CN115050939A - Preparation method and application of metal sodium negative electrode material - Google Patents
Preparation method and application of metal sodium negative electrode material Download PDFInfo
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- CN115050939A CN115050939A CN202210700011.5A CN202210700011A CN115050939A CN 115050939 A CN115050939 A CN 115050939A CN 202210700011 A CN202210700011 A CN 202210700011A CN 115050939 A CN115050939 A CN 115050939A
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- 239000011734 sodium Substances 0.000 title claims abstract description 124
- 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 title claims abstract description 101
- 229910052708 sodium Inorganic materials 0.000 title claims abstract description 101
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 59
- 239000002184 metal Substances 0.000 title claims abstract description 59
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 239000007773 negative electrode material Substances 0.000 title claims description 20
- 229920005610 lignin Polymers 0.000 claims abstract description 99
- 239000011241 protective layer Substances 0.000 claims abstract description 38
- 239000000843 powder Substances 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 30
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 28
- 239000010406 cathode material Substances 0.000 claims abstract description 12
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 8
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 claims abstract description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 30
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 239000010410 layer Substances 0.000 claims description 17
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- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 229910052786 argon Inorganic materials 0.000 claims description 15
- 239000002244 precipitate Substances 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000011261 inert gas Substances 0.000 claims description 12
- 239000012298 atmosphere Substances 0.000 claims description 11
- 238000011065 in-situ storage Methods 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 239000003513 alkali Substances 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 230000002255 enzymatic effect Effects 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 239000010405 anode material Substances 0.000 claims description 3
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- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 abstract description 49
- 230000008569 process Effects 0.000 abstract description 15
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- 238000001465 metallisation Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 239000003792 electrolyte Substances 0.000 description 10
- 238000000151 deposition Methods 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000000227 grinding Methods 0.000 description 5
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 4
- 229910006404 SnO 2 Inorganic materials 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 239000007772 electrode material Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
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- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 238000000231 atomic layer deposition Methods 0.000 description 1
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- 238000007599 discharging Methods 0.000 description 1
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- 238000009713 electroplating Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002655 kraft paper Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920005569 poly(vinylidene fluoride-co-hexafluoropropylene) Polymers 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- -1 zirconia compound Chemical class 0.000 description 1
Images
Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/362—Composites
- H01M4/366—Composites as layered products
-
- 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
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
- H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
-
- 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
- H01M4/381—Alkaline or alkaline earth metals elements
-
- 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
Abstract
The invention relates to a preparation method and application of a metal sodium cathode material rich in a C-O-Na structure lignin organic sodium salt protective layer. According to the invention, lignin powder is coated on the surface of sodium metal, so that active groups in a lignin polymer and metal sodium react spontaneously to form a lignin organic sodium salt protective layer rich in a C-O-Na structure. The lignin has wide raw material source, low cost and simple preparation method, and can be used for producing artificial protective layers in a large scale. The lignin organic sodium salt protective layer rich in the C-O-Na structure obtained by the preparation method can provide high ionic conductivity, so that relatively uniform sodium ion flux distribution is obtained, battery polarization is reduced, sodium dendrite is effectively inhibited, lower overpotential is shown in the constant current polarization process, volume change of a metal sodium cathode in the circulation process can be effectively relieved, sufficient mechanical strength is reserved, the membrane is effectively prevented from being punctured by dendrite, and the generation of sodium dendrite is effectively inhibited in the sodium metal deposition/stripping process.
Description
Technical Field
The invention belongs to the technical field of sodium metal batteries, and particularly relates to a preparation method and application of a metal sodium cathode material, in particular to a preparation method and application of a metal sodium cathode material rich in a C-O-Na structure lignin organic sodium salt protective layer.
