CN114530598B - Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof - Google Patents
Nitrogen-oxygen-sulfur doped carbon negative electrode material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 55
- LOTCVJJDZFMQGB-UHFFFAOYSA-N [N].[O].[S] Chemical compound [N].[O].[S] LOTCVJJDZFMQGB-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007773 negative electrode material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 239000010405 anode material Substances 0.000 claims abstract description 36
- 229910001414 potassium ion Inorganic materials 0.000 claims abstract description 25
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 claims abstract description 23
- 238000010438 heat treatment Methods 0.000 claims description 33
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 238000004140 cleaning Methods 0.000 claims description 16
- 150000002894 organic compounds Chemical class 0.000 claims description 16
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 16
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 11
- 239000001509 sodium citrate Substances 0.000 claims description 9
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 9
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000001508 potassium citrate Substances 0.000 claims description 4
- 229960002635 potassium citrate Drugs 0.000 claims description 4
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 4
- 235000011082 potassium citrates Nutrition 0.000 claims description 4
- YPSNMKHPDJVGEX-UHFFFAOYSA-L potassium;sodium;3-carboxy-3-hydroxypentanedioate Chemical compound [Na+].[K+].OC(=O)CC(O)(C([O-])=O)CC([O-])=O YPSNMKHPDJVGEX-UHFFFAOYSA-L 0.000 claims description 4
- 229960001790 sodium citrate Drugs 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000012298 atmosphere Substances 0.000 claims description 2
- 239000011641 cupric citrate Substances 0.000 claims description 2
- 235000019855 cupric citrate Nutrition 0.000 claims description 2
- 229960002413 ferric citrate Drugs 0.000 claims description 2
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 claims description 2
- 229940071264 lithium citrate Drugs 0.000 claims description 2
- WJSIUCDMWSDDCE-UHFFFAOYSA-K lithium citrate (anhydrous) Chemical compound [Li+].[Li+].[Li+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WJSIUCDMWSDDCE-UHFFFAOYSA-K 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- STDMRMREKPZQFJ-UHFFFAOYSA-H tricopper;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Cu+2].[Cu+2].[Cu+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O STDMRMREKPZQFJ-UHFFFAOYSA-H 0.000 claims description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 9
- 230000007547 defect Effects 0.000 abstract description 7
- 230000009286 beneficial effect Effects 0.000 abstract description 5
- 239000011148 porous material Substances 0.000 abstract description 4
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000000498 ball milling Methods 0.000 description 20
- 238000000197 pyrolysis Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 18
- 239000000047 product Substances 0.000 description 18
- 239000003575 carbonaceous material Substances 0.000 description 17
- 229940037179 potassium ion Drugs 0.000 description 17
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 15
- 239000002243 precursor Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 9
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 7
- 239000012299 nitrogen atmosphere Substances 0.000 description 7
- 239000012265 solid product Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000000967 suction filtration Methods 0.000 description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229910052760 oxygen Inorganic materials 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 3
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 229920000877 Melamine resin Polymers 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 229910052744 lithium Inorganic materials 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 229960003975 potassium Drugs 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 229910021384 soft carbon Inorganic materials 0.000 description 3
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- YASYEJJMZJALEJ-UHFFFAOYSA-N Citric acid monohydrate Chemical compound O.OC(=O)CC(O)(C(O)=O)CC(O)=O YASYEJJMZJALEJ-UHFFFAOYSA-N 0.000 description 1
- 241001391944 Commicarpus scandens Species 0.000 description 1
- OIFBSDVPJOWBCH-UHFFFAOYSA-N Diethyl carbonate Chemical compound CCOC(=O)OCC OIFBSDVPJOWBCH-UHFFFAOYSA-N 0.000 description 1
- KMTRUDSVKNLOMY-UHFFFAOYSA-N Ethylene carbonate Chemical compound O=C1OCCO1 KMTRUDSVKNLOMY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000001237 Raman spectrum Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- JHRWWRDRBPCWTF-OLQVQODUSA-N captafol Chemical compound C1C=CC[C@H]2C(=O)N(SC(Cl)(Cl)C(Cl)Cl)C(=O)[C@H]21 JHRWWRDRBPCWTF-OLQVQODUSA-N 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- PQIOSYKVBBWRRI-UHFFFAOYSA-N methylphosphonyl difluoride Chemical group CP(F)(F)=O PQIOSYKVBBWRRI-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002088 nanocapsule Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- MHEBVKPOSBNNAC-UHFFFAOYSA-N potassium;bis(fluorosulfonyl)azanide Chemical compound [K+].FS(=O)(=O)[N-]S(F)(=O)=O MHEBVKPOSBNNAC-UHFFFAOYSA-N 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of battery materials, and particularly relates to a nitrogen-oxygen-sulfur doped carbon anode material, and a preparation method and application thereof. The nitrogen-oxygen-sulfur doped material prepared by the preparation method has rich defect sites and pore channel structures, and is beneficial to improving the first-circle coulomb efficiency and the cycle stability of the potassium ion battery when being used as a negative electrode material; the adopted raw materials are wide in sources, low in cost and easy to obtain; the preparation method is simple, has mild conditions and is beneficial to large-scale production.
