CN116374997A - Carbon-based composite anode material and preparation method and application thereof - Google Patents
Carbon-based composite anode material and preparation method and application thereof Download PDFInfo
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- CN116374997A CN116374997A CN202310650847.3A CN202310650847A CN116374997A CN 116374997 A CN116374997 A CN 116374997A CN 202310650847 A CN202310650847 A CN 202310650847A CN 116374997 A CN116374997 A CN 116374997A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 122
- 239000010405 anode material Substances 0.000 title claims abstract description 52
- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 239000000203 mixture Substances 0.000 claims abstract description 44
- 150000003839 salts Chemical class 0.000 claims abstract description 29
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 28
- 239000011737 fluorine Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 27
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000411 inducer Substances 0.000 claims abstract description 20
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000003054 catalyst Substances 0.000 claims abstract description 16
- 238000003763 carbonization Methods 0.000 claims abstract description 15
- 229910052786 argon Inorganic materials 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 238000005516 engineering process Methods 0.000 claims abstract description 8
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 8
- 238000007740 vapor deposition Methods 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 5
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 4
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical group [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 22
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims description 14
- 229910001416 lithium ion Inorganic materials 0.000 claims description 14
- 229910001415 sodium ion Inorganic materials 0.000 claims description 14
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- 229910052744 lithium Inorganic materials 0.000 claims description 10
- 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 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000003792 electrolyte Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- 239000011734 sodium Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 239000010410 layer Substances 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 5
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 239000010426 asphalt Substances 0.000 claims description 4
- 229910021389 graphene Inorganic materials 0.000 claims description 4
- PAZHGORSDKKUPI-UHFFFAOYSA-N lithium metasilicate Chemical compound [Li+].[Li+].[O-][Si]([O-])=O PAZHGORSDKKUPI-UHFFFAOYSA-N 0.000 claims description 4
- 229910052912 lithium silicate Inorganic materials 0.000 claims description 4
- 229910052749 magnesium Inorganic materials 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 4
- 238000005086 pumping Methods 0.000 claims description 4
- 239000002344 surface layer Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 125000001153 fluoro group Chemical group F* 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 239000004341 Octafluorocyclobutane Substances 0.000 claims description 2
- -1 lithium halide Chemical class 0.000 claims description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N lithium oxide Chemical compound [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 claims description 2
- 229910001947 lithium oxide Inorganic materials 0.000 claims description 2
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019407 octafluorocyclobutane Nutrition 0.000 claims description 2
- 238000001771 vacuum deposition Methods 0.000 claims description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 abstract 3
- 229910052593 corundum Inorganic materials 0.000 description 11
- 239000010431 corundum Substances 0.000 description 11
- 239000000853 adhesive Substances 0.000 description 8
- 230000001070 adhesive effect Effects 0.000 description 8
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 8
- 238000009832 plasma treatment Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000006229 carbon black Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 230000003993 interaction Effects 0.000 description 4
- 230000014759 maintenance of location Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000007773 negative electrode material Substances 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000007480 spreading Effects 0.000 description 4
- 238000003892 spreading Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 239000003513 alkali Substances 0.000 description 3
- 150000001340 alkali metals Chemical class 0.000 description 3
- 239000003575 carbonaceous material Substances 0.000 description 3
- 210000001787 dendrite Anatomy 0.000 description 3
- 229910021392 nanocarbon Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- AMXOYNBUYSYVKV-UHFFFAOYSA-M lithium bromide Chemical compound [Li+].[Br-] AMXOYNBUYSYVKV-UHFFFAOYSA-M 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/058—Construction or manufacture
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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
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Abstract
The invention relates to a carbon-based composite anode material, a preparation method and application thereof, belonging to the technical field of anode materials, wherein the preparation method comprises the following steps: uniformly mixing a carbon source and a molten salt system to obtain a mixture B, adding an inducer into the mixture B, carrying out ultrasonic treatment after mixing to obtain a mixture C, heating the mixture C to a carbonization temperature under the protection of argon for constant-temperature carbonization, and then obtaining a carbon nano substrate; vacuum depositing fluorine on the carbon nano substrate by using a plasma vapor deposition method to obtain the carbon nano substrate deposited with fluorine; and coating the artificial SEI film on the surface of the carbon nano substrate deposited with fluorine, and simultaneously adding a single-atom catalyst on the surface of the artificial SEI film by utilizing a magnetron sputtering or electrostatic spinning or in-situ growth technology to obtain the carbon-based composite anode material. The invention constructs the carbon nano substrate with the three-dimensional skeleton structure by taking the fused salt and the inducer as templates, so that the cathode can stably and effectively exert the capacity and the service life of the battery can be prolonged.
