CN111755690A - Alkali metal composite negative electrode material and preparation method thereof - Google Patents
Alkali metal composite negative electrode material and preparation method thereof Download PDFInfo
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- 229910052783 alkali metal Inorganic materials 0.000 title claims abstract description 87
- 150000001340 alkali metals Chemical class 0.000 title claims abstract description 87
- 239000002905 metal composite material Substances 0.000 title claims abstract description 64
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title abstract description 28
- 239000000243 solution Substances 0.000 claims abstract description 64
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 50
- 238000011068 loading method Methods 0.000 claims abstract description 20
- 238000002791 soaking Methods 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 239000000126 substance Substances 0.000 claims abstract description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000001354 calcination Methods 0.000 claims abstract description 12
- 239000012266 salt solution Substances 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 4
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- 150000001879 copper Chemical class 0.000 claims abstract description 3
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims abstract description 3
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 claims abstract description 3
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- 239000004744 fabric Substances 0.000 claims description 97
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 83
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- 239000010405 anode material Substances 0.000 claims description 34
- 239000011787 zinc oxide Substances 0.000 claims description 32
- 238000000034 method Methods 0.000 claims description 23
- 238000002844 melting Methods 0.000 claims description 11
- 230000008018 melting Effects 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 238000004070 electrodeposition Methods 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
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- 229910000431 copper oxide Inorganic materials 0.000 claims description 6
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- 230000004913 activation Effects 0.000 claims description 5
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- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010406 cathode material Substances 0.000 abstract description 5
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
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- 239000006260 foam Substances 0.000 description 4
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- 238000001179 sorption measurement Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001721 carbon Chemical class 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 229910003473 lithium bis(trifluoromethanesulfonyl)imide Inorganic materials 0.000 description 3
- QSZMZKBZAYQGRS-UHFFFAOYSA-N lithium;bis(trifluoromethylsulfonyl)azanide Chemical compound [Li+].FC(F)(F)S(=O)(=O)[N-]S(=O)(=O)C(F)(F)F QSZMZKBZAYQGRS-UHFFFAOYSA-N 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- JDZCKJOXGCMJGS-UHFFFAOYSA-N [Li].[S] Chemical compound [Li].[S] JDZCKJOXGCMJGS-UHFFFAOYSA-N 0.000 description 2
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
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- 238000010586 diagram Methods 0.000 description 2
- 238000000724 energy-dispersive X-ray spectrum Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- IZLAVFWQHMDDGK-UHFFFAOYSA-N gold(1+);cyanide Chemical compound [Au+].N#[C-] IZLAVFWQHMDDGK-UHFFFAOYSA-N 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- WNXJIVFYUVYPPR-UHFFFAOYSA-N 1,3-dioxolane Chemical compound C1COCO1 WNXJIVFYUVYPPR-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- 229910003004 Li-O2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
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- IEJIGPNLZYLLBP-UHFFFAOYSA-N dimethyl carbonate Chemical compound COC(=O)OC IEJIGPNLZYLLBP-UHFFFAOYSA-N 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- JBTWLSYIZRCDFO-UHFFFAOYSA-N ethyl methyl carbonate Chemical compound CCOC(=O)OC JBTWLSYIZRCDFO-UHFFFAOYSA-N 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
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- 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
- H01M4/382—Lithium
-
- 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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
-
- 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
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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
- 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
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Abstract
The invention discloses an alkali metal composite negative electrode material and a preparation method thereof, wherein the alkali metal composite negative electrode material comprises a carbon-based material and alkali metal loaded on the carbon-based material, and the surface of the carbon-based material is coated with an affinity substance; the preparation method comprises the following steps: (1) preparing a modified solution, and adding a carbon-based material into the modified solution for heating and soaking; the modified solution is one of soluble zinc salt solution, soluble copper salt solution, soluble silver salt solution, soluble gold salt solution and soluble compound solution containing nitrogen and phosphorus elements; (2) calcining the infiltrated carbon-based material to obtain the carbon-based material with the surface coated with the affinity substance; (3) and (3) loading alkali metal on the surface of the carbon-based material with the surface coated with the affinity substance to obtain the alkali metal composite negative electrode material. The cathode material has good electrochemical performance, long cycle life and small overpotential; the preparation method is simple to operate and easy to implement.
Description
Technical Field
The invention belongs to the field of battery cathode materials, and particularly relates to an alkali metal composite cathode material and a preparation method thereof.