Description
Technical Field
The invention belongs to the technical field of battery materials. More particularly, relates to a nitrogen-oxygen-sulfur doped carbon anode material, a preparation method and application thereof.
Background
In recent years, lithium ion batteries are widely used in the fields of mobile electronic equipment, electric automobiles and the like, but the scarcity of lithium sources on the earth and the continuous rising of lithium-containing ore prices in the global scope seriously affect the application of the lithium batteries. Therefore, the energy storage industry is urgent to develop novel energy storage devices to replace lithium ion batteries so as to realize efficient and low-cost energy storage. Potassium has the advantages of abundant resource reserves, no regional limitation and relatively low price, and is gradually paid attention to and studied in the electrochemical field. In carbonate electrolyte, the standard redox potential of K +/K (-2.88V vs SHE) is lower than that of Li +/Li (-2.79V vs SHE) and Na +/Na (-2.56V vs SHE), which means that the potassium ion battery has higher operating voltage in a certain voltage range, and the potassium ion battery is studied by a large number of researchers because the interaction of solvent and anions with potassium ions in the electrolyte is weaker than the interaction with lithium ions, and the ion diffusion rate of potassium ions in the electrolyte is faster. Wherein, the negative electrode material in the potassium ion battery has a great influence on the performance of the potassium ion battery.
In the currently studied anode materials of potassium ion batteries, the carbon materials are mainly used, and the anode materials have the advantages of good conductivity, good flexibility and low intercalation voltage platform (more than or equal to 0.2V vs K +/K), but the carbon materials have low specific capacity, low initial coulombic efficiency and poor multiplying power performance. In order to overcome the defects of low specific capacity, low initial coulombic efficiency and poor multiplying power performance of the carbon material, nonmetallic heteroatoms are often doped in the carbon material, for example Liu et al synthesize a nitrogen-doped soft carbon, the long cycle stability of the nitrogen-doped soft carbon is improved to a certain extent, the capacity retention rate is 85.5% after the carbon material is cycled for 500 circles under the current density of 1 A.g -1, but the carbon material still has a large lifting space from practical application; and the initial circle coulomb efficiency is lower, only 30.9％(Liu C,Xiao N,Li H,et al.Nitrogen-doped soft carbon frameworks built of well-interconnected nanocapsules enabling a superior potassium-ion batteries anode[J].Chemical Engineering Journal,2020,382:121759.).
Disclosure of Invention
The invention aims to overcome the defects that the long-cycle stability of the existing potassium ion battery anode material needs to be further improved and the initial coulomb efficiency is low, and provides a preparation method of a nitrogen-oxygen-sulfur doped carbon anode material.
The invention aims to provide a nitrogen-oxygen-sulfur doped carbon anode material.
The invention further aims to provide an application of the nitrogen-oxygen-sulfur doped carbon anode material in preparing the anode material of the potassium ion battery.