Description
Technical Field
The invention belongs to the technical field of negative electrode materials, and particularly relates to a carbon-based composite negative electrode material, and a preparation method and application thereof.
Background
The alkali metal battery has the advantages of rich reserve, low cost, high output voltage, strong adaptability, environmental friendliness, no pollution, wide working temperature, quick charge and discharge and high energy density. However, many problems still remain in the practical application process. The negative electrode material represented by alkali metal lithium and sodium has high reactivity, and when the negative electrode material is contacted with an electrolyte, an unstable SEI film (solid electrolyte interface film) can be spontaneously generated due to thermodynamic instability, and uncontrollable dendrite growth and infinite volume expansion can occur in the later cycle process. These phenomena can cause lower coulombic efficiency, capacity loss, shorter cycle life and serious potential safety hazards of the alkali metal cell, and bring resistance to practical application of the alkali metal cell.
The carbon material has low mass density (1.8 g.cm) -3 ) Is the most potential light-weight host material, and is commonly applied to the host materials of lithium and sodium metal cathodes. The key point of the method is that the thermodynamic stability and the reaction kinetic performance of the cathode are enhanced by modifying and regulating the physical and chemical properties of a main body material. And the structure and morphology, defects, microcrystalline structure, functional groups and the like of the pure carbon material can influence the deposition and growth of alkali metals. Therefore, morphology regulation and functionalization of the surface of the carbonaceous matrix is key to inhibiting dendrite formation and SEI film damage.
Based on the above, the invention provides a carbon-based composite anode material, and a preparation method and application thereof.
Disclosure of Invention
Aiming at the problems, the invention provides a carbon-based composite anode material, and a preparation method and application thereof.
The first object of the present invention can be achieved by the following technical scheme:
a preparation method of a carbon-based composite anode material comprises the following steps:
uniformly mixing a carbon source and a molten salt system to obtain a mixture B, adding an inducer into the mixture B, carrying out ultrasonic treatment after mixing to obtain a mixture C, heating the mixture C to a carbonization temperature under the protection of argon gas for constant-temperature carbonization, cooling along with a furnace, washing and drying to obtain a carbon nano substrate;
vacuum depositing fluorine on the carbon nano substrate by using a plasma vapor deposition method to obtain the carbon nano substrate deposited with fluorine;
and coating the artificial SEI film on the surface of the carbon nano substrate deposited with fluorine, and simultaneously adding a single-atom catalyst on the surface of the artificial SEI film by utilizing a magnetron sputtering or electrostatic spinning or in-situ growth technology to obtain the carbon-based composite anode material.
Further, the carbon source is one of nanoscale graphene, asphalt, carbon nanotubes, conductive graphite powder and nano carbon black.
Further, the molten salt system is NaCl/KCl system, liCl/NaCl system or CaCl 2 One of the systems of/NaCl system, liCl/NaCl/KCl.
Further, the inducer is one or a mixture of a plurality of N-methyl pyrrolidone, dimethylacetamide and dimethylformamide in any ratio.
Further, the mass ratio of the carbon source to the molten salt system is 1:10-1:30, and the volume ratio of the inducer to the mixture B is 1:1-2:1.
Further, the heating rate of the heating is 3-10 ℃/min, the carbonization temperature is 700-900 ℃, and the carbonization time is 1-4h.
Further, the vacuum deposition fluorine specifically comprises the following steps: and (3) pumping in octafluorocyclobutane gas, continuously pumping in the whole process, maintaining the vacuum degree at 20-30Pa, and simultaneously applying plasma with the power of 150-300W for 5-20min.
