CN114203952A - Sodium ion battery cathode, preparation method and application - Google Patents
Sodium ion battery cathode, preparation method and application Download PDFInfo
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- CN114203952A CN114203952A CN202111403340.5A CN202111403340A CN114203952A CN 114203952 A CN114203952 A CN 114203952A CN 202111403340 A CN202111403340 A CN 202111403340A CN 114203952 A CN114203952 A CN 114203952A
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 40
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- 239000005016 bacterial cellulose Substances 0.000 claims abstract description 41
- 229920002749 Bacterial cellulose Polymers 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000012528 membrane Substances 0.000 claims abstract description 22
- 238000005245 sintering Methods 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229910052961 molybdenite Inorganic materials 0.000 claims description 20
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 10
- 239000011609 ammonium molybdate Substances 0.000 claims description 10
- 238000004108 freeze drying Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 8
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000003139 buffering effect Effects 0.000 claims description 3
- 238000007710 freezing Methods 0.000 claims description 3
- 230000008014 freezing Effects 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- -1 polytetrafluoroethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 102000020897 Formins Human genes 0.000 claims 1
- 108091022623 Formins Proteins 0.000 claims 1
- 238000007605 air drying Methods 0.000 claims 1
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000002028 Biomass Substances 0.000 abstract description 3
- 239000007833 carbon precursor Substances 0.000 abstract description 2
- 239000000872 buffer Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 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 5
- 229910052708 sodium Inorganic materials 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000001351 cycling effect Effects 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000006258 conductive agent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 239000003365 glass fiber Substances 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 239000007773 negative electrode material Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- ZUHZGEOKBKGPSW-UHFFFAOYSA-N tetraglyme Chemical compound COCCOCCOCCOCCOC ZUHZGEOKBKGPSW-UHFFFAOYSA-N 0.000 description 2
- 238000009777 vacuum freeze-drying Methods 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910021201 NaFSI Inorganic materials 0.000 description 1
- 229910019398 NaPF6 Inorganic materials 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000002134 carbon nanofiber Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 1
- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920001021 polysulfide Polymers 0.000 description 1
- 239000005077 polysulfide Substances 0.000 description 1
- 150000008117 polysulfides Polymers 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical compound CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 229910001488 sodium perchlorate Inorganic materials 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910001495 sodium tetrafluoroborate Inorganic materials 0.000 description 1
- YLKTWKVVQDCJFL-UHFFFAOYSA-N sodium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Na+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F YLKTWKVVQDCJFL-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Images
Classifications
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
-
- 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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
-
- 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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
- H01M4/625—Carbon or graphite
-
- 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
Abstract
The invention belongs to the technical field of sodium ion battery cathodes, and particularly relates to a MoS with a flexible and self-supporting structure2The @ C electrode and the preparation method and the application of the @ C electrode as the negative electrode of the sodium-ion battery. The invention takes a biomass bacterial cellulose membrane as a carbon precursor, and MoS directly grows on the carbonized bacterial cellulose membrane in a load way by high-temperature sintering and one-step hydrothermal method2Obtaining the integrated MoS with a flexible and self-supporting structure2The @ C electrode is used as a negative electrode of the sodium-ion battery without using conductive carbon and a binder, and the method is simple, direct, safe, effective and easy to control.
Description
Technical Field
The invention belongs to the technical field of sodium ion battery cathodes, and particularly relates to a MoS with a flexible and self-supporting structure2@ C electrodeA preparation method and application thereof as a negative electrode of a sodium-ion battery.
Background
With the increasingly scarcity of global resources and the increasing problem of environmental pollution, the development of clean and sustainable energy has become a hot spot of research in all countries around the world. The widespread use of lithium ion batteries greatly alleviates this problem. But because of the limited and uneven distribution of lithium resources around the world, the price thereof continues to rise. Therefore, based on abundant resources, the development of low-cost energy storage systems has attracted extensive attention of researchers. Sodium ion batteries have many advantages over lithium ion batteries. The sodium resource is rich, the distribution is wide, the price is low, and the chemical property is similar to that of lithium, so the sodium ion battery becomes a research hotspot in the field of energy storage, and is expected to replace a lithium ion battery in the fields of large-scale energy storage and low-speed electric vehicles, thereby being widely applied in a large scale.