Background
The sodium metal cathode has very high theoretical capacity (approximatively 1166 mAh.g) -1 ) Low redox potential (voltage is-2.71V compared with SHE), high energy density and the like. In addition, the sodium metal cathode can be coupled with a high-potential anode without element sodium, so that the selection range of the battery anode is widened. Based on the above multiple advantages, the sodium metal negative electrode can be used for developing the next generation of high energy density secondary sodium metal battery, and thus has received much attention. However, sodium metal batteries still need to overcome some of the challenges before practical commercial use. The highly active sodium metal negative electrode inevitably reacts with the electrolyte to spontaneously form a Solid Electrolyte Interface (SEI) layer on the surface thereof. During charging and discharging, due to the large volume change of the sodium metal cathode, the interface layer is easy to break in the cycle process, and newly exposed sodium metal can continuously react with the electrolyte to form a new SEI layer so as to consume the electrolyte, so that the battery has low coulombic efficiency and short cycle life. Secondly, sodium dendrites are easily formed on the negative electrode surface of the sodium metal due to uneven sodium ion deposition, and the sodium dendrites penetrate through the diaphragm to cause short circuit inside the battery, so that safety accidents are caused. Sodium dendrites are also susceptible to structural collapse during sodium metal stripping to form "dead sodium" into the electrolyte. The above problems are seriously hinderedPreventing further development of sodium metal batteries.
To overcome the inherent disadvantages and safety problems of rechargeable sodium metal batteries, various methods have been developed to optimize the sodium metal negative electrode to improve its electrochemical stability. Among them, constructing a stable artificial SEI protective layer on the surface of a sodium metal negative electrode has proven to be one of the most effective methods. The main basis is that a protective layer capable of isolating the metal sodium cathode from electrolyte is constructed on the surface of the metal sodium cathode, so that the metal sodium cathode can be prevented from being corroded by the electrolyte in the circulating process and inhibits the growth of dendrites, and the safety and the cycle life of the metal sodium battery are effectively improved. Therefore, how to design a stable and efficient artificial SEI protective layer to realize uniform reversible deposition of sodium ions on the surface of the sodium metal negative electrode has important significance.
American academy reported a method of coating a Na metal surface with a thin layer of Al by a low temperature atomic layer deposition process 2 O 3 Layer, which can enhance its cycling stability. However, the method has the defects of complex process, high cost and difficulty in batch preparation; korean scholars reported a self-supporting thin film directly coated on the surface of sodium metal, the thin film being made of Al 2 O 3 And polyvinylidene fluoride-hexafluoropropylene (PVDF-HFP). Although the method is simple and easy to operate, the film is easy to fall off after multiple cycles, and the problem of the sodium metal cathode cannot be completely solved. Therefore, it is very urgent to develop a protective layer with low cost, simple preparation method and easy operation, so that the sodium metal has high coulombic efficiency and long cycle life.
Disclosure of Invention
The invention mainly aims to solve the problems of low coulombic efficiency, short cycle life, poor stability and the like of a metal sodium cathode material in the prior art, so that a C-O-Na structure-rich lignin organic sodium salt protective layer is constructed on the surface of a metal sodium cathode by utilizing lignin, the ionic conductivity and the mechanical property of the metal sodium electrode material are obviously improved, the change of the interface volume is effectively relieved, and the problem that a sodium metal battery is easy to form sodium dendrite in the charge-discharge cycle process is solved.
In order to achieve the above object, the present invention is realized by:
the invention provides a preparation method of a sodium metal negative electrode material, which comprises the following steps:
(1) adding lignin into ultrapure water, stirring thoroughly, separating insoluble brown precipitate, and vacuum drying brown precipitate to obtain lignin powder;
(2) under the atmosphere of inert gas, removing an oxide layer on the surface of the metal sodium, and then preparing a metal sodium sheet with uniform thickness;
(3) uniformly coating the lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an inert gas atmosphere, and carrying out in-situ reaction;
(4) and (4) after the reaction in the step (3) is carried out fully, removing unreacted lignin powder on the surface of the metal sodium sheet to obtain the metal sodium cathode material rich in the C-O-Na structure lignin organic sodium salt protective layer.
Preferably, the lignin in step (1) is selected from one or more of alkali lignin, enzymatic lignin and organic solvent lignin.
Preferably, the amount of the lignin used in the step (1) is 10-15g, and the volume of the ultrapure water is 100-200 mL.