Further, the artificial SEI film is one of a lithium silicate artificial SEI film, a lithium carbonate artificial SEI film, a lithium oxide artificial SEI film and a lithium halide artificial SEI film, and the atomic catalyst is one or a mixture of any ratio of nano metal vanadium, metal titanium and metal magnesium.
Further, the carbon source is one of nanoscale graphene, asphalt, carbon nanotubes, conductive graphite powder and nano carbon black.
Further, the atomic catalyst is one or a mixture of several of nano metal vanadium, metal titanium and metal magnesium in any ratio.
The second object of the present invention can be achieved by the following technical scheme:
the carbon-based composite anode material is prepared by the preparation method of the carbon-based composite anode material and comprises a carbon nano substrate bottom layer 1 modified with fluorine element 2 and an artificial SEI film surface layer 3 embedded with a single-atom catalyst 4.
The third object of the present invention can be achieved by the following technical scheme:
an application of a carbon-based composite anode material, wherein the carbon-based composite anode material is applied to a lithium/sodium alkali battery and comprises the following components:
rolling and die-cutting the carbon-based composite anode material to prepare an anode of a lithium/sodium battery;
and then the obtained negative electrode is assembled with a diaphragm, a positive electrode plate, electrolyte and a shell, so that the lithium/sodium ion battery is obtained.
The invention has the beneficial effects that:
1. the preparation of the carbon nano substrate uses a molten salt method, breaks through the barrier of liquid phase synthesis of a high-covalent bond material at high temperature by a solvent method, and generates the carbon nano substrate under a control condition;
2. the carbon nano substrate obtained by the invention is different from the traditional carbon-based material, the carbon nano substrate with a three-dimensional skeleton structure is constructed by taking the molten salt and the inducer as templates, the formation of the three-dimensional skeleton structure is favorable for nucleating on the surface of the carbon nano substrate, the rate performance of a battery is improved, the service life of the battery is prolonged while the negative electrode stably and effectively plays a role in capacity, and the principle of constructing the carbon nano substrate with the three-dimensional skeleton structure by taking the molten salt and the inducer as templates is as follows: the molten salt is used as a reaction medium to realize a fluid template consisting of polar anions and cations at high temperature, realize the synthesis reaction of reaction elements at atomic level, and then add an inducer to obtain the three-dimensional skeleton structure carbon nanomaterial, wherein the three-dimensional skeleton structure can be stepped (the carbon source is graphene or asphalt or conductive graphite powder), can also be three-dimensional ellipsoidal stacked (the carbon source is carbon black) or can also be three-dimensional filiform wound (the carbon source is carbon nano tube) due to different carbon sources;
3. fluorine is introduced onto the carbon nano substrate by a plasma means, and the plasma C-F has higher conductivity than C-F connected by covalent bonds, and simultaneously has excellent electric conductor or semiconductor properties, thereby being more beneficial to further improving the electrochemical performance of the battery;
4. a stable artificial SEI film structure is constructed on a carbon nano substrate bottom layer modified with fluorine elements, and is modified by a single-atom catalyst, so that the SEI damage condition can be avoided, the electrode activity is enhanced, dendrite formation can be inhibited, and the cycle life and the cycle stability of the lithium/sodium alkali battery are improved when the obtained carbon-based composite anode material is applied to the lithium/sodium alkali battery.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention may be realized and attained by the structure particularly pointed out in the written description and claims hereof as well as the appended drawings.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 shows a flow chart of a method of preparing a carbon-based composite anode material according to an embodiment of the invention;
FIG. 2 is a schematic cross-sectional view showing a carbon-based composite anode material according to an embodiment of the present invention;
in the figure: 1. a nano-substrate bottom layer; 2. fluorine element; 3. an artificial SEI film surface layer; 4. monoatomic catalysts.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
As shown in fig. 1, a preparation method of a carbon-based composite anode material includes:
uniformly mixing a carbon source and a molten salt system to obtain a mixture B, adding an inducer into the mixture B, carrying out ultrasonic treatment after mixing to obtain a mixture C, heating the mixture C to a carbonization temperature in a programmed manner under the protection of argon gas to carry out constant-temperature carbonization, cooling along with a furnace, washing and drying to obtain a carbon nano substrate;
vacuum depositing fluorine on the carbon nano substrate by using a plasma vapor deposition method to obtain the carbon nano substrate deposited with fluorine;
and coating the artificial SEI film on the surface of the carbon nano substrate deposited with fluorine, and simultaneously adding a single-atom catalyst on the surface of the artificial SEI film by utilizing a magnetron sputtering or electrostatic spinning or in-situ growth technology to obtain the carbon-based composite anode material.