The performance of the sodium ion battery mainly depends on the used electrode material, the positive electrode material has made remarkable progress at present, but research on the negative electrode material is still needed to improve the specific capacity, the cycle life and the rate capability of the sodium ion battery. The hard carbon cathode has a low sodium storage capacity. MoS2Has a two-dimensional layered structure, is beneficial to sodium ion storage, and has higher theoretical sodium storage capacity (669mA h g)-1) It is one of the ideal negative electrode materials of sodium ion batteries at present. But the conductivity is poor, and the rate performance of the electrode is influenced; the electrode structure is easy to be pulverized and fall off from a current collector due to larger volume deformation in the charging and discharging processes, so that the cycling stability of the electrode is influenced; and the intermediate product polysulfide generated in the charging and discharging process is dissolved and transferred in the electrolyte, so that the coulombic efficiency of electrode circulation is low. Currently, MoS will be2The composite material with carbon base and other conducting material is one effective way of raising its electrochemical performance. The carbon-based material not only can effectively improve the conductivity of the active material and promote ion migration and electron transfer, but also can effectively buffer MoS2The electrode deforms in the charging and discharging process, and the stable structure of the electrode is maintained.
Based on the above problems, the present invention utilizes bacterial cellulose having a three-dimensional cross-linked network structureCarbon as a flexible, self-supporting substrate on which MoS is grown on a three-dimensional network structure2Thereby preparing MoS2The @ C electrode is used for the negative electrode of the sodium ion battery, has a flexible, self-supporting and integrated structure, does not need a conductive agent, a binder and a current collector, and can effectively improve the energy density of the battery. The bacterial cellulose carbon with the three-dimensional cross-linked structure can effectively improve the electron and ion conduction rate and simultaneously can effectively buffer MoS2The volume deformation in the charging and discharging process maintains the stable structure of the electrode, thereby improving the electrochemical cycling stability of the electrode.
Disclosure of Invention
Aiming at the prior art and the current MoS2Problems with materials, the present invention provides an integrated MoS with a flexible, self-supporting structure2The @ C electrode and a preparation method thereof. The sodium ion battery cathode provided by the invention has higher specific capacity, stable cycle performance and excellent rate performance.
In order to achieve the technical purpose and achieve the related technical requirements, the invention is implemented by the following technical scheme:
flexible, self-supporting structure's integrated MoS2@ C sodium ion battery negative electrode. Wherein, the carbonized bacterial cellulose membrane with a three-dimensional cross-linked network structure is taken as a flexible and self-supporting base, and MoS grows uniformly on the three-dimensional cross-linked network structure2. Promotion of ion migration and electron transport using three-dimensional cross-linked conductive networks of bacterial cellulose carbon and buffering of MoS2The volume deformation in the charging and discharging process makes the electrode structure keep stable. Assembling the sodium ion battery and testing the electrochemical performance of the sodium ion battery at 30mA h g-1The specific capacity under the current density can reach 450mA h g-1The specific capacity can still reach 380mA h g after 60 cycles-1. G at 30mA h-1、100mA h g-1、200mA h g-1、400mA h g-1、800mA h g-1The current density is still 450mA h g respectively-1、310mA h g-1、300mA h g-1、260mA h g-1And 240mA h g-1The specific capacity of (A).
As a preference, the first and second liquid crystal compositions are,flexible, self-supporting structure MoS2In bacterial cellulose carbon composite electrodes, MoS2Uniformly growing on the surface of the cellulose carbon of the bacteria. Wherein bacterial cellulose carbon having a three-dimensional cross-linked network structure is used as MoS2Flexible self-supporting carrier of (1), prevention of MoS2The problem of structural collapse occurs due to volume deformation in the process of charging and discharging.
The invention also provides an integrated MoS with a flexible and self-supporting structure2The preparation method of the @ C sodium-ion battery negative electrode comprises the following steps:
(1) pre-freezing the bacterial cellulose membrane soaked in the deionized water by using liquid nitrogen, then freeze-drying by using a freeze dryer, and sintering at high temperature by using a tubular furnace to obtain the bacterial cellulose carbon membrane;
(2) fully dissolving ammonium molybdate and thiourea in deionized water according to a certain mass ratio, and uniformly stirring to form a mixed solution;
(3) adding the mixed solution obtained in the step (2) into a stainless steel reaction kettle, adding the bacterial cellulose carbon film obtained in the step (1), sealing and carrying out hydrothermal reaction at a certain temperature to obtain a product;
(4) after cooling, washing the product obtained in the step (3) by deionized water, and carrying out vacuum drying in a vacuum drying oven; thereby obtaining an integrated MoS with a flexible, self-supporting structure2@ C sodium ion battery negative electrode.
