CN112133902A - Sodium metal negative electrode deposition matrix and preparation method and application thereof - Google Patents
Sodium metal negative electrode deposition matrix and preparation method and application thereof Download PDFInfo
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- CN112133902A CN112133902A CN202011078094.6A CN202011078094A CN112133902A CN 112133902 A CN112133902 A CN 112133902A CN 202011078094 A CN202011078094 A CN 202011078094A CN 112133902 A CN112133902 A CN 112133902A
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- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 title claims abstract description 71
- 239000011159 matrix material Substances 0.000 title claims abstract description 51
- 230000008021 deposition Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 82
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 77
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 77
- 239000011734 sodium Substances 0.000 claims abstract description 77
- 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 abstract description 73
- 238000000151 deposition Methods 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000001465 metallisation Methods 0.000 claims abstract description 26
- 238000005096 rolling process Methods 0.000 claims abstract description 26
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 20
- 238000000576 coating method Methods 0.000 claims abstract description 17
- 239000000758 substrate Substances 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 25
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 24
- 239000002131 composite material Substances 0.000 claims description 21
- 239000000843 powder Substances 0.000 claims description 20
- 239000000463 material Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- 238000005520 cutting process Methods 0.000 claims description 14
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 10
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 8
- 239000011889 copper foil Substances 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 6
- 235000010413 sodium alginate Nutrition 0.000 claims description 6
- 239000000661 sodium alginate Substances 0.000 claims description 6
- 229940005550 sodium alginate Drugs 0.000 claims description 6
- 235000012431 wafers Nutrition 0.000 claims description 6
- ZMVMBTZRIMAUPN-UHFFFAOYSA-H [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [Na+].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O ZMVMBTZRIMAUPN-UHFFFAOYSA-H 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 5
- 239000010439 graphite Substances 0.000 claims description 5
- 239000004317 sodium nitrate Substances 0.000 claims description 5
- 235000010344 sodium nitrate Nutrition 0.000 claims description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 5
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 238000003825 pressing Methods 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 239000011888 foil Substances 0.000 claims description 3
- 238000004108 freeze drying Methods 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 235000010378 sodium ascorbate Nutrition 0.000 claims description 3
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 claims description 3
- 229960005055 sodium ascorbate Drugs 0.000 claims description 3
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 238000003287 bathing Methods 0.000 claims description 2
- 238000007599 discharging Methods 0.000 claims description 2
- 238000000926 separation method Methods 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 238000012360 testing method Methods 0.000 abstract description 13
- 210000001787 dendrite Anatomy 0.000 abstract description 9
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000010899 nucleation Methods 0.000 abstract description 6
- 230000006911 nucleation Effects 0.000 abstract description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001301 oxygen Substances 0.000 abstract description 4
- 229910052760 oxygen Inorganic materials 0.000 abstract description 4
- 125000000524 functional group Chemical group 0.000 abstract description 3
- 210000004027 cell Anatomy 0.000 description 17
- 239000003792 electrolyte Substances 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 description 8
- 239000011521 glass Substances 0.000 description 8
- -1 sodium hexafluorophosphate Chemical compound 0.000 description 8
- 239000012528 membrane Substances 0.000 description 6
- 239000000835 fiber Substances 0.000 description 5
- 229920001410 Microfiber Polymers 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 239000003658 microfiber Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000007784 solid electrolyte Substances 0.000 description 3
- 238000010345 tape casting Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
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- 238000012986 modification Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
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- 230000005764 inhibitory process Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
Images
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
-
- 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
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
-
- 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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/027—Negative electrodes
-
- 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 relates to the technical field of sodium ion batteries, in particular to a sodium metal negative electrode deposition matrix and a preparation method and application thereof; the preparation method of the sodium metal negative electrode deposition matrix comprises the following steps: porous graphene is prepared, and then a sodium metal deposition matrix is prepared by a blade coating method or a rolling method. The sodium metal cathode deposition substrate provided by the invention is a deposition substrate based on porous graphene, has a large specific surface area, can effectively reduce local current density and homogenize sodium ion flow, has rich oxygen-containing functional groups, and can increase the surface sodium affinity, so that the uniform nucleation and deposition of sodium are guided, the formation of sodium dendrite is effectively inhibited, and excellent performance is shown in tests of half batteries and symmetrical batteries.