Background
The metal lithium is expected to become the most ideal cathode material for the next generation of lithium ion batteries due to the characteristics of high theoretical discharge capacity (3860mAh/g), lowest potential (-3.040Vvs. standard hydrogen electrode) and the like. When the metal lithium is used as the cathode of the Li/S battery and the Li-O2 battery, the energy density of the metal lithium is respectively expected to reach 650Wh/kg and 950Wh/kg, which is 2-3 times of the energy density of the lithium ion battery commercialized at present, and the metal lithium battery has wide market prospect.
However, in the practical application of the battery using the metal lithium as the negative electrode, the following problems are often present:
(1) in the process of charging and discharging of the metal lithium battery, because the surface reaction of the lithium negative electrode is uneven and dendritic crystals are easily generated, the growth of the lithium dendritic crystals is initiated, so that the SEI film is induced to thicken and even dead lithium is formed, the impedance and the overpotential of the battery are increased, the fluctuation and the reduction of coulombic efficiency are caused, and the electrochemical performance of the lithium metal battery is seriously influenced; furthermore, there is a risk of puncturing the separator, causing short-circuiting of the battery, resulting in irreversible capacity loss and potential safety hazard.
(2) Metallic lithium is also accompanied by almost unlimited volume expansion during cycling, which also results in extreme instability of the surface SEI film, further aggravating the formation of metallic lithium dendrites. This infinite volume expansion due to dendrite formation greatly limits the practical application of metallic lithium cathodes.
(3) The lithium metal has high reactivity, is easy to react with the electrolyte to form an interface film, consumes the electrolyte and the lithium metal, and causes low lithium utilization rate and low battery coulombic efficiency.
(4) The interface film is unstable, the interface film formed by the metal lithium and the dendrite of the electrolyte is fragile, and the interface film is easy to crack in the charging and discharging process, so that exposed fresh lithium is continuously consumed; meanwhile, the component distribution of the interfacial film is not uniform, so that the lithium ion transmission coefficient difference is caused, local over-high lithium ion concentration is easily formed on the surface of the electrode, the growth of dendritic crystals is promoted, and the coulombic efficiency and the stability of the battery are reduced.
In order to solve the problems of the metal lithium, for example, chinese patent with application publication No. CN108695488A discloses a zinc oxide-metal lithium composite negative electrode, a preparation method thereof, and a metal lithium secondary battery, which mainly deposit a zinc oxide nano-layer on the surface of copper foam by a hydrothermal method, and then absorb liquid lithium formed after melting solid metal lithium in a three-dimensional copper foam skeleton to obtain a zinc oxide-metal lithium composite negative electrode material; however, during the melting process, the liquid metal lithium corrodes the copper foam, which results in poor surface state consistency of the copper foam. For example, chinese patent with application publication No. CN110085870A discloses "an alkali metal composite negative electrode, a preparation method and its application in the preparation of solid-state alkali metal batteries", in an inert atmosphere, a support layer is placed in molten alkali metal, and is fully infiltrated and then cooled to obtain an alkali metal composite negative electrode; the alkali metal composite negative electrode comprises a supporting layer and alkali metal loaded on the surface and in gaps of the supporting layer; the supporting layer is carbon cloth, 3D porous graphene, a nickel net, a copper net or an aluminum net. According to the technical scheme, the alkali metal is deposited on the carbon cloth by a melting method to obtain the alkali metal composite cathode, but the carbon cloth has poor affinity to metal lithium, and the alkali metal is difficult to deposit on the fiber surface and in gaps of the carbon cloth, so that the control effect of the reaction uniformity of the cathode surface is poor in the charging and discharging process, and the effect of inhibiting lithium dendrite is not ideal.
Disclosure of Invention
The invention aims to solve the technical problems, overcome the defects and defects in the background technology and provide an alkali metal composite negative electrode material and a preparation method thereof.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
an alkali metal composite anode material includes a carbon-based material and an alkali metal supported on the carbon-based material; the surface of the carbon-based material is coated with affinity substances.
The design idea of the technical scheme is that the carbon-based material is coated with the compact affinity substance coating layer, so that the affinity of the carbon-based material for alkali metal can be improved, the stability of the structure is improved, the alkali metal is induced to be uniformly deposited on the surface of the composite structure in the charging and discharging process, the local current density can be reduced, the growth of dendrites and the formation of dead lithium are inhibited, and the electrochemical properties such as the Kunlun efficiency, the cycle performance and the like of the alkali metal composite negative electrode material are improved.
