CN115849342B - Coil-shaped nitrogen-sulfur-oxygen co-doped sodium-ion battery anode material and preparation method thereof - Google Patents
Coil-shaped nitrogen-sulfur-oxygen co-doped sodium-ion battery anode material and preparation method thereof Download PDFInfo
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- 229910001415 sodium ion Inorganic materials 0.000 title claims abstract description 51
- 239000010405 anode material Substances 0.000 title claims abstract description 50
- LOTCVJJDZFMQGB-UHFFFAOYSA-N [N].[O].[S] Chemical compound [N].[O].[S] LOTCVJJDZFMQGB-UHFFFAOYSA-N 0.000 title claims abstract description 49
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920005989 resin Polymers 0.000 claims abstract description 26
- 239000011347 resin Substances 0.000 claims abstract description 26
- UREVLELSVZQJTM-UHFFFAOYSA-N benzene-1,4-diol;formaldehyde Chemical compound O=C.OC1=CC=C(O)C=C1 UREVLELSVZQJTM-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000002074 nanoribbon Substances 0.000 claims abstract description 20
- 238000003763 carbonization Methods 0.000 claims abstract description 17
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 13
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 13
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 8
- 238000010438 heat treatment Methods 0.000 claims description 20
- 229910021385 hard carbon Inorganic materials 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012046 mixed solvent Substances 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 7
- 238000010000 carbonizing Methods 0.000 claims description 7
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- 238000004140 cleaning Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 claims description 2
- 239000011258 core-shell material Substances 0.000 claims description 2
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 2
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 11
- 239000003792 electrolyte Substances 0.000 abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 239000002994 raw material Substances 0.000 abstract description 11
- 229910052717 sulfur Inorganic materials 0.000 abstract description 9
- 239000011593 sulfur Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
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- 239000000126 substance Substances 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 2
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- 230000002035 prolonged effect Effects 0.000 abstract 1
- 208000028659 discharge Diseases 0.000 description 22
- 238000003756 stirring Methods 0.000 description 14
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 11
- 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 11
- 239000000203 mixture Substances 0.000 description 11
- 239000007773 negative electrode material Substances 0.000 description 11
- 229910052708 sodium Inorganic materials 0.000 description 11
- 239000011734 sodium Substances 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000003575 carbonaceous material Substances 0.000 description 9
- 239000006230 acetylene black Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 8
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- 238000005406 washing Methods 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- 239000001301 oxygen Substances 0.000 description 6
- 229960001124 trientine Drugs 0.000 description 6
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 5
- -1 polytetrafluoroethylene Polymers 0.000 description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
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- RUOJZAUFBMNUDX-UHFFFAOYSA-N propylene carbonate Chemical group CC1COC(=O)O1 RUOJZAUFBMNUDX-UHFFFAOYSA-N 0.000 description 4
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- 125000005842 heteroatom Chemical group 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
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- 238000004626 scanning electron microscopy Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
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- 239000011780 sodium chloride Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
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- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
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- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- 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 relates to a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material and a preparation method thereof, wherein a hydroquinone formaldehyde resin nanoribbon coil is used as a substrate, ethylene amine substances, carbon disulfide and carbon dioxide are promoted to be polymerized on the surface of the substrate in situ in a high-pressure reaction kettle, a carbon precursor raw material containing sulfur/nitrogen elements is obtained, and the coil-shaped nitrogen-sulfur-oxygen co-doped anode material is obtained through a simple one-step carbonization method, so that the volume expansion of the anode material in the charge and discharge process can be effectively relieved, the anode is prevented from being damaged, and the cycle stability is prolonged. Through simple one-step carbonization, the polymer material containing nitrogen/sulfur forms a coating shell on the surface of the hydroquinone formaldehyde resin derived carbon, the structure can improve the first charge and discharge efficiency of the anode material, and simultaneously the nitrogen-sulfur-oxygen co-doping can improve the wettability of the anode and electrolyte and shorten the sodium ion transmission distance.
Description
Technical Field
The invention relates to the technical field of sodium ion battery negative electrode materials, in particular to a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery negative electrode material and a preparation method thereof.