Description
Technical Field
The invention relates to the technical field of sodium ion batteries, in particular to a sodium metal negative electrode deposition matrix and a preparation method and application thereof.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
With the ever-increasing demand for high energy density energy storage devices for mobile electronic devices, metal cathodes have been rapidly developed. The sodium metal cathode has 1166mA h g at low electrode potential-1The sodium metal negative electrode is an indispensable material for constructing new high-energy density batteries such as sodium/oxygen batteries, sodium/sulfur batteries and the like. However, due to the inherent activity of metallic sodium, sodium metal negative electrodes suffer from the formation of unstable solid electrolyte interfacial films and sodium dendrites, leading to problems of low coulombic efficiency, infinite volume change and non-uniform sodium deposition, poor cycle stability, etc., which severely hamper the practical application of this material. Therefore, the construction of a uniform and stable solid electrolyte interfacial film, the homogenization of sodium ion flow and the inhibition of the growth of sodium dendrites are very important for realizing a stable sodium metal negative electrode.
In order to solve the problems of the sodium metal negative electrode, various strategies for realizing the long-cycle-life sodium metal negative electrode are adopted in the prior art: (1) the growth of the sodium dendrite is effectively relieved by optimizing the electrolyte formula and constructing an artificial interface layer to form an artificial solid electrolyte interface film on the sodium surface. (2) The current collectors (aluminum foil and copper foil) are made into porous structures, so that volume change can be relieved, and dendritic crystal growth can be inhibited. (3) The metal is limited in a three-dimensional matrix in a melting mode, so that the stability of the sodium metal negative electrode can be improved. However, the inventors have found that these methods make the sodium negative electrode less stable at high current densities or the preparation conditions are severe. In addition, theoretical calculation shows that the oxygen-containing group has stronger binding energy with sodium, can effectively attract the sodium and guide the uniform nucleation of the sodium. Therefore, the 'sodium affinity' deposition matrix is designed, the nucleation and growth of sodium are regulated and controlled in the initial stage of the formation of sodium dendrites, the formation of the sodium dendrites is inhibited in a convenient mode, the cycle stability of the sodium metal negative electrode is improved, and the method has important significance for realizing the stable sodium metal negative electrode.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a sodium metal cathode deposition substrate and a preparation method and application thereof, the sodium metal cathode deposition substrate provided by the invention is a deposition substrate based on porous graphene, the deposition substrate has a large specific surface area, can effectively reduce local current density and homogenize sodium ion flow, has rich oxygen-containing functional groups, and can increase the surface 'sodium affinity', so that the uniform nucleation and deposition of sodium are guided, the formation of sodium dendrite is effectively inhibited, and excellent performance is shown in tests of half-cells and symmetric cells.
One of the purposes of the invention is to provide a preparation method of a sodium metal negative electrode deposition matrix, which comprises the following steps: porous graphene is prepared, and then a sodium metal deposition matrix is prepared by a blade coating method or a rolling method.
The blade coating method comprises the following steps: mixing porous graphene powder and sodium alginate according to a certain proportion, adding a proper amount of water, grinding into slurry, then blade-coating the slurry on a copper foil by using a scraper, drying and cutting into wafers to obtain a sodium metal deposition matrix;
the rolling method comprises the following steps: cutting fresh sodium metal into small pieces in a glove box filled with argon gas, rolling into a flat sheet, adding porous graphene powder in batches, repeatedly folding and rolling to ensure that the color of the porous graphene/sodium composite material is uniform, and uniformly dispersing the porous graphene in sodium; rolling and pressing the uniformly mixed materials until the thickness is uniform, and cutting into round pieces to obtain the sodium metal deposition matrix.
The invention also aims to provide the sodium metal negative electrode deposition matrix prepared by the method.
The invention also aims to provide the application of the sodium metal negative electrode deposition matrix in the sodium-ion battery.
The invention also provides a sodium ion symmetric battery, which is assembled by taking the sodium metal cathode deposition matrix as a positive electrode and a negative electrode.
The fifth purpose of the invention is to provide a sodium ion full cell, wherein the sodium metal negative electrode deposition substrate is used as a negative electrode, and the graphene composite vanadium sodium phosphate is used as a positive electrode.