Preferably, the affinity substance is nanoparticles of one or more of zinc oxide, zinc sulfide, noble metal, copper oxide, nitrogen-oxygen co-doped carbon material and nitrogen-phosphorus co-doped carbon material. The substances and materials with the nano structures have lower lithium nucleation overpotential, so that the affinity of the carbon-based material to the alkali metal can be obviously improved, and the combination state of the carbon-based material and the alkali metal is improved.
Preferably, the coating thickness of the affinity substance on the surface of the carbon-based material is 200 to 500 nm. The thickness of the coating layer is determined mainly based on consideration of the loading effect of the alkali metal and the overall thickness of the loaded negative electrode material, if the coating layer is too thin, the non-uniform coating region may cause poor affinity effect of the alkali metal, and if the coating layer is too thick, the volume of the negative electrode material is increased, and finally the energy density of the assembled battery is reduced.
Preferably, the carbon-based material is one or more of carbon cloth, carbon paper, graphene oxide, carbon nanotubes and porous carbon. The carbon-based materials have a three-dimensional porous structure and a high specific surface area, can effectively increase the reaction area of the electrode, improve the deposition effect of alkali metal, improve the mechanical property and structural stability of the negative electrode material, avoid collapse of the matrix material structure after the alkali metal is separated, and have small volume expansion effect and longer cycle life compared with a pure alkali metal negative electrode.
Based on the same technical concept, the invention also provides a preparation method of the alkali metal composite anode material, which comprises the following steps:
(1) preparing a modified solution, and adding the carbon-based material into the modified solution for heating and soaking; the modified solution is one of soluble zinc salt solution, soluble copper salt solution, soluble silver salt solution, soluble gold salt solution and soluble compound solution containing nitrogen and phosphorus elements;
(2) calcining the infiltrated carbon-based material to obtain the carbon-based material with the surface coated with the affinity substance;
(3) and loading alkali metal on the surface of the carbon-based material coated with the affinity substance to obtain the alkali metal composite negative electrode material.
The design idea of the technical scheme is that the carbon-based material with the surface coated with the affinity substance is prepared by the soaking and calcining method, and then the alkali metal is loaded on the carbon-based material, so that a compact coating layer and the alkali metal composite anode material with a stable structure can be simply and effectively formed.
Preferably, in the above aspect, the concentration of the modifying solution is 0.08M to 1.0M. The concentration of the modified solution mainly controls the distribution density of the modified particles on the carbon-based material, the concentration range has a good effect after being verified, the too low modified concentration can cause the load effect to be poor, and the too high modified concentration can cause the load effect to be uncontrollable.
As a preferable mode of the above technical solution, in the step (1), the carbon-based material is further subjected to an activation treatment before being added to the modification solution, and the specific operation of the activation treatment is: adding the carbon-based material into a concentrated sulfuric acid solution, carrying out constant temperature treatment for 3-12 h at 50-120 ℃, then transferring the carbon-based material into a concentrated nitric acid solution, and carrying out constant temperature treatment for 3-12 h at 70-130 ℃. The strong oxidation concentrated acid activation treatment is mainly used for improving the surface activity of the carbon-based material, more oxygen-containing groups such as hydroxyl, alkyl and the like are obtained on the surface of the carbon-based material, and the groups and a modified solute have physicochemical action so as to realize better coating uniformity and anchoring.
Preferably, in the step (2), the calcination temperature for the calcination treatment of the carbon-based material is 380 to 600 ℃, and the calcination time is 4 to 10 hours. Since the precursor of the coating material can be decomposed substantially in this sintering strength range, the calcination treatment under the above-mentioned parameters gives the best coating effect of the product, and if the calcination strength is too high, the decomposition of the carbon-based material or the coating material product is deteriorated.
In the above-described embodiment, in the step (3), the method of supporting the alkali metal on the surface of the carbon-based material is preferably a melting method or an electrodeposition method.
Preferably, in the melting method, the melting temperature is 70-350 ℃.