Preferably, the separation in step (1) is selected from one or more of vacuum filtration and centrifugation.
Preferably, the vacuum drying conditions in step (1) are: the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
Preferably, the specification of the metal sodium sheet in the step (2) is as follows: the thickness is 100-150 μm and the size is 5X 5 cm.
Preferably, the inert gas in step (2) and step (3) is selected from one or more of argon and nitrogen.
Preferably, in the step (2) and the step (3), the oxygen content is 0.05-0.1ppm and the water content is 0.05-0.1ppm under the inert gas atmosphere.
Preferably, the lignin powder is used in an amount of 0.1 to 0.5g in step (3).
Preferably, the in situ reaction time in step (3) is 6-12 h.
The invention provides a sodium metal anode material prepared according to the preparation method.
The invention provides a sodium-ion battery, which comprises the metallic sodium negative electrode material prepared according to the preparation method.
The invention provides the application of lignin in improving the stability of the metallic sodium cathode material.
Preferably, the lignin is selected from one or more of alkali lignin, enzymatic lignin and organic solvent lignin.
The fifth aspect of the invention provides a method for improving the stability of a sodium metal anode material, which comprises the following steps:
(1) adding lignin into ultrapure water, stirring fully, separating out insoluble tan precipitate, and vacuum drying the tan precipitate to obtain lignin powder;
(2) under the atmosphere of inert gas, removing an oxide layer on the surface of the metal sodium, and then preparing a metal sodium sheet with uniform thickness;
(3) uniformly coating the lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an inert gas atmosphere, and carrying out in-situ reaction;
(4) and (4) after the full reaction in the step (3), removing unreacted lignin powder on the surface of the metal sodium sheet to obtain the metal sodium sheet.
Preferably, the lignin in step (1) is selected from one or more of alkali lignin, enzymatic lignin and organic solvent lignin.
Preferably, the amount of the lignin used in the step (1) is 10-15g, and the volume of the ultrapure water is 100-200 mL.
Preferably, the separation in step (1) is selected from one or more of vacuum filtration and centrifugal separation.
Preferably, the vacuum drying conditions in step (1) are: the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
Preferably, the specification of the metal sodium sheet in the step (2) is as follows: the thickness is 100-150 μm and the size is 5X 5 cm.
Preferably, the inert gas in step (2) and step (3) is selected from one or more of argon and nitrogen.
Preferably, in the step (2) and the step (3), the oxygen content is 0.05-0.1ppm and the water content is 0.05-0.1ppm under the inert gas atmosphere.
Preferably, the lignin powder is used in an amount of 0.1 to 0.5g in step (3).
Preferably, the in situ reaction time in step (3) is 6-12 h.
According to the invention, lignin is used as a raw material, and lignin powder is coated on the surface of the metallic sodium cathode, so that active groups (such as phenolic hydroxyl and carbonyl) in a lignin structure and metallic sodium spontaneously react to generate a lignin organic sodium salt protective layer rich in a C-O-Na structure.
Compared with the prior art, the invention has the following beneficial effects:
(1) compared with other sodium metal modification methods, the method has the advantages of wide source of lignin raw materials, low cost and simple preparation method, and can be used for producing artificial protective layers in a large scale.
(2) The lignin organic sodium salt protective layer rich in the C-O-Na structure obtained by the preparation method can provide high ionic conductivity, thereby obtaining relatively uniform and high sodium ion flux, reducing battery polarization and effectively inhibiting sodium dendrite.
(3) The lignin organic sodium salt protective layer rich in the C-O-Na structure obtained by the preparation method has the flexibility of a polymer, can effectively relieve the volume change of a metal sodium cathode in the circulation process, simultaneously retains enough mechanical strength, and can effectively prevent a membrane from being punctured by a sodium dendrite.
(4) When the lignin organic sodium salt protective layer obtained by the preparation method is used in a sodium metal battery, unstable SEI components can be prevented from being generated in the circulation process, the SEI components are more compact, and meanwhile, the corrosion of electrolyte can be inhibited.
Drawings
FIG. 1 is a schematic diagram of the reaction of lignin with sodium metal.