Compared with the prior art, one or more embodiments in the invention have the following advantages or beneficial effects:
(1) the sodium metal deposition matrix is prepared by a blade coating method, and the method is simple and efficient, does not need heating and melting, has low requirements on experimental equipment and low energy consumption, and is more beneficial to large-scale application; porous graphene and metal sodium are uniformly mixed by a rolling method, so that a stable sodium metal cathode is obtained, the method is simple and efficient, a heating melting or electrodeposition process is not needed, the requirement on experimental equipment is low, the energy consumption is low, and the large-scale application is facilitated.
(2) According to the invention, sodium is deposited on the porous graphene, and the large specific surface area and abundant sodium-philic functional groups on the surface of the porous graphene material can effectively reduce the nucleation overpotential of sodium, promote uniform nucleation of sodium, stabilize the deposition/stripping of sodium in the circulation process and inhibit the growth of sodium dendrites.
(3) The sodium metal cathode deposition matrix provided by the invention has higher coulombic efficiency and stable cycle performance in tests of half-cells and symmetrical cells.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
Fig. 1 is a scanning electron microscope photograph of the porous graphene prepared in example 1.
FIG. 2 shows the assembled half cell of example 2 at 0.5mA cm-2Current density of 1mA h cm-2Sodium deposition/stripping voltage curve at area capacity.
FIG. 3 shows the assembled half-cell of example 2 and comparative example 1The pool is at 0.5mA cm-2Current density of 1mA h cm-2Plating/stripping coulombic efficiency at area capacity of (a).
FIG. 4 shows the cell assembly of example 4 and comparative example 2 at 3mA cm-2Current density of 1mA h cm-2Sodium plating/stripping voltage curve at area capacity of (a).
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As described in the background art, the prior art has a problem that the stability of the sodium metal negative electrode under a large current density is poor or the preparation conditions are harsh, and in order to solve the technical problem, the first aspect of the present invention provides a preparation method of a sodium metal negative electrode deposition matrix, which comprises the following steps: porous graphene is prepared, and then a sodium metal deposition matrix is prepared by a blade coating method or a rolling method.
The blade coating method comprises the following steps: mixing porous graphene powder and sodium alginate (CMC) according to a certain proportion, adding a proper amount of water, grinding into slurry, then coating the slurry on a current collector by a scraper, drying and cutting into wafers to obtain the sodium metal deposition matrix.
The rolling method comprises the following steps: cutting fresh sodium metal into small pieces in a glove box filled with argon gas, rolling into a flat sheet, adding porous graphene powder in batches, repeatedly folding and rolling to ensure that the color of the porous graphene/sodium composite material is uniform, and uniformly dispersing the porous graphene in sodium. Rolling and pressing the uniformly mixed materials until the thickness is uniform, and then cutting the materials into round pieces to obtain the sodium metal deposition matrix.
In one or more embodiments of the present invention, in the knife coating method, the mass ratio of the porous graphene powder to sodium alginate (CMC) is 9: 1; the diameter of the round piece is 10-14 mm.
In one or more embodiments of the present invention, in the rolling method, the porous graphene powder accounts for 3 wt% of the total mass of the sodium lumps and the porous graphene;
preferably, the diameter of the disc is 10-14mm, and the uniformly mixed material is rolled to a thickness of 0.5-1.2 μm.
Preferably, the current collector is a copper foil or an aluminum foil.
In one or more embodiments of the present invention, the preparation steps of the porous graphene are:
1) under the condition of continuous stirring, sequentially mixing concentrated sulfuric acid, graphite and sodium nitrate, uniformly stirring, and slowly adding potassium permanganate in batches;
2) dissolving the above materials in water bath, stirring to obtain a viscous state, adding water, and slowly adding hydrogen peroxide until the color changes from brown to yellow. Precipitating, centrifuging, washing with hydrochloric acid and water sequentially, centrifuging, and dialyzing for one week.
3) Taking out the dialyzed substance in the step 2), adding a proper amount of hydrogen peroxide, performing oil bath under continuous stirring, performing centrifugal separation and water washing, and dispersing into a porous graphene oxide solution.
4) Adding sodium ascorbate into the porous graphene oxide solution, uniformly dispersing under continuous ultrasonic and stirring, then placing in an oil bath for a period of time, taking out, washing with water, and freeze-drying to obtain porous graphene powder.