As shown in fig. 2, a schematic cross-sectional structure of a carbon-based composite anode material obtained in the embodiment of the present invention includes a carbon nano-substrate bottom layer 1 modified with a fluorine element 2 and an artificial SEI film surface layer 3 embedded with a single-atom catalyst 4.
Example 1
Preparation of carbon-based composite anode material:
the carbon source of this example was selected as pitch, the template-molten salt system required for the reaction was NaCl/KCl, and the inducer was Dimethylacetamide (DMA).
Step one: firstly, mixing molten salt in a ball mill for 30min according to a molar ratio of 1:1 to prepare a uniformly mixed molten salt system which is a mixture A;
step two: mixing a carbon source and molten salt in a mass ratio of 1:15 to form a mixture B, wherein an inducer with a volume ratio of 1:1 to the mixture B can be added, and after mixing, performing ultrasonic treatment for 60min to form a black mixture C;
step three: placing the mixture C into a corundum crucible, placing the corundum crucible into a tubular furnace, heating to 800 ℃ at 5 ℃ under the protection of argon gas, maintaining the temperature for 2 hours for carbonization, then cooling to room temperature along with the furnace, fully washing and filtering the obtained product by absolute ethyl alcohol, 0.5M dilute hydrochloric acid and hot deionized water (80 ℃) respectively, and drying at 80 ℃ for 12 hours to obtain a carbon nano substrate;
step four: spreading carbon nano-substrate in a wide-mouth corundum boat, placing in a vacuum chamber of a plasma vapor deposition machine, exhausting the chamber with argon to hollow, and then introducing C 4 F 8 The flow rate of the gas is controlled at 20mL/min, the whole process is continuously vacuumized, the vacuum degree is maintained at 30Pa, the applicable plasma power is 200W, the carbon nano-substrate is subjected to plasma treatment, and the carbon nano-substrate deposited with fluorine is finally obtained by controlling the plasma treatment time for 10 min;
step five: and then coating the artificial SEI film lithium silicate on the surface of the carbon nano substrate deposited with fluorine to ensure that the electrode has a stable SEI film, and simultaneously adding a single-atom catalyst nano metal vanadium on the surface of the artificial SEI film by a magnetron sputtering technology to improve the activity of the electrode by the interaction of metal and a matrix to obtain the carbon-based composite anode material.
Example 2
Application of the carbon-based composite anode material obtained in example 1:
the first step, the carbon-based composite anode material obtained in the embodiment 1 is processed by rolling and die cutting means according to the required shape of the electrode to form a battery anode, wherein a necessary amount of conductive adhesive is added in the anode forming process according to the knowledge of the person skilled in the art, and the kind and specific addition amount of the conductive adhesive are not repeated in the embodiment;
and a second step of: and finally, assembling the negative electrode obtained in the first step with a diaphragm, a positive electrode plate, electrolyte and a shell to obtain the lithium/sodium ion battery, wherein the lithium/sodium ion battery can be subjected to a cycle test.
Experimental results: at 1 mA.cm -2 The capacity retention rate of more than 98.0% can be maintained after 400 circles of stable circulation under the current density, the assembled symmetrical battery can be stabilized for 3500h with 10mV overpotential without obvious polarization, and the carbon-based composite anode material obtained in the embodiment 1 has better circulation stability when being used for accessories of lithium/sodium ion batteries.
Example 3
The carbon source of this example was chosen to be carbon nanotubes (50 nm), the template-molten salt system required for the reaction was NaCl/LiCl, and the inducer was N-methylpyrrolidone (NMP).