The prior technical scheme of the invention is as follows:
in the step (1), the bacterial cellulose membrane is soaked in deionized water for 72 hours. The freeze drying condition is below 20Mpa, the temperature is-35 ℃ to-20 ℃, and the freeze drying is carried out for 24 hours. The preferable freeze drying condition is 18MPa pressure and 25 deg.C temperature for 24 hr. The sintering process specifically comprises: putting the bacterial cellulose membrane into a tube furnace, preferably, the sintering process in the invention specifically comprises the following steps: under inert atmosphere, at 2 deg.C for min-1Heating to 500 deg.C, maintaining for 1h, and heating at 5 deg.C for min-1The heating rate is increased to 800 ℃, and the temperature is kept for 2 hours. Preferably, the bacterial cellulose carbon film obtained by sintering has better flexibility (as shown in figure 1), and can be used as a flexible carbon filmMoS in charge-discharge process of effective buffering of sexual and self-supporting substrate2The volume of (c) is changed.
In the step (2), the mass ratio of ammonium molybdate to thiourea to deionized water is 5-7: 9-12: 350-600, and further preferably, the mass ratio of ammonium molybdate, thiourea and deionized water is 7: 10: 400.
in the step (3), the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle. And a hydrothermal reaction method is adopted, the hydrothermal temperature is 170-220 ℃, and the hydrothermal time is 16-24 hours. Further preferably, the hydrothermal temperature is 180-200 ℃ and the hydrothermal time is 18-24 h. Preferably, the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 h.
The integrated sodium-ion battery cathode with the flexible and self-supporting structure, which is prepared by the invention, has higher electron and ion conduction rates, higher specific capacity, higher cycling stability and higher rate capability. The three-dimensional interconnected conductive network can fully buffer the volume deformation of the metal sulfide in the charging and discharging processes. The MoS2The bacterial cellulose carbon material is used as a novel flexible, self-supporting and integrated structure cathode and is applied to a sodium ion battery.
Compared with the prior art, the invention has the following advantages:
the invention takes a biomass bacterial cellulose membrane as a carbon precursor, and MoS directly grows on the carbonized bacterial cellulose membrane in a load way by high-temperature sintering and one-step hydrothermal method2Obtaining the integrated MoS with a flexible and self-supporting structure2The @ C electrode is used as a negative electrode of the sodium-ion battery without using conductive carbon and a binder, and the method is simple, direct, safe, effective and easy to control.
The electrode obtained by the invention has a three-dimensional cross-linked network structure and a larger specific surface area, and can provide more active sites for sodium ions, thereby effectively improving the sodium storage capacity.
The three-dimensional interconnected carbon network used by the invention is formed by pyrolyzing low-cost biomass material bacterial cellulose, can be used as a good electronic conductive network to improve the electrode conductivity, and can be used as a mechanical buffer substrate to buffer MoS in the circulating process2The volume of the glass fiber is deformed,the structural stability of the electrode is improved, and the electrochemical performance of the electrode is further improved.
Drawings
FIG. 1 is an integrated MoS with a flexible, self-supporting structure2The @ C electrode.
Fig. 2 is an SEM image of bacterial cellulose carbon.
FIG. 3 shows MoS2TEM pattern of bacterial cellulose carbon.
FIG. 4 shows MoS2Circulation performance of bacterial cellulose carbon.
FIG. 5 shows MoS2Rate capability of bacterial fiber carbon.
Detailed Description
The technical solution of the present invention will be clearly and completely described below. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. 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 addition, the technical features involved in the different embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Example 1
An integrated MoS that provides a flexible, self-supporting structure in this example2The preparation method of the @ C sodium-ion battery negative electrode comprises the following steps:
1) and (3) rapidly pre-freezing the bacterial cellulose membrane soaked in the deionized water for 72h in liquid nitrogen to keep the self-inherent three-dimensional porous structure. Then freeze-drying for 24h by a freeze dryer under the conditions of 18Mpa and the temperature of minus 25 ℃. Then the obtained dried bacterial cellulose membrane was placed in a tube furnace under inert atmosphere at 2 ℃ for min-1After the temperature is raised to 500 ℃, the temperature is kept for 1h, and then the temperature is raised for 5 min-1Heating to 800 ℃, keeping the temperature for 2h, and naturally cooling to obtain a bacterial cellulose carbon film with a flexible and self-supporting structure;
2) weighing 700mg of ammonium molybdate to dissolve in 40ml of deionized water, adding 1g of thiourea, and fully stirring to dissolve to form a mixed solution;
3) soaking the bacterial cellulose carbon film obtained in the step 1) in the mixed solution obtained in the step 2), standing for 24 hours to fully soak the carbon film, transferring all products into a 60ml stainless steel high-pressure reaction kettle, sealing, and carrying out hydrothermal reaction in a blast oven. At 5 ℃ for min-1Heating to 180 ℃ and keeping the temperature for 24 hours;
4) after cooling, the product was washed with deionized water. And the final product is dried in a vacuum drying oven for 12 hours at the temperature of 100 ℃.
