 5 ℃, then dropwise adding 0.02mol of ethylenediamine, reacting for 1h at 70 ℃, and then reacting for 7h at 130 ℃ in a nitrogen atmosphere to obtain light yellow viscous liquid amino-terminated hyperbranched polyamide.
An embodiment of the present invention provides a flexible sodium-ion battery, referring to fig. 1, including: an electrode assembly 1, an electrolyte, and an outer package 2; the electrode assembly 1 comprises a diaphragm 11, a negative electrode 12, a diaphragm 11, a positive electrode 13 and a diaphragm 11 (the negative electrode 12 and the positive electrode 13 are arranged in plurality and are arranged at intervals through the diaphragm 11); the cathode 12 comprises a carbon nanotube film 121 and a nickel sulfide cathode material 122 growing on the carbon nanotube film 121 in situ;
further, the mass of the nickel sulfide negative electrode material 122 in-situ grown on the carbon nanotube film 121 is 0.3-1mg/cm 2 ；
Further, the thickness of the carbon nanotube film 121 is 1 to 5 μm;
further, the micro-morphology of the nickel sulfide negative electrode material 122 is a secondary microsphere composed of a plurality of nanorods, the diameter of the nanorods is 10-30nm, and the diameter of the secondary microsphere is 1-200 μm;
further, the positive electrode 13 includes a positive electrode current collector 131 and active material layers 132 attached on the front and back surfaces of the positive electrode current collector 131;
further, the positive current collector 131 is a carbon nanotube film with a thickness of 1-5 μm;
further, the raw materials of the active material layer 132 include, in mass percent: 90-95% of sodium vanadium phosphate, 3-7% of conductive carbon black (SP) and 2-5% of PVDF;
further, the compacted density of the positive electrode 13 obtained after the roll-pressing treatment is 1.8 to 2.4g/cm 3 。
Further, the ratio of N/P in the electrode assembly 1 is 1.06-1.2:1;
further, the diaphragm 11 is made of a single-sided ceramic double-sided adhesive mixed coating diaphragm 9+2 μm;
further, the electrolyte is 1mol/L sodium hexafluorophosphate solution, and the solvent is ethylene glycol dimethyl ether;
further, the outer package 2 is made of polydimethylsiloxane, and is prepared by using a prepolymer A and a cross-linking agent B as raw materials (the prepolymer A mainly comprises a poly-dimethylvinylsiloxane prepolymer and a trace platinum catalyst, the cross-linking agent B comprises a prepolymer with a vinyl side chain and a cross-linking agent poly (dimethylhydrogensiloxane), and by mixing the prepolymer A and the cross-linking agent poly (dimethylhydrogensiloxane), the vinyl and a silicon hydrogen bond can undergo a hydrosilylation reaction to form a three-dimensional network structure, the mass ratio of the prepolymer A to the cross-linking agent B is 10.
The specific embodiment of the invention provides a preparation method of a flexible sodium-ion battery, which comprises the following steps:
(1) Preparation of the negative electrode 12: firstly, dispersing amino-terminated hyperbranched polyamide, a nickel source and a sulfur source into an organic solvent for mixing treatment to obtain a precursor solution; wherein, the nickel source is selected from one or more of nickel acetate, nickel sulfate and nickel chloride, and the sulfur source is selected from one or more of sulfur powder, thiourea and sodium persulfate; the molar ratio of the amino-terminated hyperbranched polyamide to nickel element in the nickel source and sulfur element in the sulfur source is (1-8): 1:3, the mass concentration of the amino-terminated hyperbranched polyamide in the precursor solution is 0.05-0.5mol/L; then adding the carbon nano tube film 121 into the precursor solution, carrying out hydrothermal reaction at 160-200 ℃ for 12-24h, and after the reaction is finished, sequentially carrying out filtration treatment, washing treatment and drying treatment at 60-80 ℃ for 6-20h to obtain the nickel sulfide material 122 (with the mass of 0.3-1 mg/cm) growing on the carbon nano tube film 121 in situ 2 ) The flexible sodium ion battery negative electrode 12.
(2) Preparation of the positive electrode 13: dispersing the raw material of the active material layer 132 in NMP to prepare slurry, then coating the slurry on the positive current collector 131 (carbon nanotube film), and then drying and rolling to prepare the positive electrode 13; the compacted density of the positive electrode 13 obtained after the rolling treatment is 1.8 to 2.4g/cm 3 ；
(3) Preparation of electrode assembly 1: the electrode assembly 1 is obtained by laminating a separator 11, a negative electrode 12, a separator 11, a positive electrode 13 and a separator 11 from top to bottom, and the N/P ratio in the electrode assembly 1 is 1.06-1.2:1;
(4) Preparing a flexible sodium-ion battery: the preparation method comprises the steps of taking prepolymer A and cross-linking agent B as raw materials, carrying out curing treatment and demolding treatment in a mold to prepare an outer packaging body 2 made of polydimethylsiloxane, then filling an electrode assembly 1 and electrolyte into the outer packaging body 2, and then sealing by using the polydimethylsiloxane to obtain the flexible sodium-ion battery.