Step one: firstly, mixing molten salt in a ball mill for 40min according to a molar ratio of 1:1 to prepare a uniformly mixed molten salt system which is a mixture A;
step two: mixing a carbon source and molten salt in a mass ratio of 1:20 to form a mixture B, wherein an inducer with a volume ratio of 2:1 to the mixture B can be added, and after mixing, performing ultrasonic treatment for 45min to form a black mixture C;
step three: placing the mixture C into a corundum crucible, placing the corundum crucible into a tubular furnace, heating to 900 ℃ at 7 ℃ under the protection of argon gas, maintaining the temperature for 2 hours for carbonization, then cooling to room temperature along with the furnace, fully washing and filtering the obtained product by absolute ethyl alcohol, 1M dilute hydrochloric acid and hot deionized water (80 ℃) respectively, and drying at 90 ℃ for 10 hours to obtain the carbon nano-substrate.
Step four: spreading the obtained carbon nano substrate in a wide-mouth corundum boat, placing in a vacuum chamber of a plasma vapor deposition machine, exhausting the chamber with argon to hollow, and thenC is introduced into 4 F 8 The flow rate of the gas is controlled at 15mL/min, the whole process is continuously vacuumized, the vacuum degree is maintained at 20Pa, the applicable plasma power is 250W, the obtained carbon nano-substrate is subjected to plasma treatment, and the carbon nano-substrate deposited with fluorine is finally obtained by controlling the plasma treatment time for 15 min;
step five: and then coating the artificial SEI film lithium silicate on the surface of the carbon nano substrate deposited with fluorine to ensure that the electrode has a stable SEI film, and simultaneously adding a single-atom catalyst nano metal titanium on the surface of the artificial SEI film by a magnetron sputtering technology, and improving the activity of the electrode by the interaction of a metal matrix to obtain the carbon-based composite anode material.
Example 4
Application of the carbon-based composite anode material obtained in example 3:
the first step, the carbon-based composite anode material obtained in the embodiment 3 is processed by rolling and die cutting means according to the required shape of the electrode to form a battery anode, wherein a necessary amount of conductive adhesive is added in the anode forming process according to the knowledge of the person skilled in the art, and the kind and specific addition amount of the conductive adhesive are not repeated in the embodiment;
and a second step of: and finally, assembling the negative electrode obtained in the first step with a diaphragm, a positive electrode plate, electrolyte and a shell to obtain the lithium/sodium ion battery, wherein the lithium/sodium ion battery can be subjected to a cycle test.
Experimental results: at 3 mA.cm -2 The capacity retention rate of more than 97.5% can be maintained after the carbon-based composite anode material is stably circulated for 300 circles under the current density, and the assembled symmetrical battery can be stably circulated for 3000 hours at the overpotential of 10mV without obvious polarization, so that the carbon-based composite anode material obtained in the embodiment 3 has better circulation stability when used for accessories of lithium/sodium ion batteries.
Example 5:
the carbon source of this example was selected as conductive graphite powder (100 nm), the template-molten salt system required for the reaction was NaCl/LiCl/KCl, and the inducer was N-methylpyrrolidone (NMP).
Step one: firstly, mixing molten salt in a ball mill for 50min according to a molar ratio of 1:1:1 to prepare a uniformly mixed molten salt system which is a mixture A;
step two: mixing a carbon source and molten salt into a mixture B in a mass ratio of 1:25, wherein an inducer with a volume ratio of 2:1 to the mixture B can be added, and after mixing, performing ultrasonic treatment for 60min to form a black mixture C;
step three: placing the mixture C into a corundum crucible, placing into a tube furnace, heating to 700 ℃ at 5 ℃ under the protection of argon, and carbonizing at constant temperature for 4 hours; cooling to room temperature along with a furnace, washing and filtering the obtained product by absolute ethyl alcohol, 1.5M dilute hydrochloric acid and hot deionized water (90 ℃) fully, and drying for 16 hours at 70 ℃ to obtain a carbon nano substrate;
step four: spreading carbon nano-substrate in a wide-mouth corundum boat, placing in a vacuum chamber of a plasma vapor deposition machine, exhausting the chamber with argon to hollow, and then introducing C 4 F 8 The flow rate of the gas is controlled at 25mL/min, the whole process is continuously vacuumized, the vacuum degree is maintained at 30Pa, the applicable plasma power is 300W, the carbon nano-substrate is subjected to plasma treatment, and the carbon nano-substrate deposited with fluorine is finally obtained by controlling the plasma treatment time for 5 min;
step five: and then coating the artificial SEI film lithium carbonate on the surface of the carbon nano substrate deposited with fluorine to ensure that the electrode has a stable SEI film, and simultaneously adding a single-atom catalyst nano metal magnesium on the surface of the artificial SEI film by a magnetron sputtering technology to improve the activity of the electrode by the interaction of a metal-matrix so as to obtain the carbon-based composite anode material.