In one or more embodiments of the present invention, in step 1), the mass-to-volume ratio of graphite to concentrated sulfuric acid, sodium nitrate, and potassium permanganate is: (2-4) g, (60-80) mL, (1.3-1.6) g, (8-10) g.
Preferably, in the step 1), before adding the potassium permanganate, the temperature is controlled below 20 ℃;
preferably, in step 2), the concentration of hydrochloric acid is 1.2mol L-1The amount of the hydrochloric acid is 250-300 ml;
preferably, in the step 2), the water bath temperature is 30-40 ℃, and the stirring time is 20-30 min;
preferably, in step 2), the volume ratio of water to hydrogen peroxide is 125: 3.
In one or more embodiments of the invention, in step 3), the dialyzed material is taken out and prepared into a solution of 2mg/mL, and then mixed with hydrogen peroxide;
preferably, in step 3), the volume ratio of the dialyzed solution to the hydrogen peroxide is 10: 1.
Preferably, in step 3), the oil bath conditions are as follows: oil-bathing at 100 deg.C for 3-5 h;
preferably, in the step 3), the graphene oxide is dispersed into a porous graphene oxide solution of 2mg/mL after being washed with water;
in one or more embodiments of the present invention, in step 4), the volume-to-mass ratio of the porous graphene oxide solution to the ascorbic acid is: 0.01g in 10 mL.
Preferably, in step 4), the oil bath conditions are as follows: placing in an oil bath at 100 ℃ for 2-3 h.
The invention provides a sodium metal negative electrode deposition matrix prepared by the method.
In a third aspect, the invention provides the use of a sodium metal negative deposition matrix in a sodium ion battery.
The invention provides a sodium ion symmetric battery, which is assembled by taking the sodium metal cathode deposition matrix as a positive electrode and a negative electrode;
preferably, when a sodium metal cathode deposition substrate prepared by a blade coating method is adopted, the substrate is pre-embedded with sodium to obtain a porous graphene/sodium composite electrode, and then the porous graphene/sodium composite electrode is used as a positive electrode and a negative electrode to assemble a symmetrical battery;
the method for pre-embedding sodium comprises the following steps: circulating the half-cell containing sodium metal deposition matrix under 0.01-1V and 0.05mA current for 5 circles, and then circulating at 1mA cm-2Is discharged for 8h at a current density ofThen taken out of the glove box and pre-embedded with 8mA h cm-2Sodium metal deposition matrix of sodium, i.e. porous graphene/sodium composite electrode.
The fifth aspect of the invention provides a sodium ion full cell, wherein the sodium metal negative electrode deposition substrate is used as a negative electrode, and the graphene composite vanadium sodium phosphate is used as a positive electrode;
preferably, when the sodium metal negative electrode deposition matrix prepared by a blade coating method is adopted, the matrix is pre-embedded with sodium to obtain the porous graphene/sodium composite electrode, and then the porous graphene/sodium composite electrode is used as a negative electrode to assemble a sodium ion full battery.
In order to make the technical solution of the present invention more clearly understood by those skilled in the art, the technical solution of the present invention will be described in detail below with reference to specific examples and comparative examples.
Example 1
The preparation method of the porous graphene comprises the following steps:
1) 3g of graphite is added to 70mL of concentrated sulfuric acid with continuous stirring, and then 1.5g of sodium nitrate is added and stirred uniformly. The temperature is controlled below 20 ℃, and 9g of potassium permanganate is slowly added in batches.
2) Transferring the beaker containing the solution into a water bath at 35 ℃, and stirring for 30min to form a sticky state. Then 500mL of water are added, stirred for 15min and 12mL of hydrogen peroxide are slowly added until the color changes from brown to yellow. Precipitating, centrifuging, and adding 250mL of 1.2mol L-1Washed with hydrochloric acid and repeatedly washed with water, then centrifuged and dialyzed for one week.
3) The dialyzed material was taken out to prepare a 2mg/mL solution, 50mL of which was taken out and then 5mL of hydrogen peroxide was added, and the mixture was subjected to 100 ℃ oil bath for 4 hours with continuous stirring. The mixture was then centrifuged, washed several times with water and dispersed into a 2mg/mL porous graphene oxide solution.