The bacterial cellulose carbon film obtained in example 1 was subjected to scanning electron microscope testing (as shown in FIG. 3). It can be seen that nanofibers with a diameter of about 20nm are interwoven to form a highly developed porous network structure. The highly developed network structure of the bacterial cellulose carbon film can be MoS in an electrochemical process2The volume deformation of (2) reserves sufficient space, effectively buffers the stress generated by the volume deformation of the electrode, and maintains the stable structure of the electrode. The final product MoS is obtained2@ C Transmission Electron microscopy was performed (as shown in FIG. 3). The load MoS can be seen2Thereafter, the bacterial cellulose carbon film still maintains a good continuous conductive network while a large amount of MoS2Uniformly growing on the surface of the carbon nanofiber.
Example 2
An integrated MoS having a flexible, self-supporting structure is provided in this example2The preparation method of the @ C sodium-ion battery negative electrode comprises the following steps:
1) adding 100mg of ammonium molybdate and 1.2g of thiourea into 60mL of deionized water, stirring for 4 hours at room temperature, and fully dissolving;
2) mixing the bacterial cellulose membrane with the solution obtained in the step 1), standing for 24 hours, and fully infiltrating;
3) prefreezing the bacterial cellulose membrane obtained in the step 2) by using liquid nitrogen to keep the original structure, immediately entering a freeze dryer for vacuum freeze drying, and freeze-drying for 24 hours at the temperature of-25 ℃ under 18 Mpa;
4) placing the product obtained in the step 3) in a tubular furnace under inert atmosphere at 3 ℃ for min-1After the temperature is raised to 500 ℃ at the temperature raising rate, the temperature is kept for 1h, and then the temperature is raised for 4 min-1Rate of temperature rise ofHeating to 800 ℃, keeping the temperature for 2 hours, and naturally cooling to obtain MoS2Bacterial cellulose carbon composites;
5) drying the final product in a vacuum drying oven at 100 ℃ for 12h to obtain the integrated MoS with a flexible and self-supporting structure2@ C sodium ion battery negative electrode.
Comparative example 1
Example 2 was a change of the desired ammonium molybdate and thiourea masses to 100mg and 1.2g and a change of the deionized water volume to 60 ml.
Example 2 difference from hydrothermal reaction method of example 1, MoS was synthesized2And directly sintering the bacterial cellulose membrane which fully absorbs the ammonium molybdate and the thiourea.
Example 2 sintering ramp rate 3 deg.C min-1Heating to 500 deg.C, keeping the temperature for 1h, and keeping the temperature at 4 deg.C for min-1The temperature is raised to 800 ℃ and then the temperature is kept for 2 h.