Example 6
Application of the carbon-based composite anode material obtained in example 5:
the first step, the carbon-based composite anode material obtained in the embodiment 5 is processed by rolling and die cutting means according to the required shape of the electrode to form a battery anode, wherein a necessary amount of conductive adhesive is added in the anode forming process according to the knowledge of the person skilled in the art, and the kind and specific addition amount of the conductive adhesive are not repeated in the embodiment;
and a second step of: and finally, assembling the negative electrode obtained in the first step with a diaphragm, a positive electrode plate, electrolyte and a shell to obtain the lithium/sodium ion battery, wherein the lithium/sodium ion battery can be subjected to a cycle test.
Experimental results: at 1.5 mA.cm -2 The capacity retention rate of more than 99% can be maintained after 400 circles of stable circulation under the current density, and the assembled symmetrical battery can be stably circulated for 2500 hours at an overpotential of 10mV without obvious polarization, which indicates that the carbon-based composite anode material obtained in the embodiment 5 has better circulation stability for accessories of lithium/sodium ion batteries.
Example 7:
the carbon source of this example was selected as nano carbon black, the template-molten salt system required for the reaction was NaCl/LiCl, and the inducer was Dimethylformamide (DMF).
Step one: firstly, mixing molten salt in a ball mill for 20min according to a molar ratio of 1:1 to prepare a uniformly mixed molten salt system which is a mixture A;
step two: mixing a carbon source and molten salt in a mass ratio of 1:10 to form a mixture B, wherein an inducer with a volume ratio of 1.5:1 to the mixture B can be added, and after mixing, performing ultrasonic treatment for 80min to form a black mixture C;
step three: placing the mixture C into a corundum crucible, placing the corundum crucible into a tubular furnace, heating to 800 ℃ at 6 ℃ under the protection of argon gas, maintaining the temperature for 3 hours for carbonization, then cooling to room temperature along with the furnace, fully washing and filtering the obtained product by absolute ethyl alcohol, 1M dilute hydrochloric acid and hot deionized water (70 ℃) respectively, and drying at 80 ℃ for 10 hours to obtain a carbon nano substrate;
step four: spreading carbon nano-substrate in a wide-mouth corundum boat, placing in a vacuum chamber of a plasma vapor deposition machine, exhausting the chamber with argon to hollow, and then introducing C 4 F 8 The flow rate of the gas is controlled at 15mL/min, the whole process is continuously vacuumized, the vacuum degree is maintained at 30Pa, the applicable plasma power is 250W, the plasma treatment is carried out on the D, and the carbon nano-substrate deposited with fluorine is finally obtained by controlling the plasma treatment time for 10 min;
step five: and then coating the 1:1 mixture of the lithium chloride and the lithium bromide of the artificial SEI film on the surface of the carbon nano substrate deposited with fluorine, ensuring that the electrode has a stable SEI film, adding a single-atom catalyst nano metal vanadium on the surface of the artificial SEI film through a magnetron sputtering technology, and improving the activity of the electrode through the interaction of a metal-matrix, thereby obtaining the carbon-based composite anode material.