The above object of the present invention is achieved by the following technical solutions:
a preparation method of a nitrogen-oxygen-sulfur doped carbon anode material comprises the following steps:
uniformly mixing citrate with an organic compound containing N and S, performing heat treatment at 400-900 ℃ in an inert gas atmosphere, and cleaning to obtain the organic compound;
The organic compound containing N and S is one or more of thiourea, melamine, dicyandiamide or cyanuric acid.
The invention creatively adopts the citrate which is simple and easy to obtain as the oxygen source, the carbon source and the in-situ template agent. The citrate is heated and decomposed in the heat treatment process to generate a large amount of oxygen, and oxygen elements are doped in the carbon material to improve the wettability of the carbon material; the citrate partial structure is heated and decomposed to generate alkaline carbonate in situ and release carbon dioxide, and the alkaline carbonate and the carbon dioxide have an activating effect on the carbon material, so that a microporous structure is formed.
Meanwhile, organic components of the citrate are pyrolyzed with organic compounds containing N and S in the heat treatment process to form a carbon layer, carbonate can be generated in situ by the pyrolysis of the citrate as a template to be wrapped in the carbon layer, the carbon layer grows along the template, deionized water or dilute acid is used for removing the carbonate template, and the carbon layer after the template is removed forms a unique three-dimensional stacked structure, so that the nitrogen-oxygen-sulfur three-doped carbon negative electrode material is obtained.
Moreover, the organic compound containing N and S provides abundant heteroatom elements (such as sulfur and nitrogen elements) when being heated and decomposed, the heteroatom elements are doped into the carbon material, so that the carbon material is promoted to generate abundant defect sites, the interlayer spacing of the carbon material is enlarged, and the electronic structure of the carbon material is regulated, thereby improving the first-circle coulomb efficiency and the cycle stability of the potassium ion battery.
In addition, the citrate is blended with the organic compound containing N and S, and the nitrogen-oxygen-sulfur doped carbon anode material is prepared by one-step pyrolysis, so that the operation is simple, the process flow is simple, the economic benefit is higher, and the method is suitable for large-scale production.
Further, the citrate is one or more of lithium citrate, potassium citrate, sodium citrate, potassium sodium citrate, ferric citrate, cupric citrate, magnesium citrate, ammonium citrate and the above citrate hydrate.
Preferably, the citrate is potassium citrate, sodium citrate or potassium sodium citrate.
Further, the organic compound containing N and S is thiourea, melamine or dicyandiamide.
Further, the temperature of the heat treatment is 450-700 ℃.
Preferably, the temperature of the heat treatment is 500 ℃.
Further, the time of the heat treatment is 30-360 min.
Preferably, the time of the heat treatment is 30 to 240 minutes.
More preferably, the time of the heat treatment is 60 minutes.
Further, the heating rate of the heat treatment is 1-10 ℃/min.
Preferably, the heating rate of the heat treatment is 1-5 ℃/min.
More preferably, the heating rate of the heat treatment is 3 ℃/min.
Further, the mass ratio of the citrate to the organic compound containing N and S is 1 (0.05-2).
Preferably, the mass ratio of the citrate to the organic compound containing N and S is1 (0.1-2).
Further, the inert gas comprises nitrogen and argon.
Further, the method for evenly mixing is ball milling.
Preferably, the rotation speed of the ball milling is 100-900 r/min.
More preferably, the rotational speed of the ball mill is 300-600 r/min.
Most preferably, the rotational speed of the ball mill is 450r/min.
Preferably, the ball milling time is 10-60 min.
More preferably, the ball milling time is 20 to 45 minutes.
Most preferably, the ball milling time is 30 minutes.
Under the selection conditions of the reaction raw materials and the ball milling rotating speed, reactants can be uniformly mixed, so that the chemical environment of the reactants in the heat treatment process is uniform, and the distribution of sulfur elements in the product obtained by the reaction is uniform.
Further, the preparation method further comprises the steps of washing and drying after the heat treatment.