Preferably, in the above technical solution, the electrolyte solution used in the electrodeposition method is lithium bistrifluoromethylsulfonyl imide, and the solvent is a mixture of solvents in a volume ratio of 1: 1 dioxolane and ethylene glycol dimethyl ether; or the solute of the electrolyte is lithium hexafluorophosphate, and the solvent is a mixture of the following components in a volume ratio of 1: 1: 1 ethylene carbonate, ethyl methyl carbonate and dimethyl carbonate.
Preferably, the concentration of the electrolyte is 0.5-4.0M, and preferably 2.0M.
Preferably, the melting method and the electrodeposition method are both performed in a protective atmosphere, and the protective atmosphere is one of argon, helium and nitrogen.
Preferably, the alkali metal composite anode material obtained in the step (3) is further subjected to rolling and punching treatment, wherein the rolling thickness is 200-400 μm, and preferably 250-350 μm.
Compared with the prior art, the invention has the beneficial effects that:
(1) the alkali metal composite negative electrode material has good electrochemical performance, long cycle life and small overpotential, and can effectively inhibit dendritic crystal growth and volume expansion effect;
(2) the coating layer prepared by the preparation method of the metal composite negative electrode material is compact, the alkali metal deposition effect is good, the operation is simple, the implementation is easy, and the industrial large-scale industrial production is facilitated.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of a process for preparing an alkali metal composite anode material according to example 1;
FIG. 2 is an SEM topography of a modified carbon cloth (ZnO @ CC) of example 1;
FIG. 3 is an EDS spectrum of modified carbon cloth (ZnO @ CC) of example 1;
FIG. 4 is a photograph of an embodiment of an alkali metal composite anode material (Li/ZnO @ CC) according to example 1;
FIG. 5 is a photograph of a real object of the alkali metal composite anode material electrodeposition (Li/Au @ CC) of example 6;
FIG. 6 is an SEM topography of an alkali metal composite anode material (Li/ZnO @ CC) of example 1;
FIG. 7 shows an alkali metal composite anode material (Li/ZnO @ CC) and a pure lithium metal anode of example 1 at 0.5mA/cm2The lower symmetrical cell voltage-time plot;
FIG. 8 shows the negative electrode material of alkali metal composite (Li/ZnO @ CC) and pure lithium metal of example 1 at 0.5mA/cm2A lower asymmetric battery coulombic efficiency-cycle period curve graph;
FIG. 9 is a graph of solid state battery discharge capacity versus cycle time at 0.3C rate for the alkali metal composite anode material (Li/ZnO @ CC) and a pure metal lithium anode of example 1;
FIG. 10 is a plot of lithium sulfur battery discharge capacity versus cycle length at 0.5C rate for the alkali metal composite anode material (Li/ZnO @ CC) and a pure metal lithium anode of example 1.
Detailed Description
In order to facilitate understanding of the invention, the invention will be described more fully and in detail with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
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 stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
the alkali metal composite negative electrode material comprises carbon cloth, zinc oxide coated on the surface of the carbon cloth and metal lithium loaded on the carbon cloth, wherein the coating thickness of the zinc oxide is 200 nm.
As shown in fig. 1, the preparation method of the alkali metal composite anode material of the embodiment is simple in process, and is suitable for industrial mass production, and specifically includes the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 1.756g of zinc acetate dihydrate was dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to be completely dissolved, to prepare a 0.08M modified solution of zinc acetate.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the zinc acetate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Putting the carbon cloth obtained in the step (4) into a tubular furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the zinc oxide modified carbon cloth (ZnO @ CC), wherein the ZnO loading capacity is 0.15mg/cm2。
(6) Preparation of Li/ZnO @ CC: heating at 300 deg.C in argon atmosphere with a heating plateMelting metal lithium, naturally contacting the zinc oxide modified carbon cloth in the step (5) with the molten lithium, and adsorbing the metal lithium on the surface and in gaps of the zinc oxide modified carbon cloth in a self-adsorption mode to prepare the Li/ZnO @ CC composite negative electrode material, wherein the loading capacity of the metal lithium is 6.05mg/cm2。
(7) And (4) rolling and punching the Li/ZnO @ CC composite negative electrode material in the step (6), wherein the thickness of a negative electrode wafer is 240 micrometers, and the diameter of the negative electrode wafer is 19 mm.
Fig. 2 and fig. 3 are SEM topography (the four images in fig. 2 are magnified from top left to bottom right) and EDS (the EDS spectrum accessory of the scanning electron microscope can represent the element distribution state on the surface of the material) of the zinc oxide modified carbon cloth (ZnO @ CC) in this embodiment.