Example 8
Application of the carbon-based composite anode material obtained in example 7:
the first step, the carbon-based composite anode material obtained in the embodiment 7 is processed by rolling and die cutting means according to the required shape of the electrode to form a battery anode, wherein a necessary amount of conductive adhesive is added in the anode forming process according to the knowledge of the person skilled in the art, and the kind and specific addition amount of the conductive adhesive are not repeated in the embodiment;
and a second step of: and finally, assembling the negative electrode obtained in the first step with a diaphragm, a positive electrode plate, electrolyte and a shell to obtain the lithium/sodium ion battery, wherein the lithium/sodium ion battery can be subjected to a cycle test.
Experimental results: at 1 mA.cm -2 The capacity retention rate of more than 99% can be maintained after the carbon-based composite anode material is stably circulated for 300 circles under the current density, and the assembled symmetrical battery can be stably circulated for 2500 hours at an overpotential of 10mV without obvious polarization, so that the carbon-based composite anode material obtained in the embodiment 7 has better circulation stability when being used for accessories of lithium/sodium ion batteries.
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 technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the carbon-based composite anode material is characterized by comprising the following steps:
uniformly mixing a carbon source and a molten salt system to obtain a mixture B, adding an inducer into the mixture B, carrying out ultrasonic treatment after mixing to obtain a mixture C, heating the mixture C to a carbonization temperature under the protection of argon gas for constant-temperature carbonization, cooling along with a furnace, washing and drying to obtain a carbon nano substrate;
vacuum depositing fluorine on the carbon nano substrate by using a plasma vapor deposition method to obtain the carbon nano substrate deposited with fluorine;
and coating the artificial SEI film on the surface of the carbon nano substrate deposited with fluorine, and simultaneously adding a single-atom catalyst on the surface of the artificial SEI film by utilizing a magnetron sputtering or electrostatic spinning or in-situ growth technology to obtain the carbon-based composite anode material.
2. The method for preparing a carbon-based composite anode material according to claim 1, wherein the carbon source is one of nanoscale graphene, asphalt, carbon nanotubes, conductive graphite powder and carbon nano-black.
3. The method for preparing a carbon-based composite anode material according to claim 1, wherein the molten salt system is NaCl/KCl system, liCl/NaCl system, caCl 2 One of the systems of/NaCl system, liCl/NaCl/KCl.
4. The method for preparing a carbon-based composite anode material according to claim 1, wherein the inducer is one or a mixture of several of N-methylpyrrolidone, dimethylacetamide and dimethylformamide in any ratio.
5. The method for preparing the carbon-based composite anode material according to claim 1, wherein the mass ratio of the carbon source to the molten salt system is 1:10-1:30, and the volume ratio of the inducer to the mixture B is 1:1-2:1.
6. The method for preparing a carbon-based composite anode material according to claim 1, wherein the heating rate of heating is 3-10 ℃/min, the carbonization temperature is 700-900 ℃, and the carbonization time is 1-4h.
7. The method for preparing a carbon-based composite anode material according to claim 1, wherein the vacuum deposition fluorine specifically comprises the following steps: and (3) pumping in octafluorocyclobutane gas, continuously pumping in the whole process, maintaining the vacuum degree at 20-30Pa, and simultaneously applying plasma with the power of 150-300W for 5-20min.
8. The method for preparing a carbon-based composite anode material according to any one of claims 1 to 7, wherein the artificial SEI film is one of a lithium silicate artificial SEI film, a lithium carbonate artificial SEI film, a lithium oxide artificial SEI film and a lithium halide artificial SEI film, and the atomic catalyst is one or a mixture of several of nano metal vanadium, metal titanium and metal magnesium in any ratio.
9. The carbon-based composite anode material is characterized by being prepared by the preparation method of the carbon-based composite anode material according to any one of claims 1-8, and comprises a carbon nano substrate bottom layer (1) modified with fluorine (2) and an artificial SEI film surface layer (3) embedded with a single-atom catalyst (4).
10. Use of the carbon-based composite anode material of claim 9 in a lithium/sodium alkaline battery, comprising:
rolling and die-cutting the carbon-based composite anode material to prepare an anode of a lithium/sodium battery;
and then the obtained negative electrode is assembled with a diaphragm, a positive electrode plate, electrolyte and a shell, so that the lithium/sodium ion battery is obtained.
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