Background
The sustainable development and utilization of green energy are not separated from the development of high-performance energy storage equipment, and in a new secondary battery system, a sodium ion battery is considered to be the most promising to replace a lithium ion battery, because the sodium ion battery and the lithium ion battery have similar electrochemical mechanisms, meanwhile, the storage amount of sodium in the crust reaches 2.64 percent, which is 421 times that of lithium, sodium ores are uniformly distributed in the global scope, the extraction is not complicated, each ton of lithium carbonate serving as a main raw material of the lithium battery needs tens of thousands of yuan, each ton of sodium chloride serving as a main raw material of the sodium battery only needs thousands of yuan, the price of the sodium chloride serving as a main raw material of the sodium battery is tens of times as low as that of the lithium ores, so the sodium ion battery has more advantages in terms of raw material cost, besides, the sodium battery has superior electrolyte stability, can normally work in an environment of minus 40 ℃ to 80 ℃, the capacity of about 90% is still kept in a navigation even in an extremely cold environment of minus 20 ℃, and the problem of continuous shrinkage of an electric automobile in winter is relieved to a certain extent.
Although sodium ion batteries have a plurality of advantages, the traditional high-conductivity graphite negative electrode is not suitable for the larger ion radius of sodium ions, the carbon layer spacing of the graphitized negative electrode material is small, and the large volume expansion generated by intercalation and deintercalation of sodium ions cannot be met, so that the negative electrode material is cracked and the capacity of the sodium ion battery is rapidly attenuated in the charge and discharge process. And hard carbon with larger carbon interlayer spacing is adopted as a cathode material, so that the cathode material has poor wettability with electrolyte and poor electrode conductivity. Although the prior art improves the cathode material, the improvement of the sodium ion cathode performance is still limited, and side effects such as coating of excessive conductive materials and excessive doping are accompanied, so that the specific capacity of the cathode material is easily reduced.
In view of this, the present invention has been made.
Disclosure of Invention
One of the purposes of the invention is to provide a preparation method of a string-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material.
The second purpose of the invention is to provide the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material prepared by the preparation method.
The invention further provides a sodium ion battery, which comprises the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material.
In order to achieve the above object of the present invention, the following technical solutions are specifically adopted:
in a first aspect, the invention provides a preparation method of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium-ion battery anode material, which comprises the following steps:
(1) Mixing hydroquinone formaldehyde resin nanoribbon coils, ethylene amine and a solvent under ice water bath, adding carbon disulfide, heating to 25-30 ℃, supplementing carbon dioxide to 1-2 MPa after the system pressure reaches saturated vapor pressure, performing constant temperature reaction, and separating, cleaning and drying a product;
(2) And carbonizing the dried product in inert atmosphere to obtain the string-like nitrogen-sulfur-oxygen co-doped sodium ion battery anode material.
The steps are described in detail below.
Step (1)
In this step, the source of the hydroquinone formaldehyde resin nanoribbon coils is not particularly limited, and the hydroquinone formaldehyde resin nanoribbon coils can be obtained commercially or prepared by self according to the existing known method.
In some embodiments, the ethyleneamine is a mixture of one or more acyclic polymers selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, and the like.
In some embodiments, the solvent is a mixed solvent of water and ethylenediamine, wherein the volume ratio of water to ethylenediamine is from 1:1 to 4:1.
In some embodiments, the ratio of the mass of the hydroquinone formaldehyde resin nanoribbon coils to the molar amount of the ethylene amine is 30 to 100mg:0.25mol.
In some embodiments, the concentration of the hydroquinone formaldehyde resin nanoribbon coils in the solvent is between 0.375 and 1.25g/L.
In some embodiments, the molar ratio of the ethylene amine to the carbon disulfide is from 1:2 to 1:5.
Carbon dioxide is added into the system, so that on one hand, the pressure of the system can be increased, the penetration of ethylene amine and carbon disulfide into pores of the phenolic resin matrix is promoted, and the polymerization and the matrix are tightly combined; on the other hand, carbon dioxide is taken as a raw material to participate in the reaction, and ethylene amine has the function of adsorbing carbon dioxide and can partially react with the carbon dioxide to increase the carbon content of a final product.
The separation method is not particularly limited, and a centrifugal separation method may be employed.
The washing method is not particularly limited, and washing methods known in the art may be employed, and the washing solvent may be an alcohol such as ethanol.
The drying temperature is not particularly limited, and may be carried out at 60 to 80℃and the drying time is not particularly limited until the weight is constant.
Step (2)
In this step, the inert gas may be nitrogen, argon, helium, or the like.