Fig. 4 is a picture of an alkali metal composite anode material (Li/ZnO @ CC) prepared in this example, and it can be seen from the picture that metallic lithium with silvery white metallic luster is uniformly adsorbed on the carbon cloth.
Fig. 6 is an SEM topography (upper left and upper right pictures in the four pictures in fig. 6 are surface topography of the alkali metal composite anode material under different magnifications, and lower left and lower right pictures are cross-sectional topography of the alkali metal composite anode under different magnifications) of the alkali metal composite anode material (Li/ZnO @ CC) prepared in this example, and SEM characteristics show that metal lithium is distributed in gaps between carbon cloth fibers and on the surface of the carbon cloth fibers, and the thickness of the alkali metal composite anode is about 280 μm.
FIG. 7 shows that the negative electrodes of the alkali metal composite negative electrode material (Li/ZnO @ CC) and the pure lithium metal prepared in this example are at 0.5mA/cm2The result of the voltage-time curve graph of the lower symmetrical battery shows that the curve of the Li/ZnO @ CC | Li/ZnO @ CC symmetrical battery is more stable, and the overpotential is lower than that of the Li | Li symmetrical battery and is only about 20 mV.
FIG. 8 shows that the negative electrodes of the alkali metal composite negative electrode material (Li/ZnO @ CC) and the pure lithium metal prepared in this example are at 0.5mA/cm2Lower asymmetric cell coulombic efficiency-cycle curveThe line graph shows that the Li/ZnO @ CC | | Cu asymmetric battery has excellent cycle performance, no water-skipping phenomenon is found when the battery is cycled for 130 weeks, and the corresponding coulombic efficiency value is 97.51% (the Li | | | Cu asymmetric battery begins to skip water when the battery is cycled for 70 weeks).
Fig. 9 is a discharge capacity-cycle period curve diagram of the solid-state battery at 0.3C rate of the alkali metal composite negative electrode material (Li/ZnO @ CC) and the pure metal lithium negative electrode prepared in this embodiment, and the result shows that the Li/ZnO @ CC | | NCM523 solid-state battery has excellent cycle performance, a discharge capacity of 140.5 from 0.3C cycle to 100 weeks, and a cycle retention rate of 92.98% (the discharge capacity of the Li | | NCM523 solid-state battery from 0.3C cycle to 100 weeks is 134.1, and the cycle retention rate is 86.68%).
Fig. 10 is a discharge capacity-cycle period curve diagram of the lithium-sulfur battery at a rate of 0.5C for the alkali metal composite negative electrode material (Li/ZnO @ CC) and the pure metal lithium negative electrode according to the embodiment of the present invention, and the result shows that the first discharge capacity at a rate of 0.5C for the Li/ZnO @ CC S battery is 757.8mAh/g (the first discharge capacity at a rate of 0.5C for the Li | | S battery is 637.3 mAh/g).
Example 2:
the alkali metal composite negative electrode material comprises carbon cloth, copper oxide coated on the surface of the carbon cloth and metal sodium loaded on the carbon cloth, wherein the coating thickness of the copper oxide is 300 nm.
Fig. 5 is a picture of an alkali metal composite anode material (Na/ZnO @ CC) prepared in this example, and it can be seen from the picture that metallic sodium with silvery white metallic luster is uniformly adsorbed on the carbon cloth.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 1.756g of copper nitrate was dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to be completely dissolved, to prepare a 0.08M modified solution of copper nitrate.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the copper nitrate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Placing the carbon cloth obtained in the step (4) in a tubular furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the copper oxide modified carbon cloth (CuO @ CC), wherein the CuO loading capacity is 0.15mg/cm2。
(6) Preparation of Na/ZnO @ CC: adopting a metallic sodium foil as an auxiliary electrode, adopting copper oxide modified carbon cloth (CuO @ CC) as a working electrode, and carrying out electrodeposition in an ether solvent of LiTFSI with the molar concentration of 2mol/L, wherein the working voltage is 2.5V, the deposition time is 8h, and the Na/CuO @ CC composite negative electrode material is prepared, wherein the metallic sodium loading is 6.41mg/cm2。
(7) And (4) rolling and punching the Na/CuO @ CC composite anode material in the step (6), wherein the thickness of the anode wafer is 245 mu m, and the diameter of the anode wafer is 19 mm.