FIG. 2 is an infrared spectrum of lignin (dotted line) and the lignin organic sodium salt protective layer (solid line) of example 1.
FIG. 3 is a scanning electron microscope image of a sodium metal cathode with a protective layer of lignin organic sodium salt of example 1.
FIG. 4 is a graph showing the Young's modulus distribution of the surface of the metallic sodium negative electrode having the lignin-organic sodium salt protective layer of example 1.
FIG. 5 shows a 0.5mAh cm symmetric cell assembled by the sodium metal cathode with the lignin organic sodium salt protective layer prepared in example 1 and the pure sodium metal cathode prepared in comparative example 1 -2 ，0.5mAh·cm -2 (upper) and 1mAh · cm -2 ，1mAh·cm -2 Voltage profile of galvanostatic cycling measured under (lower) conditions.
Fig. 6 is a scanning electron microscope image of the surface of the metal sodium cathode with the lignin organic sodium salt protective layer prepared in example 1 after 10 cycles.
Fig. 7 is a scanning electron microscope image of the electrode surface of the pure sodium metal negative electrode prepared in comparative example 1 after 10 cycles.
Detailed Description
In order to make the objects, technical solutions and effects of the present invention clearer and clearer, the present invention is described in further detail below with reference to examples. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods. The lignin used in the examples and comparative examples of the present invention is alkali lignin as an example, and it should be understood that the lignin is used only as a raw material for providing a carbon source, and the specific type of the lignin has no significant influence on the properties of the finished catalyst, and when the catalyst preparation is performed by using other lignin types such as Longli enzymatic hydrolysis lignin, kraft paper lignin, Russian wood sodium and the like, the obtained catalyst performance is not significantly different from that of the alkali lignin, and thus, the alkali lignin is not listed any more.
Example 1
A preparation method of a metallic sodium negative electrode material has a reaction principle shown in figure 1, and comprises the following steps:
(1) adding 10g of alkali lignin into 200mL of ultrapure water, fully stirring to remove water-soluble inorganic salts, centrifugally separating out insoluble tan precipitate, drying the tan precipitate at 60 ℃ in vacuum for 12 hours, and grinding to obtain lignin powder;
(2) in an argon-filled glove box (oxygen content 0.05ppm, water content 0.05 ppm), the oxide layer on the surface of the metallic sodium was removed, and then rolled into a sodium sheet having a thickness of 100 μm and a size of 5X 5 cm;
(3) uniformly coating 0.1g of lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an argon-filled glove box (with the oxygen content of 0.05ppm and the water content of 0.05 ppm) to perform in-situ reaction;
(4) and (4) after the reaction is carried out for 6 hours in the step (3), removing unreacted lignin powder on the surface of the metal sodium sheet by using a brush to obtain the metal sodium cathode material rich in the C-O-Na structure lignin organic sodium salt protective layer.
Example 2
A preparation method of a sodium metal negative electrode material comprises the following steps:
(1) adding 15g of alkali lignin into 100mL of ultrapure water, fully stirring to remove water-soluble inorganic salts, centrifugally separating out insoluble tan precipitate, drying the tan precipitate at 60 ℃ in vacuum for 12 hours, and grinding to obtain lignin powder;
(2) in an argon-filled glove box (oxygen content 0.1ppm, water content 0.1 ppm), the oxide layer on the surface of the metallic sodium was removed, and then rolled into a sodium sheet having a thickness of 100 μm and a size of 5X 5 cm;
(3) uniformly coating 0.1g of lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an argon-filled glove box (with the oxygen content of 0.1ppm and the water content of 0.1 ppm) to perform in-situ reaction;
(4) and (4) after the reaction is carried out for 6 hours in the step (3), removing unreacted lignin powder on the surface of the metal sodium sheet by using a brush to obtain the metal sodium cathode material rich in the C-O-Na structure lignin organic sodium salt protective layer.