Preferably, the washed solution is dilute sulfuric acid, dilute hydrochloric acid, dilute nitric acid or deionized water.
More preferably, the washed solution is dilute sulfuric acid, dilute hydrochloric acid or deionized water.
Most preferably, the washed solution is deionized water.
The invention further provides a nitrogen-oxygen-sulfur doped carbon anode material, which is prepared by the preparation method.
The invention further protects application of the nitrogen-oxygen-sulfur doped carbon anode material in preparation of the anode material of the potassium ion battery.
Compared with the prior art, the invention has the following beneficial effects:
the nitrogen-oxygen-sulfur doped material prepared by the preparation method has rich defect sites and pore channel structures, and is beneficial to improving the first-circle coulomb efficiency and the cycle stability of the potassium ion battery when being used as a negative electrode material; the adopted raw materials are wide in sources, low in cost and easy to obtain; the preparation method is simple, has mild conditions and is beneficial to large-scale production.
Drawings
FIG. 1 shows the microscopic morphology of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention under a field emission Scanning Electron Microscope (SEM).
Fig. 2 is an elemental distribution diagram (EDS) of a nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention.
Fig. 3 is an X-ray diffraction pattern (XRD) of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention.
Fig. 4 is a raman spectrometer of a nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention.
Fig. 5 shows the rate performance of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention at different current densities.
FIG. 6 shows the initial coulombic efficiency of the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 of the present invention, and the long cycle performance of 1000 cycles at a current density of 1 A.g -1.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
Reagents and materials used in the following examples are commercially available unless otherwise specified.
Example 1 preparation method of Nitrogen-oxygen-sulfur doped carbon negative electrode Material
S1, uniformly ball-milling and mixing sodium citrate and thiourea with the mass ratio of 1:1 at the room temperature by using a ball milling method at the rotating speed of 450r/min for 30min to obtain a precursor;
S2, heating the precursor obtained in the step S1 to 500 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 60min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 2 preparation method of Nitrogen-oxygen-sulfur doped carbon negative electrode Material
S1, uniformly ball-milling and mixing potassium citrate and thiourea with the mass ratio of 10:1 at room temperature for 30min by using a ball milling method at the rotating speed of 450r/min to obtain a precursor;
s2, heating the precursor obtained in the step S1 to 800 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 60min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 3 preparation method of Nitrogen-oxygen-sulfur doped carbon negative electrode Material
S1, uniformly ball-milling and mixing sodium citrate and melamine in a mass ratio of 5:1 at room temperature for 30min by using a ball milling method at a rotating speed of 300r/min to obtain a precursor;
S2, heating the precursor obtained in the step S1 to 600 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 150min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with dilute sulfuric acid, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 4 preparation method of Nitrogen-oxygen-sulfur doped carbon negative electrode Material
S1, uniformly ball-milling and mixing potassium sodium citrate and dicyandiamide in a mass ratio of 15:1 at room temperature for 60min by using a ball milling method at a rotating speed of 600r/min to obtain a precursor;
S2, heating the precursor obtained in the step S1 to 700 ℃ at a heating rate of 1 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 120min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with dilute hydrochloric acid, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Example 5 preparation method of Nitrogen-oxygen-sulfur doped carbon negative electrode Material
S1, uniformly ball-milling and mixing sodium citrate and thiourea with the mass ratio of 20:1 at the room temperature for 45min by using a ball milling method at the rotating speed of 300r/min to obtain a precursor;
S2, heating the precursor obtained in the step S1 to 900 ℃ at a heating rate of 10 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 360min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
Comparative example 1: preparation method of nitrogen-oxygen-sulfur doped carbon anode material
S1, uniformly ball-milling and mixing citric acid and thiourea with the mass ratio of 1:1 at room temperature for 30min by using a ball milling method at the rotating speed of 450r/min to obtain a precursor;
S2, heating the precursor obtained in the step S1 to 500 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 60min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
In step S1, the sodium citrate of example 1 was replaced with the citric acid of comparative example, and in the pyrolysis, citric acid was used as an oxygen-containing carbon source only, and no alkaline carbonate was formed during the decomposition, so that the pore structure in the product was less.