In some embodiments, the process parameters of the carbonization treatment are: heating to 500-900 ℃ at a speed of 5 ℃/min, and then preserving heat for 1.5-3 h.
As shown in fig. 1, the preparation process principle of the invention is as follows:
According to the invention, hydroquinone formaldehyde resin nanoribbon coils are taken as a resin substrate, ethylene amine substances, carbon disulfide and carbon dioxide are promoted to be polymerized on the surface of the substrate in situ in a high-pressure reaction kettle (high molecular polymers containing nitrogen and sulfur are grown on the surface of the hydroquinone formaldehyde resin nanoribbon coils in situ), so as to obtain a carbon precursor raw material containing sulfur/nitrogen elements, and then the high molecular polymers are pyrolyzed and converted into a nitrogen-sulfur-oxygen co-doped hard carbon material by a simple one-step carbonization method, wherein the material still keeps a ribbon coil structure, the inside is a carbon skeleton derived from hydroquinone formaldehyde resin, and the outer coating layer is a nitrogen-sulfur-oxygen doped hard carbon shell layer.
In order to solve the problem that the negative electrode such as graphite and hard carbon is not suitable for sodium ion batteries, the negative electrode material is generally modified by adopting the processes such as the structural design of the negative electrode, doping of hetero atoms, surface coating of the negative electrode material and the like, but the single strategy has limited improvement on the performance of the sodium ion negative electrode, and side effects are associated, such as coating of excessive conductive materials and excessive doping, so that the specific capacity of the negative electrode material is easy to reduce. Based on the structure, the invention provides the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material, the damage to the electrode material caused by volume expansion is avoided, a carbon structure network which is communicated with each other is beneficial to rapid charge transfer, a sodium ion diffusion path is shortened, and diffusion resistance is reduced. Meanwhile, nitrogen-sulfur-oxygen co-doping of the anode material in situ is realized, the doping of nitrogen element can obviously improve the conductivity of the hard carbon anode material, and the doping of sulfur/oxygen and other elements can manufacture more defect sites on the surface of the hard carbon, improve the interlayer distance of carbon atoms, improve the wettability of the anode and electrolyte, shorten the sodium ion transmission distance and accelerate the mass transfer efficiency of sodium ions. Therefore, the anode material has good rate capability and excellent cycle stability. The preparation method overcomes the limitation of a single negative electrode modification strategy, is simple and is suitable for large-scale industrial production.
In a specific embodiment, the preparation method of the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material specifically comprises the following steps:
Preparing a mixed solvent of water and ethylenediamine according to a certain proportion, adding the mixed solvent into a polytetrafluoroethylene lining of a high-pressure reaction kettle, adding a certain amount of hydroquinone formaldehyde resin nanoribbon coils and a certain amount of ethylene amine into the mixed solvent, sealing the reaction kettle, and magnetically stirring the mixture under the ice water bath condition. Slowly injecting a certain amount of carbon disulfide through a reserved feed inlet of a reaction kettle cover by using an injector, then heating to 25 ℃, supplementing a certain amount of carbon dioxide to 1MPa after the system pressure reaches the saturated vapor pressure, stirring at constant temperature for 2 hours under the pressure, centrifuging and cleaning the product after the reaction is finished, and drying to constant weight at 60-80 ℃. And (3) under the protection of inert gas, carrying out one-step carbonization treatment on the dried sample, and slowly cooling to room temperature after carbonization is finished to obtain the string-like nitrogen-sulfur-oxygen co-doped anode material.
In a second aspect, the invention provides a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material, which is prepared by the method;
The coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material is hard carbon with a ribbon coil structure, the hard carbon is in a core-shell structure, an inner core is a carbon skeleton derived from hydroquinone formaldehyde resin, and the surface of the inner core is coated with a nitrogen-sulfur-oxygen doped carbon shell layer.
In a third aspect, the invention provides a sodium ion battery, comprising the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material.
The negative electrode material is coated on the negative electrode sheet as a negative electrode active material layer to form a negative electrode, and the sodium ion battery may have a structure and components conventional in sodium ion batteries in the art, for example, a positive electrode, an electrolyte, a separator, an aluminum plastic film, and the like, in addition to the negative electrode. There are no particular restrictions on the positive electrode, the electrolyte, the separator, and the aluminum plastic film, nor on the structure and the assembly method of the sodium battery, and any structure and assembly method known in the art that can be used for a sodium battery may be employed.