Example 3
A preparation method of a sodium metal negative electrode material comprises the following steps:
(1) adding 10g of enzymatic hydrolysis lignin into 200mL of ultrapure water, fully stirring to remove water-soluble inorganic salts, centrifugally separating out insoluble tan precipitate, vacuum-drying the tan precipitate at 80 ℃ for 24 hours, and grinding to obtain lignin powder;
(2) in an argon-filled glove box (oxygen content 0.05ppm, water content 0.05 ppm), the oxide layer on the surface of the metallic sodium was removed, and then rolled into a sodium sheet having a thickness of 150 μm and a size of 5X 5 cm;
(3) uniformly coating 0.5g of lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an argon-filled glove box (with the oxygen content of 0.05ppm and the water content of 0.05 ppm) to perform in-situ reaction;
(4) and (4) after the reaction is carried out for 6 hours in the step (3), removing unreacted lignin powder on the surface of the metal sodium sheet by using a brush to obtain the metal sodium cathode material rich in the C-O-Na structure lignin organic sodium salt protective layer.
Example 4
A preparation method of a sodium metal negative electrode material comprises the following steps:
(1) adding 10g of organic solvent lignin into 200mL of ultrapure water, fully stirring to remove water-soluble inorganic salts, centrifugally separating out insoluble tan precipitate, vacuum-drying the tan precipitate at 60 ℃ for 24 hours, and grinding to obtain lignin powder;
(2) in an argon-filled glove box (oxygen content 0.05ppm, water content 0.05 ppm), the oxide layer on the surface of the metallic sodium was removed, and then rolled into a sodium sheet having a thickness of 150 μm and a size of 5X 5 cm;
(3) uniformly coating 0.5g of lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an argon-filled glove box (with the oxygen content of 0.05ppm and the water content of 0.05 ppm) to perform in-situ reaction;
(4) and (4) after the reaction is carried out for 12 hours in the step (3), removing unreacted lignin powder on the surface of the metal sodium sheet by using a brush to obtain the metal sodium cathode material rich in the C-O-Na structure lignin organic sodium salt protective layer.
Comparative example 1
A preparation method of a sodium metal negative electrode material comprises the following steps:
the oxide layer on the surface of the sodium metal was removed in an argon-filled glove box (oxygen content 0.05ppm, water content 0.05 ppm) and rolled into a sodium sheet of thickness 100 μm and size 5X 5cm to obtain a pure sodium metal sheet without a protective layer covering.
Comparative example 2
A preparation method of a sodium metal negative electrode material comprises the following steps:
(1) in an argon-filled glove box (oxygen content 0.05ppm, water content 0.05 ppm), the oxide layer on the surface of the metallic sodium was removed, and then rolled into a sodium sheet having a thickness of 100 μm and a size of 5X 5 cm;
(2) moving the sodium metal sheet in the step (1) into a plasma atomic deposition (PEALD) system (argon-filled atmosphere) under a vacuum condition;
(3) PEALD process: using trimethylaluminum and oxygen plasma as precursors, Ar gas as purge gas between two precursor pulsesThe temperature of the reactor is 75 ℃, and the growth rate of each period is approximately equal to 1.1 angy cy −1 (thickness is characterized by deposition on a silicon substrate);
(4) after 25 cycles in the step (3), the obtained sodium metal surface is covered with a layer of Al with the thickness of 2.8nm 2 O 3 A thin layer.
Comparative example 3
A preparation method of a sodium metal negative electrode material comprises the following steps:
(1) under an argon atmosphere, 1g of metallic sodium and 1g of gold were melted at 80 ℃, and the molten metal mixture was sufficiently stirred to be in close contact with each other, thereby forming a uniform Na — Au alloy. (ii) a
(2) After cooling to room temperature, the sheet was rolled to a thickness of 100 μm and a size of 5X 5cm using a controlled thickness roller press.