Comparative example 2: preparation method of carbon anode material
S1, uniformly ball-milling and mixing sodium citrate at room temperature for 30min by using a ball milling method at a rotating speed of 450r/min to obtain a precursor;
S2, heating the precursor obtained in the step S1 to 500 ℃ at a heating rate of 3 ℃/min under the protection of nitrogen atmosphere, and then preserving heat for 60min to obtain a pyrolysis product;
S3, stirring and cleaning the pyrolysis product obtained in the step S2 with deionized water, performing suction filtration to obtain a solid product, and repeatedly cleaning for three times to obtain the catalyst.
In comparison with example 1, no organic compound containing N and S was added in step S1, and there were fewer defective sites and fewer active sites in the product.
Characterization test:
scanning electron microscope test: the nitrogen-oxygen-sulfur doped carbon cathode material prepared in example 1 was subjected to Scanning Electron Microscope (SEM) testing. As shown in FIG. 1, the prepared nitrogen-oxygen-sulfur doped carbon negative electrode material is formed by aggregating small particles with the average particle diameter of 176nm, and as can be seen from FIG. 2, N, O, S elements in the nitrogen-oxygen-sulfur doped carbon negative electrode material are uniformly doped into the carbon material, so that the element dispersibility is proved to be good.
X-ray diffraction test: the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 was subjected to phase analysis using an X-ray diffractometer. As a result, as shown in FIG. 3, two broad diffraction peaks appear near 2 theta of 25.8 DEG and 43.8 DEG, corresponding to the (002) crystal plane peak and the (101) crystal plane peak of the nitrogen-oxygen-sulfur doped carbon anode material, respectively, but the two diffraction peaks are wider, which means that the disorder degree of the prepared material is higher, and the product is in an amorphous form.
Raman spectrum test: the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in example 1 was subjected to chemical composition analysis by using a raman spectrometer. As shown in FIG. 4, two standard peaks (D peak and G peak) belonging to the nitrogen-oxygen-sulfur doped carbon negative electrode material appear near 1350cm -1 and 1580cm -1, the peak shape is wider and not sharp, the I D/IG is 0.99, and the defect sites contained in the material are more and the graphitization degree is lower.
Electrochemical performance test:
The nitrogen-oxygen-sulfur doped carbon anode material is applied to a potassium ion half battery, can be assembled by using the prior art means, takes a CR2032 button battery shell as a shell, takes a metal potassium sheet as an anode, takes a loaded nitrogen-oxygen-sulfur doped carbon anode material, carbon black and sodium carboxymethylcellulose copper foil as an anode (the mass ratio of the nitrogen-oxygen-sulfur doped carbon anode material, the carbon black and the sodium carboxymethylcellulose is 8:1:1), takes 1M difluoro sulfonimide potassium (KFSI) ester electrolyte (a composite solvent with the volume ratio of ethylene carbonate to diethyl carbonate is 1:1) as electrolyte, and takes a glass fiber diaphragm as a battery diaphragm.
The nitrogen-oxygen-sulfur doped carbon anode material is used as a potassium ion half-cell anode, and the electrochemical performance of the anode material can be tested by using the prior art means.
The initial coulomb efficiency of the nitrogen-oxygen-sulfur doped carbon anode materials prepared in each example and comparative example when the nitrogen-oxygen-sulfur doped carbon anode materials are used as the anode of the potassium ion battery, and the average capacity attenuation rate of each circle after 500 circles of circulation under the current density of 1 A.g -1 are shown in table 1:
Table 1: the initial coulombic efficiency of each example and comparative example when applied to the negative electrode of a potassium ion battery, and the average capacity decay rate per cycle after 500 cycles at a current density of 1 A.g -1
As can be seen from Table 1, the electrochemical properties of the nitrogen-oxygen-sulfur doped carbon anode materials prepared in each example are better than those of the comparative example, wherein the nitrogen-oxygen-sulfur doped carbon anode material prepared in example 1 has the best properties, the initial coulomb efficiency reaches 51%, and the average capacity attenuation rate per round after 500 rounds of circulation is only 0.0457%.