The sodium ion battery has the same advantages as the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material, and the details are not repeated here.
The beneficial effects are that:
(1) The nitrogen-sulfur-oxygen co-doped anode material prepared by the invention has a coil-shaped structure, and the structure can effectively buffer the volume expansion in the sodium ion intercalation and deintercalation process. The structure can inhibit the formation of SEI film on the surface of the negative electrode and improve the first charge and discharge efficiency of the negative electrode material. The in-situ nitrogen-sulfur-oxygen co-doping can introduce a defect structure on the surface of the carbon material, improve the wettability of the cathode and electrolyte, simultaneously improve the conductivity of the electrode and accelerate the mass transfer efficiency of sodium ions, and the nitrogen-sulfur-oxygen co-doped cathode material has good multiplying power performance and excellent cycle stability.
(2) The preparation method is simple, has a novel structure, can be used for large-scale production, and has excellent industrial prospect.
The present invention has been described in detail hereinabove, but the above embodiments are merely exemplary in nature and are not intended to limit the present invention. Furthermore, there is no intention to be bound by any theory presented in the preceding prior art or summary or the following examples.
Unless explicitly stated otherwise, numerical ranges throughout this application include any subrange therein and any numerical value incremented by the smallest subunit in which a given value is present. Unless explicitly stated otherwise, numerical values throughout this application represent approximate measures or limits to include minor deviations from the given value and ranges of embodiments having about the stated value and having the exact value noted. Except in the operating examples provided last, all numerical values of parameters (e.g., amounts or conditions) in this document (including the appended claims) should be construed in all cases as modified by the term "about" whether or not "about" actually appears before the numerical value. "about" means that the recited value allows for slight imprecision (with some approximation to the exact value; approximately or reasonably close to the value; approximated). "about" as used herein at least means variations that can be produced by ordinary methods of measuring and using these parameters if the imprecision provided by "about" is not otherwise understood in the art with this ordinary meaning. For example, "about" may include a change of less than or equal to 10%, less than or equal to 5%, less than or equal to 4%, less than or equal to 3%, less than or equal to 2%, less than or equal to 1%, or less than or equal to 0.5%.
Drawings
Fig. 1 is a schematic diagram of the preparation of a cluster-shaped nitrogen-sulfur-oxygen co-doped sodium-ion battery anode material according to the invention.
FIG. 2 is a schematic structural view of an autoclave used in the present invention.
Fig. 3 is an SEM picture of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material prepared in example 1 of the present invention, wherein the left side is high magnification, and the right side is low magnification.
Fig. 4 is an XPS analysis result of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material prepared in example 1 of the present invention.
FIG. 5 is a graph showing impedance test comparison of EIS electrode materials of nitrogen-sulfur-oxygen co-doped hard carbon material prepared in example 1 of the present invention and undoped hard carbon material prepared in comparative example 1.
Detailed Description
The invention is further illustrated by the following examples, which are provided for illustrative purposes only and are not to be construed as limiting the scope of the invention as claimed.
Unless otherwise indicated, all materials, reagents, methods and the like used in the examples are those conventionally used in the art.
The hydroquinone formaldehyde resin nanoribbon coils are prepared by the following method:
1.65g of hydroquinone (0.015 mol), 2.5mL of 37wt% formaldehyde and 115mL of 10wt% hydrochloric acid were thoroughly mixed in a 200mL Teflon lined autoclave. The autoclave was then sealed and heated at 180℃for 12 hours. The resulting black sponge-like product was filtered and washed with water. The filter cake was dried under vacuum at 60℃for 6 hours. Finally, 2.0g of light dark brown powder were collected.
Triethylene tetramine solution is purchased from Shanghai Ara Ding Gongsi, analytically pure AR (+.95%);
The remaining drugs were all from the microphone reagent.
Scanning Electron Microscopy (SEM) employs a field-emission SU-70 microscope; elemental analysis used X-ray photoelectron spectroscopy (XPS, ELEMENTAR VARIO MICRO CUBE, germany).