Example 3:
the alkali metal composite negative electrode material comprises carbon cloth, a nitrogen-phosphorus coating layer coated on the surface of the carbon cloth and metal potassium loaded on the carbon cloth, wherein the coating thickness is 500 nm.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 3.512g of ammonium dihydrogen phosphate was dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to be completely dissolved, thereby preparing a 0.16M ammonium dihydrogen phosphate-modified solution.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the ammonium dihydrogen phosphate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath kettle.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Placing the carbon cloth obtained in the step (4) in a tubular furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the nitrogen-phosphorus compound modified carbon cloth, wherein the loading capacity of the nitrogen-phosphorus compound is 0.34mg/cm2。
(6) Preparation of K/Nitrogen phosphorus Compound @ CC: melting potassium metal at 300 ℃ by using a heating plate in an argon atmosphere, naturally contacting the nitrogen-phosphorus compound modified carbon cloth in the step (5) with the molten potassium, and adsorbing the potassium metal on the surface and in gaps of the zinc oxide modified carbon cloth in a self-adsorption manner to prepare the K/nitrogen-phosphorus compound @ CC composite negative electrode material, wherein the loading capacity of the potassium metal is 8mg/cm2。
(7) And (4) rolling and punching the K/nitrogen-phosphorus compound @ CC composite negative electrode material obtained in the step (6), wherein the thickness of a negative electrode wafer is 255 mu m, and the diameter of the negative electrode wafer is 19 mm.
Example 4:
the alkali metal composite negative electrode material comprises carbon cloth, zinc oxide coated on the surface of the carbon cloth and metal lithium loaded on the carbon cloth, wherein the coating thickness of the zinc oxide is 300 nm.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 3.512g of zinc acetate dihydrate were dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to dissolve completely, to prepare a 0.16M modified solution of zinc acetate.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the zinc acetate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Putting the carbon cloth obtained in the step (4) into a tube furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the zinc oxide modified carbon cloth (ZnO @ CC), wherein the ZnO loading capacity is 0.34mg/cm2。
(6) Preparation of Li/ZnO @ CC: adopting a metal lithium foil as an auxiliary electrode, adopting zinc oxide modified carbon cloth (ZnO @ CC) as a working electrode, carrying out electrodeposition in an ether solvent of Li/0TFSI with the molar concentration of 2mol/L, wherein the working voltage is 2.5V, the deposition time is 8h, and preparing the Li/ZnO @ CC composite negative electrode material, wherein the metal lithium loading capacity is 7.40mg/cm2。
(7) And (4) rolling and punching the Li/ZnO @ CC composite negative electrode material in the step (6), wherein the thickness of a negative electrode wafer is 250 micrometers, and the diameter of the negative electrode wafer is 19 mm.
Example 5:
the alkali metal composite negative electrode material comprises carbon cloth, zinc oxide coated on the surface of the carbon cloth and metal lithium loaded on the carbon cloth, wherein the coating thickness of the zinc oxide is 400 nm.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 7.0244g of zinc acetate dihydrate were dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to dissolve completely, to prepare a 0.32M modified solution of zinc acetate.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the zinc acetate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Putting the carbon cloth obtained in the step (4) into a tube furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the zinc oxide modified carbon cloth (ZnO @ CC), wherein the ZnO loading capacity is 0.70mg/cm2。
(6) Preparation of Li/ZnO @ CC: melting metal lithium at 300 ℃ by using a heating plate in an argon atmosphere, naturally contacting the zinc oxide modified carbon cloth in the step (5) with the molten lithium, and adsorbing the metal lithium on the surface and in gaps of the zinc oxide modified carbon cloth in a self-adsorption mode to prepare the Li/ZnO @ CC composite negative electrode material, wherein the loading capacity of the metal lithium is 10.02mg/cm2。
(7) And (4) rolling and punching the Li/ZnO @ CC composite negative electrode material in the step (6), wherein the thickness of a negative electrode wafer is 268 mu m, and the diameter of the negative electrode wafer is 19 mm.