In the comparative example 1, citric acid is selected to react with thiourea, in the reaction process, the citric acid is only used as an oxygen-containing carbon source, no alkaline carbonate is generated in the pyrolysis process, a pore channel structure cannot be formed in a carbon material, and activation effect cannot be generated on the carbon material to form micropores, so that electrolyte cannot be fully infiltrated, the contact between an internal material and the electrolyte is poor, and potassium ion diffusion is affected. Meanwhile, in the electrochemical circulation process, the electrode material is easy to break and fall off, the electrochemical performance is poor, and after 100 circles of circulation, the electrode material is irreversibly hard deactivated.
In comparative example 2, sodium citrate is directly carbonized, no organic compound containing N and S is added, and no N, S hetero atoms are doped in the pyrolysis process, so that the obtained carbon material has fewer defect sites, fewer active sites and low initial coulombic efficiency of only 20%. In the electrochemical circulation process, the slurry ground by mixing the comparative example 2 with carbon black and sodium carboxymethylcellulose has poor adhesion on the surface of the copper foil, is easy to fall off from the surface of the copper foil and causes poor contact, so that the circulation stability is poor, and irreversible inactivation occurs after 50 circles of circulation under the current density of 1 A.g -1.
The rate performance and long cycle performance of the nitrogen-oxygen-sulfur doped carbon anode material prepared in example 1 as the anode of the potassium ion battery are shown in fig. 5 and 6. As can be seen from FIG. 5, the nitrogen-oxygen-sulfur doped carbon negative electrode material prepared in the embodiment 1 of the invention has good multiplying power performance and small current circulation stability, and after multiplying power circulation is completed, the specific capacity is not obviously reduced after the circulation is continued for 70 circles under the condition of small current (current density is 0.1 A.g -1). As can be seen from FIG. 6, the material has good long-cycle stability, after 1000 cycles of circulation under the current density of 1 A.g -1 (three activated cycles under the current density of 0.1 A.g -1), the specific capacity is not obviously reduced, and the capacity retention rate reaches 95%.
The above examples are preferred embodiments of the present invention, but the embodiments of the present invention are not limited to the above examples, and any other changes, modifications, substitutions, combinations, and simplifications that do not depart from the spirit and principle of the present invention should be made in the equivalent manner, and the embodiments are included in the protection scope of the present invention.
Claims (5)
1. The application of the nitrogen-oxygen-sulfur doped carbon anode material in preparing the anode material of the potassium ion battery is characterized in that the preparation method of the nitrogen-oxygen-sulfur doped carbon anode material comprises the following steps:
Uniformly mixing citrate with an organic compound containing N and S, performing heat treatment at 400-900 ℃ in an inert gas atmosphere, and cleaning to obtain the organic compound;
the organic compound containing N and S is thiourea;
The citrate is one or more of lithium citrate, potassium citrate, sodium citrate, potassium sodium citrate, ferric citrate, cupric citrate, magnesium citrate and ammonium citrate;
The mass ratio of the citrate to the organic compound containing N and S is 1 (0.05-2).
2. The application of the nitrogen-oxygen-sulfur doped carbon anode material in preparing the anode material of the potassium ion battery according to claim 1, wherein the temperature of the heat treatment is 450-700 ℃.
3. The application of the nitrogen-oxygen-sulfur doped carbon anode material in preparing the anode material of the potassium ion battery according to claim 1, wherein the heat treatment time is 30-360 min.
4. The application of the nitrogen-oxygen-sulfur doped carbon anode material in preparing the anode material of the potassium ion battery according to claim 1, wherein the mass ratio of the citrate to the organic compound containing N and S is 1 (0.1-2).
5. The use of the nitrogen-oxygen-sulfur doped carbon negative electrode material according to claim 1 for preparing a negative electrode material of a potassium ion battery, wherein the inert gas comprises nitrogen and argon.
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