The present invention will be described in further detail with reference to specific examples.
Embodiment 1 a method of making a flexible sodium-ion battery, comprising:
(1) Preparing a flexible sodium-ion battery cathode:
firstly, the mol ratio of amino-terminated hyperbranched polyamide to nickel acetate to thiourea is 2:1:3, adding the mixture into 70mL of methanol, and stirring and mixing for 1h to obtain a precursor solution; the precursor solution was then transferred to a 100mL teflon-lined stainless steel autoclave, to which was added a 2 μm thick carbon nanotube film (5 x 10cm in area of the carbon nanotube film) 2 ) Performing hydrothermal reaction at 180 ℃ for 20h, cooling to room temperature, performing filtration treatment to obtain a carbon nano tube film with a nickel sulfide negative electrode material grown in situ, ultrasonically washing the carbon nano tube film with methanol for several times, drying the carbon nano tube film at 70 ℃ for 10h, and performing roll-pressing treatment to obtain the nickel sulfide negative electrode material grown in situ on the carbon nano tube film with the mass of 0.46mg/cm 2 The flexible sodium-ion battery negative electrode (fig. 2 is an XRD pattern of the nickel sulfide negative electrode material in the flexible sodium-ion battery negative electrode prepared in example 1 of the present invention, and fig. 3 is an SEM image of the flexible sodium-ion battery negative electrode);
(2) Preparation of the positive electrode: firstly, mixing sodium vanadium phosphate, SP and PVDF in NMP according to a mass ratio of 92 2 Then the mixture is subjected to vacuum drying and rolling treatment to obtain the compact density of 2g/cm 3 A positive electrode;
(3) Preparing an electrode assembly: the N/P ratio of the electrode assembly is 1.15, and the separator, the negative electrode, the separator and the positive electrode are arranged from top to bottom (the area of the positive electrode current collector, namely the carbon nano tube film is 5 x 10 cm) 2 ) Stacking the diaphragm structures to obtain an electrode assembly, wherein the number of the negative electrodes is 10, and the number of the positive electrodes is 10;
(4) Preparing a flexible sodium-ion battery: the external packaging body made of polydimethylsiloxane is prepared by taking the prepolymer A and the cross-linking agent B as raw materials and carrying out curing treatment and demoulding treatment in a mould, then the electrode assembly and an electrolyte (saturated solution of sodium hexafluorophosphate, solvent of glycol dimethyl ether) are loaded into the external packaging body, and then the external packaging body is sealed by the polydimethylsiloxane to obtain the flexible sodium-ion battery with the capacity of 110mAh (fig. 4 is a real figure of the flexible sodium-ion battery prepared in the embodiment 1 of the invention).
Comparative example 1 preparation method of flexible sodium-ion battery
Comparative example 1 differs from example 1 in (1) preparation of flexible sodium-ion battery negative electrode: firstly, the mol ratio of amino-terminated hyperbranched polyamide to nickel acetate to thiourea is 2:1:3, adding the mixture into 70mL of methanol, and stirring and mixing for 1h to obtain a precursor solution; then transferring the precursor solution into a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 180 ℃ for 20h, cooling to room temperature, and carrying out filtration treatment and washing treatment to obtain a nickel sulfide negative electrode material; then, mixing the nickel sulfide negative electrode material, SP and CMC in deionized water according to a mass ratio of 92 2 ) The density of the coated surface is 0.46mg/cm 2 Then carrying out vacuum drying and rolling treatment to obtain the flexible sodium-ion battery cathode; the rest is the same as in example 1.
Comparative example 2 preparation method of sodium ion battery
Comparative example 2 differs from example 1 in that: (1) preparing a negative electrode of the sodium-ion battery: firstly, the mol ratio of amino-terminated hyperbranched polyamide to nickel acetate to thiourea is 2:1:3, adding the mixture into 70mL of methanol, and stirring and mixing for 1h to obtain a precursor solution; then transferring the precursor solution into a 100mL stainless steel high-pressure reaction kettle with a polytetrafluoroethylene lining, carrying out hydrothermal reaction at 180 ℃ for 20h, cooling to room temperature, and carrying out filtration treatment and washing treatment to obtain a nickel sulfide negative electrode material; and then mixing the nickel sulfide negative electrode material, SP and CMC in deionized water according to a mass ratio of 92Coating on copper foil with thickness of 2 μm and coating surface density of 0.46mg/cm 2 Then carrying out vacuum drying and rolling treatment to obtain a sodium ion battery cathode;
(2) Firstly, mixing sodium vanadium phosphate, SP and PVDF in NMP according to a mass ratio of 92 2 Then the mixture is subjected to vacuum drying and rolling treatment to obtain the compact density of 2g/cm 3 A sodium ion battery positive electrode; the rest is the same as in example 1.