Example 6:
the alkali metal composite negative electrode material comprises carbon cloth, an Au coating layer coated on the surface of the carbon cloth and metal lithium loaded on the carbon cloth, wherein the coating thickness of the Au coating layer is 350 nm.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 7.0244g of gold cyanide was dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to dissolve completely, to prepare a 0.32M gold cyanide-modified solution.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the gold cyanide modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Subjecting the product obtained in step (4)Placing the carbon cloth in a tube furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5h, and naturally cooling to obtain the Au modified carbon cloth, wherein the Au loading capacity is 0.70mg/cm2。
(6) Preparation of Li/ZnO @ CC: adopting metal lithium foil as an auxiliary electrode, adopting gold modified carbon cloth as a working electrode, and carrying out electrodeposition in an ether solvent of LiTFSI with the molar concentration of 2mol/L, wherein the working voltage is 2.5V, the deposition time is 8h, and the Li/Au @ CC composite cathode material is prepared, wherein the metal Au loading capacity is 8.02mg/cm2。
(7) And (4) rolling and punching the Li/Au @ CC composite negative electrode material in the step (6), wherein the thickness of a negative electrode wafer is 254 micrometers, and the diameter of the negative electrode wafer is 19 mm.
Example 7:
the alkali metal composite negative electrode material comprises carbon cloth, zinc oxide coated on the surface of the carbon cloth and metal lithium loaded on the carbon cloth, wherein the coating thickness of the zinc oxide is 300 nm.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 8.7804g of zinc acetate dihydrate were dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to dissolve completely, to prepare a 0.40M modified solution of zinc acetate.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the zinc acetate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Putting the carbon cloth obtained in the step (4) into a tubular furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the zinc oxide modified carbon cloth (ZnO @ CC), wherein the ZnOThe loading capacity is 0.80mg/cm2。
(6) Preparation of Li/ZnO @ CC: melting metal lithium at 300 ℃ by using a heating plate in an argon atmosphere, naturally contacting the zinc oxide modified carbon cloth in the step (5) with the molten lithium, and adsorbing the metal lithium on the surface and in gaps of the zinc oxide modified carbon cloth in a self-adsorption mode to prepare the Li/ZnO @ CC composite negative electrode material, wherein the loading capacity of the metal lithium is 11.90mg/cm2。
(7) And (4) rolling and punching the Li/ZnO @ CC composite negative electrode material in the step (6), wherein the thickness of a negative electrode wafer is 280 micrometers, and the diameter of the negative electrode wafer is 19 mm.
Example 8:
the alkali metal composite negative electrode material comprises carbon cloth, zinc oxide coated on the surface of the carbon cloth and metal lithium loaded on the carbon cloth, wherein the coating thickness of the zinc oxide is 200 nm.
The preparation method of the alkali metal composite anode material comprises the following steps:
(1) pretreatment: cutting carbon cloth, ultrasonically cleaning for 120min under acetone, ethanol and ultrapure water respectively, and drying to remove water; and (3) soaking the dried carbon cloth in a 98 wt% concentrated sulfuric acid solution at 80 ℃ for 6h, and then soaking in a 68 wt% concentrated nitric acid solution at 90 ℃ for 6 h. Finally, ultrasonically cleaning and drying the mixture by using ethanol and ultrapure water for later use.
(2) Preparing a modified solution: 8.7804g of zinc acetate dihydrate were dissolved in 100mL of methanol solvent and stirred with a magnetic stirrer to dissolve completely, to prepare a 0.40M modified solution of zinc acetate.
(3) And (3) adding the carbon cloth pretreated in the step (1) into the zinc acetate modified solution in the step (2), and reacting for 5 hours at a constant temperature of 50 ℃ by using an oil bath.
(4) And (4) drying the carbon cloth obtained in the step (3) in a drying oven at 60 ℃ for 2 h.
(5) Putting the carbon cloth obtained in the step (4) into a tube furnace, heating to 400 ℃ at a speed of 3 ℃/min in an argon atmosphere, keeping the temperature for 5 hours, and naturally cooling to obtain the zinc oxide modified carbon cloth (ZnO @ CC), wherein the ZnO loading capacity is 0.80mg/cm2。
(6) Preparation of Li/ZnO @ CC: miningUsing metal lithium foil as an auxiliary electrode, using zinc oxide modified carbon cloth (ZnO @ CC) as a working electrode, and carrying out electrodeposition in an ether solvent of LiTFSI with the molar concentration of 2mol/L, wherein the working voltage is 2.5V, the deposition time is 8h, and the Li/ZnO @ CC composite negative electrode material is prepared, wherein the metal lithium loading capacity is 8.33mg/cm2。
(7) And (4) rolling and punching the Li/ZnO @ CC composite negative electrode material in the step (6), wherein the thickness of a negative electrode wafer is 256 micrometers, and the diameter of the negative electrode wafer is 19 mm.