4) 10mL of porous graphene oxide solution is taken out, 0.01g of sodium ascorbate is added, and the solution is uniformly dispersed under continuous ultrasonic and stirring. And then placing the graphene powder in an oil bath at 100 ℃ for 2h, taking out the graphene powder, washing the graphene powder with water, placing the graphene powder in a refrigerator for 12h, and then freeze-drying the graphene powder to obtain porous graphene powder.
Example 2
Preparation of sodium Metal deposition matrix by knife coating:
mixing the porous graphene powder prepared in the example 1 and sodium alginate (CMC) according to a mass ratio of 9:1, adding a proper amount of water, grinding into slurry, then blade-coating the slurry on a copper foil by using a scraper, drying, and cutting into a circular sheet with the diameter of 12mm to obtain the sodium metal deposition matrix.
Assembly and testing of half-cells:
and assembling the CR2032 button cell in a glove box by taking the prepared sodium metal deposition matrix as a positive electrode and a metal sodium sheet as a negative electrode. The electrolyte is 1M sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the membrane is glass microfine fiber Whatman GF/F. First, 5 cycles at a current of 0.05mA between 0.01 and 1V (small current cycles can remove impurities on the surface to form a stable SEI film), and then 0.5mA cm-2-3mA cm-2Current density of 1mA h cm-2Capacity of (c) was tested for coulombic efficiency.
Example 3
Preparing a sodium metal deposition matrix by a rolling method:
cutting fresh sodium metal into small pieces in a glove box filled with argon gas, rolling the small pieces into a flat sheet, adding 3 wt% of the porous graphene powder prepared in example 1 in batches, and repeatedly folding and rolling the porous graphene/sodium composite material to ensure that the color of the porous graphene/sodium composite material is uniform, so that the porous graphene is uniformly dispersed in the sodium. Rolling and pressing the uniformly mixed materials until the thickness is uniform and consistent and about 1 mu m, and then cutting the materials into round pieces with the diameter of 12mm to obtain the sodium metal deposition matrix.
Assembly and testing of half-cells:
and assembling the CR2032 button cell in a glove box by taking the prepared sodium metal deposition matrix as a positive electrode and a metal sodium sheet as a negative electrode. The electrolyte is 1M sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the membrane is glass microfine fiber Whatman GF/F. Circulating at 0.01-1V at 0.05mA current for 5 circles, and then at 0.5mA cm-2～3mA cm-2Current density of 1mA h cm-2At a capacity ofAnd (4) testing the coulomb efficiency.
Example 4
Preparation and testing of symmetric cells:
the sodium metal deposition matrix prepared in example 2 was used as a positive electrode, and a metal sodium sheet was used as a negative electrode, and assembled into a CR2032 coin cell in a glove box. The electrolyte is 1M sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the membrane is glass microfine fiber Whatman GF/F. First, the mixture was circulated at a current of 0.05mA between 0.01 and 1V for 5 cycles at 1mA cm-2Discharging for 8h at the current density of (1), and taking out the deposit of 8mA h cm in a glove box-2And a sodium electrode, namely, a symmetric battery is assembled by using a porous graphene/sodium composite electrode as a positive electrode and a negative electrode, and the current density and the area capacity are fixed for testing the cycle performance.
Example 5
Preparation of a symmetrical battery:
the sodium metal deposition matrix (porous graphene/sodium) prepared in example 3 was used as a positive electrode and a negative electrode, and assembled into a CR2032 coin cell in a glove box. The electrolyte is 1M sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the diaphragm is glass microfiber Whatman GF/F, and the test of the cycle performance is carried out at fixed current density and area capacity.
Example 6
Preparing a full battery:
the porous graphene/sodium composite electrode prepared in example 4 was used as a negative electrode, the graphene composite vanadium sodium phosphate was used as a positive electrode, and 1M sodium hexafluorophosphate serving as an electrolyte was dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the membrane is glass microfine fiber Whatman GF/F. And assembling the sodium ion battery into a CR2032 button battery in a glove box to obtain the sodium ion full battery.
Example 7
Preparing a full battery:
the sodium metal deposition matrix prepared in example 3 was used as a negative electrode, the graphene vanadium sodium phosphate complex was used as a positive electrode, and 1M sodium hexafluorophosphate as an electrolyte was dissolved in diethylene glycol dimethyl ether (1M NaPF)6 in DEGDME)，The membrane is glass microfiber Whatman GF/F. And assembling the sodium ion battery into a CR2032 button battery in a glove box to obtain the sodium ion full battery.