Preparing a sodium ion battery and testing the performance: preparing the obtained integrated MoS with flexible and self-supporting structure2The @ C electrode is a working electrode, a conductive agent and a binder do not need to be additionally used, and the sodium ion battery is assembled by taking metal sodium as a counter electrode and a reference electrode. Wherein the electrolyte comprises NaPF6、NaClO4NaFSI, NaTFSI and NaBF4And one of sodium salts and one of organic solvents selected from dimethyl carbonate, diethyl carbonate, propylene carbonate, ethylene carbonate, tetraethylene glycol dimethyl ether, diethylene glycol dimethyl ether, ethylene glycol dimethyl ether and the like. Whatman glass fiber membrane was used as a membrane. And (5) carrying out constant-current charge and discharge test by adopting a Land battery test system. The charge-discharge voltage range is 0.01-3V. The charge and discharge test is carried out on the button cell assembled by the product of the embodiment 1, and the first charge specific capacity of the sodium ion battery taking the bacterial cellulose carbon film as the negative electrode in the circulation process is 250mA h g in the observation of figure 4-1The specific discharge capacity is 670mA h g-1The reversible capacity is maintained at 200mA h g after 60 cycles-1。MoS2The initial charging specific capacity of the @ C electrode is 450mA h g-1The specific discharge capacity is 750mA h g-1. The reversible capacity is kept at 390mA h g after 60 cycles of circulation-1. Comparison of bacterial cellulose carbon membranes, MoS2The electrochemical performance of the @ C electrode is greatly improved. MoS is observed in FIG. 52@ C at 30mA g-1、100mA g-1、200mA g-1、400mA g-1、800mA g-1、1000mA g-1、2000mA g-1The current density of 10 cycles under different current densities respectively has 350mA h g-1、300mA h g-1、290mA h g-1、260mA h g-1、240mA h g-1、150mAh g-1、80mAh g-1The specific capacity of (A). Then 30mAg-1The current density of the current is circulated for 10 circles, and 360mAh g is still obtained-1The specific capacity of (A). Has very stable charge and discharge performance. The prepared electrode material has excellent rate performance.
Claims (9)
1. The negative electrode of the sodium-ion battery is characterized in that a carbonized bacterial cellulose membrane with a three-dimensional cross-linked network structure is taken as a flexible and self-supporting base, and MoS grows uniformly on the three-dimensional cross-linked network structure2Ion transport and electron transport facilitated by a three-dimensional cross-linked conductive network of bacterial cellulose carbon and buffering of MoS2The volume deformation in the charging and discharging process makes the electrode structure keep stable.
2. The preparation method of the sodium-ion battery cathode as claimed in claim 1, characterized by comprising the following steps:
(1) pre-freezing the bacterial cellulose membrane soaked in the deionized water by using liquid nitrogen, then freeze-drying by using a freeze dryer, and sintering at high temperature by using a tubular furnace to obtain the bacterial cellulose carbon membrane;
(2) fully dissolving ammonium molybdate and thiourea in deionized water according to a certain mass ratio, and uniformly stirring to form a mixed solution;
(3) adding the mixed solution obtained in the step (2) into a stainless steel reaction kettle, adding the bacterial cellulose carbon film obtained in the step (1), sealing and carrying out hydrothermal reaction at a certain temperature to obtain a product;
(4) after cooling, the product obtained in step (3) is washed with deionized water and then driedVacuum drying in an air drying box; thereby obtaining an integrated MoS with a flexible, self-supporting structure2@ C sodium ion battery negative electrode.
3. The method for preparing the negative electrode of the sodium-ion battery as claimed in claim 2, wherein in the step (1), the bacterial cellulose membrane is soaked in the deionized water for 72 hours; the freeze drying condition is below 20Mpa, the temperature is-35 ℃ to-20 ℃, and the freeze drying is carried out for 24 hours; the sintering process specifically comprises: placing the bacterial cellulose membrane into a tube furnace, and keeping the temperature at 2 ℃ for min under the condition of inert atmosphere-1Heating to 500 deg.C, maintaining for 1h, and heating at 5 deg.C for min-1The heating rate is increased to 800 ℃, and the temperature is kept for 2 hours.
4. The method for preparing the negative electrode of the sodium-ion battery as claimed in claim 3, wherein the freeze-drying condition is 18MPa pressure and-25 ℃ temperature for 24 h.
5. The method for preparing the cathode of the sodium-ion battery as claimed in claim 2, wherein in the step (2), the mass ratio of ammonium molybdate, thiourea and deionized water is 5-7: 9-12: 350-600.
6. The method for preparing the negative electrode of the sodium-ion battery as claimed in claim 5, wherein the mass ratio of the ammonium molybdate to the thiourea to the deionized water is 7: 10: 400.
7. the method for preparing the negative electrode of the sodium-ion battery as claimed in claim 2, wherein in the step (3), the reaction kettle is a polytetrafluoroethylene high-pressure reaction kettle; and a hydrothermal reaction method is adopted, the hydrothermal temperature is 170-220 ℃, and the hydrothermal time is 16-24 hours.
8. The method for preparing the negative electrode of the sodium-ion battery as claimed in claim 7, wherein the hydrothermal temperature is 180-200 ℃ and the hydrothermal time is 18-24 h.
9. The method for preparing the negative electrode of the sodium-ion battery as claimed in claim 7 or 8, wherein the hydrothermal temperature is 180 ℃ and the hydrothermal time is 24 h.
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