Claims (10)
1. An alkali metal composite anode material, characterized by comprising a carbon-based material and an alkali metal supported on the carbon-based material; the surface of the carbon-based material is coated with affinity substances.
2. The alkali metal composite anode material as claimed in claim 1, wherein the affinity substance is nanoparticles of one or more of zinc oxide, zinc sulfide, noble metal, copper oxide, nitrogen and oxygen co-doped carbon material and nitrogen and phosphorus co-doped carbon material.
3. The alkali metal composite anode material according to claim 1, wherein the affinity substance is coated on the surface of the carbon-based material to a thickness of 200 to 500 nm.
4. The alkali metal composite anode material as claimed in claim 1, wherein the carbon-based material is one or more of carbon cloth, carbon paper, graphene oxide, carbon nanotubes and porous carbon.
5. A method for producing an alkali metal composite anode material according to any one of claims 1 to 4, characterized by comprising the steps of:
(1) preparing a modified solution, and adding the carbon-based material into the modified solution for heating and soaking; the modified solution is one of soluble zinc salt solution, soluble copper salt solution, soluble silver salt solution, soluble gold salt solution and soluble compound solution containing nitrogen and phosphorus elements;
(2) calcining the infiltrated carbon-based material to obtain the carbon-based material with the surface coated with the affinity substance;
(3) and loading alkali metal on the surface of the carbon-based material coated with the affinity substance to obtain the alkali metal composite negative electrode material.
6. The method for producing an alkali metal composite anode material according to claim 5, wherein the concentration of the modification solution is 0.08M to 1.0M.
7. The method for preparing an alkali metal composite anode material according to claim 5, wherein in the step (1), the carbon-based material is further subjected to an activation treatment before being added to the modification solution, and the specific operation of the activation treatment is: adding the carbon-based material into a concentrated sulfuric acid solution, carrying out constant temperature treatment for 3-12 h at 50-120 ℃, then transferring the carbon-based material into a concentrated nitric acid solution, and carrying out constant temperature treatment for 3-12 h at 70-130 ℃.
8. The method for preparing the alkali metal composite anode material according to claim 6, wherein in the step (2), the calcination temperature of the calcination treatment of the carbon-based material is 380 to 600 ℃, and the calcination time is 4 to 10 hours.
9. The method for producing an alkali metal composite anode material according to claim 6, wherein in the step (3), the method of supporting the alkali metal on the surface of the carbon-based material is a melting method or an electrodeposition method.
10. The method for preparing an alkali metal composite anode material according to claim 9, wherein the melting method and the electrodeposition method are both performed in a protective atmosphere.
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| CN113582217A (en) * | 2021-06-08 | 2021-11-02 | 湖南师范大学 | Preparation method of ZnO/carbon composite interlayer |
| CN114824176A (en) * | 2021-01-19 | 2022-07-29 | 香港纺织及成衣研发中心 | Method for manufacturing pre-lithiated negative electrode and application of pre-lithiated negative electrode in flexible lithium battery |
| CN116544415A (en) * | 2023-06-27 | 2023-08-04 | 昆明理工大学 | Preparation of ZnO-ZnS@nitrogen doped porous carbon composite material, product and application thereof |
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| CN114824176A (en) * | 2021-01-19 | 2022-07-29 | 香港纺织及成衣研发中心 | Method for manufacturing pre-lithiated negative electrode and application of pre-lithiated negative electrode in flexible lithium battery |
| CN113054161A (en) * | 2021-02-04 | 2021-06-29 | 浙江大学 | Preparation method and application of safe and efficient potassium metal electrode material |
| CN113582217A (en) * | 2021-06-08 | 2021-11-02 | 湖南师范大学 | Preparation method of ZnO/carbon composite interlayer |
| CN116544415A (en) * | 2023-06-27 | 2023-08-04 | 昆明理工大学 | Preparation of ZnO-ZnS@nitrogen doped porous carbon composite material, product and application thereof |
| CN116544415B (en) * | 2023-06-27 | 2024-03-08 | 昆明理工大学 | Preparation of ZnO-ZnS@nitrogen doped porous carbon composite material, product and application thereof |
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