Performance detection
The flexible sodium-ion battery prepared in the embodiment 1 and the comparative example 1 and the sodium-ion battery prepared in the comparative example 2 are subjected to first discharge specific volume and cycle performance tests at room temperature (25 ℃ +/-1) and under the voltage range of 0.3-3.2V under the conditions of 100 times of unbending and manual bending respectively, and the test results are shown in the table 1;
TABLE 1
The above description is only exemplary of the invention and should not be taken as limiting the invention, as any modification, equivalent replacement, or improvement made within the spirit and principle of the invention is intended to be covered by the appended claims.
Claims (10)
1. A flexible sodium-ion battery negative electrode, comprising: the carbon nano tube cathode material comprises a carbon nano tube film and a nickel sulfide cathode material which grows on the carbon nano tube film in situ; wherein the mass of the nickel sulfide cathode material in-situ grown on the carbon nanotube film is 0.3-1mg/cm 2 (ii) a The thickness of the carbon nano tube film is 1-5 mu m.
2. The flexible sodium-ion battery cathode according to claim 1, wherein the nickel sulfide cathode material has a micro-morphology of a secondary microsphere consisting of a plurality of nanorods, the nanorods have a diameter of 10-30nm, and the secondary microsphere has a diameter of 1-200 μm.
3. A method of making the flexible sodium-ion battery negative electrode of claim 1 or 2, comprising:
s1, dispersing a template agent, a nickel source and a sulfur source into an organic solvent for mixing treatment to obtain a precursor solution;
and S2, adding the carbon nanotube film into the precursor solution, carrying out hydrothermal reaction, and after the reaction is finished, sequentially carrying out filtering treatment, washing treatment, drying treatment and compression roller treatment to obtain the flexible sodium-ion battery cathode.
4. The method according to claim 3, wherein in step S1, the template is an amino-terminated hyperbranched polyamide;
and/or the nickel source is selected from one or more of nickel acetate, nickel sulfate and nickel chloride;
and/or the sulfur source is selected from one or more of sulfur powder, thiourea and sodium persulfate;
and/or the molar ratio of the amino-terminated hyperbranched polyamide to the nickel element in the nickel source and the sulfur element in the sulfur source is (1-8): 1:3.
5. the method according to claim 4, wherein in step S1, the amino-terminated hyperbranched polyamide is prepared by: taking diethylenetriamine and methyl acrylate as reaction raw materials, dispersing the diethylenetriamine and the methyl acrylate in methanol, stirring the mixture for reaction for 10 to 15 hours at the temperature of between 0 and 10 ℃, then adding ethylenediamine for reaction for 0.5 to 2 hours at the temperature of between 60 and 80 ℃, and then reacting the mixture for 6 to 10 hours at the temperature of between 120 and 140 ℃ in a nitrogen atmosphere;
and/or the molar ratio of the diethylenetriamine to the methyl acrylate and the ethylenediamine is 2;
and/or the volume ratio of the methanol to the diethylenetriamine is 1.
6. The production method according to any one of claims 3 to 5, wherein in step S1, the organic solvent is selected from methanol and/or ethanol;
and/or the mass concentration of the template in the precursor solution is 0.05-0.5mol/L.
7. The method according to any one of claims 3 to 6, wherein in step S2, the temperature of the hydrothermal reaction is 160 to 200 ℃ and the hydrothermal reaction time is 12 to 24 hours;
and/or the drying treatment temperature is 60-80 ℃, and the drying time is 6-20h.
8. A flexible sodium ion battery, comprising: the flexible sodium-ion battery comprises an electrode assembly, electrolyte and an outer packaging body, wherein the electrode assembly and the electrolyte are packaged by the outer packaging body to prepare the flexible sodium-ion battery; wherein the electrode assembly includes: the flexible sodium-ion battery negative electrode comprises a positive electrode, a diaphragm and a negative electrode, wherein the negative electrode is the flexible sodium-ion battery negative electrode in claim 1 or 2 or the flexible sodium-ion battery negative electrode prepared by the preparation method in any one of claims 3-7.
9. The flexible sodium-ion battery of claim 8, wherein the positive electrode comprises: a positive current collector and active material layers attached to the front and back sides of the positive current collector; the active material layer comprises the following raw materials in percentage by mass: 90-95% of sodium vanadium phosphate, 3-7% of conductive carbon black and 2-5% of polyvinylidene fluoride;
and/or the positive current collector is a carbon nano tube film, and the thickness of the carbon nano tube film is 1-5 mu m;
and/or dispersing the raw material of the active material layer in N-methyl pyrrolidone to prepare slurry, then coating the slurry to attach the slurry to the positive electrode current collector, and then drying and rolling to prepare the positive electrode;
and/or the compacted density of the anode obtained after the rolling treatment is 1.8-2.4g/cm 3 。
10. The flexible sodium-ion battery of claim 8 or 9, wherein the ratio of N/P in the electrode assembly is 1.06-1.2:1;
and/or the outer packaging body is made of polydimethylsiloxane.
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