Comparative example 4
A preparation method of a sodium metal negative electrode material comprises the following steps:
（1）Na 3.4 Zr 2 Si 2.4 P 0.6 O 12 preparation of (NZSP) powder: mixing 6g NaNO 3 And 10g ZrO (NO) 3 ） 2 Dissolved in 500mL of ultrapure water, and then 11g of Si (OCH) was added to the solution in this order while stirring 2 CH 3 ） 4 And 1.5g NH 4 H 2 PO 4 To obtain a mixture of colloidal sol and zirconia compound precipitate. Drying at 80 ℃ and calcining at 1300 ℃ for 3h to obtain NZSP powder;
（2）SnO 2 @Na 3.4 Zr 2 Si 2.4 P 0.6 O 12 preparation of (NZSP): 1.9g SnCl 2 Dissolving in 10mL of N, N-Dimethylformamide (DMF), adding 12g of NZSP powder, stirring for 2 hours, drying the solution in an oven at 80 ℃ for 12 hours, grinding to obtain powder, and calcining the powder in air at 450 ℃ for 2 hours to obtain SnO 2 @NZSP；
(3) In an argon-filled glove box (oxygen content 0.05ppm, water content 0.05 ppm), 2g of metallic sodium and 2g of SnO 2 @ NZSP powder is placed in a nickel crucible, addHeating to 250 deg.C, stirring for 5 min, and completely soaking molten sodium into SnO 2 @ NZSP powder;
(4) after cooling to room temperature, the sheet was rolled to a thickness of 100 μm and a size of 5X 5cm using a controlled thickness roller press.
Verification example 1
The sodium metal negative electrode material prepared in example 1 was analyzed by an infrared spectrometer, and the result is shown in fig. 2. The result showed 1709cm -1 The peak at (corresponding to-C = O) becomes less broad, 1597 and 1035cm -1 The peak at the position (corresponding to Ar-OH) is shifted to a low wave number, which shows that carbonyl and phenolic hydroxyl in the lignin functional group react with metal sodium to form a lignin organic sodium salt protective layer rich in a C-O-Na structure on the surface of the sodium metal cathode.
Subsequently, the metallic sodium negative electrode material of example 1 was analyzed by an electron scanning microscope, and the result is shown in fig. 3. The results show that the lignin organic sodium salt layer completely covers the metal sodium and the surface distribution is uniform.
Further, by analyzing the distribution of young's modulus of the surface of the metal sodium negative electrode material in example 1, it can be seen that the elastic modulus of the artificial protective layer is 12.5 GPa, which can effectively alleviate the side reaction between sodium metal and the electrolyte, ensure the rapid ion transmission, uniform electroplating and low voltage hysteresis, and prevent the dendrite from puncturing the diaphragm (see fig. 4).
Verification example 2
Taking the sodium metal negative electrode materials prepared in the example 1 and the comparative example 1 respectively, cutting the sodium metal negative electrode materials into circular sheets with the diameter of 10mm as electrodes to assemble a symmetrical battery, wherein the electrolytic liquid system is 1M NaClO 4 EC: PC (1: 1) +5% FEC. The cell assembly process was carried out in an inert atmosphere glove box, with all water oxygen content values maintained at 0.1 ppm.
Through detection, the battery cycle performance of the metallic sodium cathode rich in the C-O-Na structure lignin organic sodium salt protective layer in the comparative example 1 and the battery cycle performance of the pure metallic sodium cathode not covered by the protective layer in the comparative example 1 can be seen, the metallic sodium cathode rich in the C-O-Na structure lignin organic sodium salt protective layer can realize uniform deposition of sodium ions, and the uniform deposition of sodium ions is keptLow overpotential and no dendrite growth at 0.5mA cm -2 ，0.5mA·cm -2 Can stably circulate for more than 1500h under the condition of 1mA cm -2 ，1mA·cm -2 Can stably circulate for more than 1300h under the condition. This indicates that the SEI interface is highly stable. The voltage polarization of the pure metal sodium sheet electrode without the protective layer is increased, the potential fluctuation is severe during the circulation process, and the short circuit occurs after about 200-300h of circulation (see figure 5).