Examples
Example 1
A preparation method of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material comprises the following steps:
(1) Preparing a precursor raw material: ethylenediamine and water are added into a polytetrafluoroethylene lining of a high-pressure reaction kettle (the structure is shown in figure 2), and the volume ratio is 1:1, preparing 80ml of mixed solvent after fully stirring, adding 80mg of hydroquinone formaldehyde resin nanoribbon coils and 0.25mol of triethylene tetramine solution into the mixed solvent, sealing a reaction kettle, magnetically stirring the mixture under the ice water bath condition, simultaneously reserving a feed port through the reaction kettle, slowly injecting 0.58mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas until the pressure of the system reaches saturated vapor pressure, stirring the mixture at constant temperature for 2h under the pressure, centrifuging and washing the product with ethanol three times after the reaction is finished, and drying to constant weight at 60 ℃.
(2) Carbonizing: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2 hours. And slowly cooling to room temperature after carbonization is finished, and obtaining the string-like nitrogen-sulfur-oxygen co-doped anode material. The SEM morphology is shown in fig. 3, it can be seen that the anode material is in a cluster shape, and in order to further determine the elemental composition of the material, XPS analysis is performed on the anode material, as shown in fig. 4, it can be seen that the anode material mainly comprises elements such as sulfur, nitrogen, carbon, oxygen, and the like.
(3) Electrochemical performance test: the CR2032 type battery shell is adopted to assemble a battery, battery slurry is prepared according to the coil-shaped nitrogen-sulfur-oxygen co-doped anode material, acetylene Black (AB) and polyvinylidene fluoride adhesive in a mass ratio of 80:10:10, and then the slurry is coated on aluminum foil after being uniformly ground and is placed in an oven at 80 ℃ for 900 minutes. The cell assembly was run in an argon-filled glove box (MBRAUN MB Labstar 1500:1500/780), with both water and oxygen contents of less than 0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is propylene carbonate with NaClO 4 (1 mol) added. Glass fibers are used as separator material. The cycle performance and charge and discharge efficiency of the battery were tested using NEWARE-BTS-4008 multichannel battery cycler. The current of the charge-discharge test is 100mA/g, the specific capacity of the charge-discharge test is 419mAh/g, the first efficiency is 89%, and the specific capacity after 100 times of circulation is 352mAh/g.
Example 2
A preparation method of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material comprises the following steps:
(1) Preparing a precursor raw material: ethylenediamine and water are added into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and the volume ratio is 1:2, preparing 80ml of mixed solvent after fully stirring, adding 60mg of hydroquinone formaldehyde resin nanoribbon coils and 0.25mol of triethylene tetramine solution into the mixed solvent, sealing a reaction kettle, magnetically stirring the mixture under the ice water bath condition, simultaneously reserving a feed port through the reaction kettle, slowly injecting 0.74mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas until the pressure of the system reaches saturated vapor pressure, stirring the mixture at constant temperature for 2h under the pressure, centrifuging and washing the product with ethanol three times after the reaction is finished, and drying to constant weight at 60 ℃.
(2) Carbonizing: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 800 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2 hours. And slowly cooling to room temperature after carbonization is finished, and obtaining the string-like nitrogen-sulfur-oxygen co-doped anode material.
(3) Electrochemical performance test: the CR2032 type battery shell is adopted to assemble a battery, battery slurry is prepared according to the coil-shaped nitrogen-sulfur-oxygen co-doped anode material, acetylene Black (AB) and polyvinylidene fluoride adhesive in a mass ratio of 80:10:10, and then the slurry is coated on aluminum foil after being uniformly ground and is placed in an oven at 80 ℃ for 900 minutes. The cell assembly was run in an argon-filled glove box (MBRAUN MB Labstar 1500:1500/780), with both water and oxygen contents of less than 0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is propylene carbonate with NaClO 4 (1 mol) added. Glass fibers are used as separator material. The cycle performance and charge and discharge efficiency of the battery were tested using NEWARE-BTS-4008 multichannel battery cycler. The current of the charge-discharge test is 100mA/g, the specific capacity of the charge-discharge test is 452mAh/g, the first efficiency is 85%, and the specific capacity after 100 times of circulation is 320mAh/g.
Example 3
A preparation method of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material comprises the following steps:
(1) Preparing a precursor raw material: ethylenediamine and water are added into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and the volume ratio is 1: and 3, preparing 80ml of mixed solvent after fully stirring, adding 50mg of hydroquinone formaldehyde resin nanoribbon coils and 0.25mol of triethylene tetramine solution into the mixed solvent, sealing a reaction kettle, magnetically stirring the mixture under the ice water bath condition, simultaneously reserving a feed port through the reaction kettle, slowly injecting 1mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas to the pressure of the reaction system to 1MPa after the system pressure reaches saturated vapor pressure, stirring the mixture at constant temperature for 2h under the pressure, centrifuging and washing the product with ethanol three times after the reaction is finished, and drying to constant weight at 60 ℃.