Comparative example 1:
and cleaning the copper foil, cutting the copper foil into a 12mm wafer serving as a positive electrode, taking a metal sodium sheet as a negative electrode, and assembling the wafer into the CR2032 button cell in a glove box. The electrolyte is 1M sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the membrane is glass microfine fiber Whatman GF/F. First, circulating at 0.05mA current between 0.01-1V for 5 circles, and then at 0.5mA cm-2～3mA cm-2Current density of 1mA h cm-2Capacity of (c) was tested for coulombic efficiency.
Comparative example 2:
and rolling the metal sodium into uniform sheets, cutting the uniform sheets into circular sheets with the diameter of 12mm, and assembling the circular sheets into the CR2032 button battery in a glove box by taking the metal sodium sheets as positive and negative electrodes. The electrolyte is 1M sodium hexafluorophosphate dissolved in diethylene glycol dimethyl ether (1M NaPF)6in DEGDME), the diaphragm is glass microfiber Whatman GF/F, and the circulating performance is tested by fixing current density and area capacity.
And (3) performance testing:
the test results of the half-cell and the symmetrical cell prepared in the embodiments 2, 3, 4 and 5 of the present invention under different current density and area capacity test conditions are shown in table 1:
TABLE 1
In the full cells prepared in examples 6 and 7 of the present invention, the mass of the active material at the positive electrode was 5.6mg cm-2，100mA g-1The test results at current densities of (a) are shown in table 2:
TABLE 2
As can be seen from table 1, the sodium metal deposition matrices prepared by the knife coating method and the rolling method provided by the present invention both exhibit excellent cycling stability. FIG. 2 shows the assembled half cell of example 2 at 0.5mA cm-2Current density of 1mA h cm-2The area capacity of sodium, the curve showing that after different cycles the voltage hysteresis remains very stable during the cycle, about 18mV, with a smaller voltage hysteresis showing a faster reaction kinetics, favoring a uniform deposition of metallic sodium. FIG. 3 shows the half-cells assembled between example 2 and comparative example 1 at 0.5mA cm-2Current density of 1mA h cm-2The plating/stripping coulombic efficiency at area capacity of (a), the coulombic efficiency of the porous graphene deposition matrix after 500 cycles of circulation is about 99.8% which is significantly better than that of comparative example 1. FIG. 4 shows the cell assembly of example 4 and comparative example 2 at 3mA cm-2Current density of 1mA h cm-2According to the sodium electroplating/stripping voltage curve of the area capacity, the porous graphene/sodium symmetrical battery can be circulated for more than 500 hours, and the overpotential is less than 20mV, which indicates that the 'sodium-philic' porous graphene can effectively inhibit the formation of sodium dendrite and stabilize the electroplating/stripping of sodium. As can be seen from table 2, the full cell assembled by the sodium metal deposition matrix prepared by the doctor blade method and the rolling method provided by the present invention has high first-turn coulombic efficiency and capacity retention rate.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a sodium metal negative electrode deposition matrix is characterized by comprising the following steps: preparing porous graphene, and preparing a sodium metal deposition matrix by a blade coating method or a rolling method;
the blade coating method comprises the following steps: mixing porous graphene powder and sodium alginate according to a certain proportion, adding a proper amount of water, grinding into slurry, then blade-coating the slurry on a copper foil by using a scraper, drying and cutting into wafers to obtain a sodium metal deposition matrix;
the rolling method comprises the following steps: cutting fresh sodium metal into small pieces in a glove box filled with argon gas, rolling into a flat sheet, adding porous graphene powder in batches, repeatedly folding and rolling to ensure that the color of the porous graphene/sodium composite material is uniform, and uniformly dispersing the porous graphene in sodium; rolling and pressing the uniformly mixed materials until the thickness is uniform, and cutting into round pieces to obtain the sodium metal deposition matrix.
2. The preparation method of claim 1, wherein in the blade coating method, the mass ratio of the porous graphene powder to the sodium alginate is 9:1, and the diameter of the wafer is 10-14 mm.