Subsequently, by observing the morphology of the electrode surface after 10 cycles of the sodium negative electrode in comparative example 1 and comparative example 1, it can be seen that the metallic sodium negative electrode rich in the lignin organic sodium salt protective layer of the C-O-Na structure still maintains a flat surface after the end of the cycle (see fig. 6), while the pure metallic sodium sheet of comparative example 1 shows many cracks and dendrites after the cycle (see fig. 7). According to prior studies, the bulk structure with sodium dendrites generally has a high specific surface area, which further leads to electrolyte consumption, resulting in low coulombic efficiency during cycling. The results show that the lignin organic protective layer constructed by the invention has obvious improvement on the stability of the sodium metal battery.
Further, the metal sodium electrode materials prepared in example 1 and comparative examples 2 to 4 were taken and tested for cycle performance. The test results are shown in table 1 below.
Table 1 comparative table of properties of metallic sodium electrode materials of example 1 and comparative examples 2 to 4
The result shows that compared with the metallic sodium cathode material prepared by the conventional method in the prior art, the lignin organic sodium salt protective layer rich in the C-O-Na structure, which is obtained according to the invention, can effectively inhibit dendritic crystal growth and realize uniform deposition of sodium in long circulation.
According to the invention, the lignin is utilized to carry out in-situ reaction on the surface of the metal sodium, so that the lignin organic sodium salt protective layer rich in a C-O-Na structure can be formed on the surface of the metal sodium, the lignin organic sodium salt protective layer has the characteristics of obviously inhibiting dendritic crystal growth, stabilizing an interface structure and the like, the volume change of a metal sodium cathode in a circulating process is effectively relieved, meanwhile, enough mechanical strength is reserved, and the membrane can be effectively prevented from being punctured by sodium dendritic crystals. Meanwhile, unstable SEI components can be prevented from being generated in the circulation process, so that the SEI components are more compact, and meanwhile, the corrosion of the electrolyte can be inhibited. The preparation method has good guiding significance in the aspect of modification of the metal battery cathode, particularly the metal sodium battery cathode, and the method is beneficial to large-scale application of the dendrite-free alkali metal cathode.
The above detailed description section specifically describes the analysis method according to the present invention. It should be noted that the above description is only for the purpose of helping those skilled in the art better understand the method and idea of the present invention, and not for the limitation of the related contents. The present invention may be appropriately adjusted or modified by those skilled in the art without departing from the principle of the present invention, and the adjustment and modification also fall within the scope of the present invention.
Claims (10)
1. The preparation method of the metal sodium negative electrode material is characterized by comprising the following steps of:
(1) adding lignin into ultrapure water, stirring thoroughly, separating insoluble brown precipitate, and vacuum drying brown precipitate to obtain lignin powder;
(2) under the atmosphere of inert gas, removing an oxide layer on the surface of the metal sodium, and then preparing a metal sodium sheet with uniform thickness;
(3) uniformly coating the lignin powder obtained in the step (1) on the surface of the metal sodium sheet in the step (2) in an inert gas atmosphere, and carrying out in-situ reaction;
(4) and (4) after the reaction in the step (3) is carried out fully, removing unreacted lignin powder on the surface of the metal sodium sheet to obtain the metal sodium cathode material rich in the C-O-Na structure lignin organic sodium salt protective layer.
2. The preparation method according to claim 1, wherein the lignin in step (1) is one or more selected from alkali lignin, enzymatic lignin, and organosolv lignin.
3. The method according to claim 1, wherein the separation in step (1) is selected from one or more of vacuum filtration and centrifugation.
4. The method according to claim 1, wherein the vacuum drying conditions in step (1) are: the drying temperature is 60-80 ℃, and the drying time is 12-24 h.
5. The method according to claim 1, wherein the inert gas in step (2) and step (3) is one or more selected from argon and nitrogen.
6. The method according to claim 1, wherein the oxygen content in the inert gas atmosphere in the steps (2) and (3) is 0.05 to 0.1ppm, and the water content is 0.05 to 0.1 ppm.
7. The method according to claim 1, wherein the in-situ reaction time in step (3) is 6-12 h.
8. The metallic sodium anode material prepared according to the preparation method of any one of claims 1 to 7.
9. A sodium-ion battery comprising the metallic sodium negative electrode material produced by the production method according to any one of claims 1 to 7.
10. The application of lignin in improving the stability of the metal sodium negative electrode material.
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