(2) Carbonizing: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2 hours. And slowly cooling to room temperature after carbonization is finished, and obtaining the string-like nitrogen-sulfur-oxygen co-doped anode material.
(3) Electrochemical performance test: the CR2032 type battery shell is adopted to assemble a battery, battery slurry is prepared according to the coil-shaped nitrogen-sulfur-oxygen co-doped anode material, acetylene Black (AB) and polyvinylidene fluoride adhesive in a mass ratio of 80:10:10, and then the slurry is coated on aluminum foil after being uniformly ground and is placed in an oven at 80 ℃ for 900 minutes. The cell assembly was run in an argon-filled glove box (MBRAUN MB Labstar 1500:1500/780), with both water and oxygen contents of less than 0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is propylene carbonate with NaClO 4 (1 mol) added. Glass fibers are used as separator material. The cycle performance and charge and discharge efficiency of the battery were tested using NEWARE-BTS-4008 multichannel battery cycler. The current of the charge-discharge test is 100mA/g, the specific capacity of the charge-discharge test is 441mAh/g, the first efficiency is 75%, and the specific capacity after 100 times of circulation is 302mAh/g.
Example 4
A preparation method of a coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material comprises the following steps:
(1) Preparing a precursor raw material: ethylenediamine and water are added into a polytetrafluoroethylene lining of a high-pressure reaction kettle, and the volume ratio is 1:4, preparing 80ml of mixed solvent after fully stirring, adding 100mg of hydroquinone formaldehyde resin nanoribbon coils and 0.25mol of triethylene tetramine solution into the mixed solvent, sealing a reaction kettle, magnetically stirring the mixture under the ice water bath condition, simultaneously reserving a feed port through the reaction kettle, slowly injecting 1.25mol of carbon disulfide solvent into the reaction kettle, heating to 25 ℃, supplementing a certain amount of carbon dioxide gas until the pressure of the system reaches the saturated vapor pressure, stirring the mixture at constant temperature for 2h under the pressure, centrifuging and washing the product with ethanol three times after the reaction is finished, and drying to constant weight at 60 ℃.
(2) Carbonizing: and (3) carrying out one-step carbonization treatment on the dried sample, heating to 900 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2 hours. And slowly cooling to room temperature after carbonization is finished, and obtaining the string-like nitrogen-sulfur-oxygen co-doped anode material.
(3) Electrochemical performance test: the CR2032 type battery shell is adopted to assemble a battery, battery slurry is prepared according to the coil-shaped nitrogen-sulfur-oxygen co-doped anode material, acetylene Black (AB) and polyvinylidene fluoride adhesive in a mass ratio of 80:10:10, and then the slurry is coated on aluminum foil after being uniformly ground and is placed in an oven at 80 ℃ for 900 minutes. The cell assembly was run in an argon-filled glove box (MBRAUN MB Labstar 1500:1500/780), with both water and oxygen contents of less than 0.1ppm. The counter electrode is made of metal sodium sheet, and the electrolyte is propylene carbonate with NaClO 4 (1 mol) added. Glass fibers are used as separator material. The cycle performance and charge and discharge efficiency of the battery were tested using NEWARE-BTS-4008 multichannel battery cycler. The current of the charge-discharge test is 100mA/g, the specific capacity of the charge-discharge test is 500mAh/g, the first efficiency is 71%, and the specific capacity after 100 times of circulation is 314mAh/g.
Comparative example 1
The difference between the comparative example and the example 1 is that only hydroquinone formaldehyde resin nanoribbon coils are used as carbon precursors, and nitrogen/sulfur-containing high polymer materials are not polymerized on the surfaces of the hydroquinone formaldehyde resin nanoribbon coils, and the materials are hard carbon materials without nitrogen/sulfur elements after carbonization, and the specific steps are as follows: carbonizing 80mg of hydroquinone formaldehyde resin nanoribbon coils, heating to 600 ℃ at a heating rate of 5 ℃/min under the protection of inert gas, and then preserving heat for 2 hours. And slowly cooling to room temperature after carbonization is finished to obtain the hard carbon anode derived from the hydroquinone formaldehyde resin nanoribbon coils, and testing the electrochemical performance of the hard carbon anode according to the method of the example 1. The current of the charge-discharge test is 100mA/g, the first discharge specific capacity is 728mAh/g, the first efficiency is 52%, the specific capacity after 100 times of circulation is 211mAh/g, and the hetero atom doping can improve the first charge-discharge efficiency and the circulation performance of the anode material through comparison.