3. The method according to claim 1, wherein in the rolling method, the porous graphene powder accounts for 3 wt% of the total mass of the sodium block and the porous graphene;
preferably, the diameter of the round piece is 10-14mm, and the uniformly mixed materials are rolled to a piece with the thickness of 0.5-1.2 mu m;
preferably, the current collector is a copper foil or an aluminum foil.
4. The preparation method according to claim 1, wherein the porous graphene is prepared by the steps of:
1) under the condition of continuous stirring, sequentially mixing concentrated sulfuric acid, graphite and sodium nitrate, uniformly stirring, and slowly adding potassium permanganate in batches;
2) stirring the solution in a water bath to be viscous, adding water, and slowly adding hydrogen peroxide until the color is changed from brown to yellow; precipitating, centrifuging, washing with hydrochloric acid and water sequentially, centrifuging, and dialyzing for one week;
3) taking out the dialyzed substance in the step 2), adding a proper amount of hydrogen peroxide, performing oil bath under continuous stirring, performing centrifugal separation and water washing, and dispersing into a porous graphene oxide solution;
4) adding sodium ascorbate into the porous graphene oxide solution, uniformly dispersing under continuous ultrasonic and stirring, then placing in an oil bath for a period of time, taking out, washing with water, and freeze-drying to obtain porous graphene powder.
5. The preparation method according to claim 4, wherein in the step 1), the mass-to-volume ratio of graphite to concentrated sulfuric acid, sodium nitrate and potassium permanganate is as follows: (2-4) g, (60-80) mL, (1.3-1.6) g, (8-10) g;
preferably, in the step 1), before adding the potassium permanganate, the temperature is controlled below 20 ℃;
preferably, in step 2), the concentration of hydrochloric acid is 1.2mol L-1The amount of the hydrochloric acid is 250-300 ml;
preferably, in the step 2), the water bath temperature is 30-40 ℃, and the stirring time is 20-30 min;
preferably, in step 2), the volume ratio of water to hydrogen peroxide is 125: 3.
6. The method according to claim 4, wherein in step 3), the dialyzed material is taken out and prepared into a 2mg/mL solution, which is then mixed with hydrogen peroxide;
preferably, in the step 3), the volume ratio of the dialyzed solution to the hydrogen peroxide is 10: 1;
preferably, in step 3), the oil bath conditions are as follows: oil-bathing at 100 deg.C for 3-5 h;
preferably, in the step 3), the graphene oxide is dispersed into a porous graphene oxide solution of 2mg/mL after being washed with water;
preferably, in the step 4), the volume-to-mass ratio of the porous graphene oxide solution to the ascorbic acid is as follows: 0.01g of 10 mL;
preferably, in step 4), the oil bath conditions are as follows: placing in an oil bath at 100 ℃ for 2-3 h.
7. The sodium metal negative electrode deposition matrix obtained by the preparation method according to any one of claims 1 to 6.
8. Use of the sodium metal negative deposition matrix of claim 7 in a sodium ion battery.
9. A sodium ion symmetric battery, characterized in that the symmetric battery is assembled by the sodium metal cathode deposition matrix of claim 7 as the positive and negative electrodes;
preferably, when a sodium metal cathode deposition substrate prepared by a blade coating method is adopted, the substrate is pre-embedded with sodium to obtain a porous graphene/sodium composite electrode, and then the porous graphene/sodium composite electrode is used as a positive electrode and a negative electrode to assemble a symmetrical battery;
preferably, the method for pre-inserting sodium comprises the following steps: circulating the half-cell containing sodium metal deposition matrix under 0.01-1V and 0.05mA current for 5 circles, and then circulating at 1mA cm-2Discharging for 8h under the current density of (1), taking out the material in a glove box, and pre-embedding 8mA h cm-2Sodium metal deposition matrix of sodium, i.e. porous graphene/sodium composite electrode.
10. A sodium ion full cell, characterized in that the sodium metal cathode deposition matrix of claim 7 is used as a cathode, and graphene composite vanadium sodium phosphate is used as an anode;
preferably, when the sodium metal negative electrode deposition matrix prepared by a blade coating method is adopted, the matrix is pre-embedded with sodium to obtain the porous graphene/sodium composite electrode, and then the porous graphene/sodium composite electrode is used as a negative electrode to assemble a sodium ion full battery.
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