In addition, the negative electrode materials of example 1 and comparative example 1 were subjected to EIS electrode material impedance test by: the electrode potential is perturbed by alternating voltage (sine wave), which causes the electrode potential to oscillate near the balance potential, and the amplitude of the current (or voltage) signal can be recorded during the process of returning the electrode potential to the steady state, so that the alternating impedance (EIS) information of the electrode can be calculated, and the alternating impedance spectrogram can be drawn. The EIS was recorded for each cell in this experiment over a frequency range of 10 -2～105 Hz.
As a result, as shown in fig. 5, it can be seen that the resistance of the heteroatom-doped anode material is significantly lower than that of the undoped sample, which further proves that the heteroatom doping can effectively improve the conductivity of the anode material.
Comparative example 2
The difference between the comparative example and the example 1 is that the comparative example adopts the method of the patent CN 108666570A to obtain the nitrogen-oxygen co-doped nano-belt, takes the nano-belt as a substrate and further loads simple substance sulfur to obtain the nitrogen-oxygen-sulfur co-doped electrode material, and tests the sodium ion battery performance of the anode material according to the method of the example 1, wherein the current of charge and discharge tests is 100mA/g, the primary discharge specific capacity is 815mAh/g, the primary efficiency is 41%, and the specific capacity after 100 times of circulation is 151mAh/g.
By comparison, the method is different from the method for directly pyrolyzing the nitrogen-rich precursor to carry out nitrogen doping, the nitrogen-containing functional group is introduced into the obtained carbon material by the method of ammonia water activation post-treatment, the nitrogen doping amount is extremely low, and the nitrogen-sulfur-oxygen co-doped carbon nano-belt can be obtained by further mixing with elemental sulfur and heating. The specific surface area of the carbon material obtained by the method is too large, the irreversible capacity of the first charge and discharge is increased, the first charge and discharge efficiency is reduced, and meanwhile, elemental sulfur is further doped to be unfavorable for sulfur to enter the interlayer spacing of the carbon material, so that the carbon material is easy to fall off in the charge and discharge process, and the cycle performance of the anode material is poor.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the same; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (5)
1. The preparation method of the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material is characterized by comprising the following steps of:
(1) Mixing hydroquinone formaldehyde resin nanoribbon coils, ethylene amine and a solvent under ice water bath, adding carbon disulfide, heating to 25-30 ℃, supplementing carbon dioxide to 1-2 MPa after the system pressure reaches saturated vapor pressure, performing constant temperature reaction, and separating, cleaning and drying a product;
(2) Carbonizing the dried product in inert atmosphere to obtain the anode material of the cluster-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery,
Wherein in the step (1), the ratio of the mass of the hydroquinone formaldehyde resin nano-tape coil to the molar amount of the ethylene amine is 30-100 mg/0.25 mol,
The mol ratio of the ethylene amine to the carbon disulfide is 1:2-1:5,
In the step (2), the technological parameters of the carbonization treatment are as follows: heating to 500-900 ℃ at a speed of 5 ℃/min, preserving heat for 1.5-3 h, and
In the step (1), the solvent is a mixed solvent of water and ethylenediamine, wherein the volume ratio of the water to the ethylenediamine is 1:1-4:1.
2. The method according to claim 1, wherein in the step (1), the ethyleneamine is one or more selected from diethylenetriamine, triethylenetetramine, tetraethylenepentamine and pentaethylenehexamine.
3. The method of claim 1, wherein the concentration of the hydroquinone formaldehyde resin nanoribbon coils in the solvent is 0.375-1.25 g/L.
4. A coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material, which is characterized by being prepared by the preparation method of any one of claims 1-3;
The coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material is hard carbon with a ribbon coil structure, the hard carbon is in a core-shell structure, an inner core is a carbon skeleton derived from hydroquinone formaldehyde resin, and the surface of the inner core is coated with a nitrogen-sulfur-oxygen doped carbon shell layer.
5. A sodium ion battery comprising the coil-shaped nitrogen-sulfur-oxygen co-doped sodium ion battery anode material of claim 4.
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