CN115626670B - Potassium ion battery anode material and preparation method thereof - Google Patents
Potassium ion battery anode material and preparation method thereof Download PDFInfo
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- CN115626670B CN115626670B CN202211307693.XA CN202211307693A CN115626670B CN 115626670 B CN115626670 B CN 115626670B CN 202211307693 A CN202211307693 A CN 202211307693A CN 115626670 B CN115626670 B CN 115626670B
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- 229910001414 potassium ion Inorganic materials 0.000 title claims abstract description 70
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 title claims abstract description 61
- 239000010405 anode material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 49
- 238000000034 method Methods 0.000 claims abstract description 33
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 25
- 239000002243 precursor Substances 0.000 claims abstract description 22
- 238000001035 drying Methods 0.000 claims abstract description 17
- 230000008569 process Effects 0.000 claims abstract description 17
- 238000005406 washing Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 15
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 230000000630 rising effect Effects 0.000 claims abstract description 3
- SHWZFQPXYGHRKT-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;nickel Chemical compound [Ni].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O SHWZFQPXYGHRKT-FDGPNNRMSA-N 0.000 claims abstract 3
- 238000003756 stirring Methods 0.000 claims description 28
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000007773 negative electrode material Substances 0.000 claims description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 74
- 229910052759 nickel Inorganic materials 0.000 abstract description 34
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 abstract description 18
- 239000002131 composite material Substances 0.000 abstract description 16
- 238000009831 deintercalation Methods 0.000 abstract description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 5
- 239000011593 sulfur Substances 0.000 abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 abstract description 5
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 230000010287 polarization Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 47
- 239000000463 material Substances 0.000 description 16
- 239000007772 electrode material Substances 0.000 description 14
- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 10
- 238000012360 testing method Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 239000007787 solid Substances 0.000 description 7
- -1 transition metal sulfide Chemical class 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 239000003792 electrolyte Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000002086 nanomaterial Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 3
- 229910001413 alkali metal ion Inorganic materials 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010335 hydrothermal treatment Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 2
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000004108 freeze drying Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910001416 lithium ion Inorganic materials 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 238000004729 solvothermal method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 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 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- HMDDXIMCDZRSNE-UHFFFAOYSA-N [C].[Si] Chemical compound [C].[Si] HMDDXIMCDZRSNE-UHFFFAOYSA-N 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000011267 electrode slurry Substances 0.000 description 1
- 239000002001 electrolyte material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000037427 ion transport Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000013557 residual solvent Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 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
- H01M4/362—Composites
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/40—Electric properties
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The preparation method of the anode material of the potassium ion battery comprises the following steps: s1: dissolving nickel acetylacetonate in a solvent to form a uniform first solution; s2: dispersing graphene into the first solution to form a first turbid liquid; s3: adding dodecyl mercaptan into the first turbid liquid, and uniformly mixing to obtain a precursor solution; s4: the precursor solution is subjected to temperature rising, reaction, filtration, washing and drying in sequence to obtain a potassium ion battery anode material; the method has the advantages that dodecyl mercaptan is used as a sulfur source, nickel acetylacetonate is used as a nickel source, nickel sulfide is loaded on the surface of graphene in a hot solvent to form a nickel sulfide-graphene composite material, potassium ions can have a faster potassium ion deintercalation rate when the composite material is used as an electrode of a potassium ion battery, and meanwhile, due to the combination of one-dimensional nickel sulfide nano particles and two-dimensional graphene, the conductivity of the electrode is greatly improved, and meanwhile, the polarization of the electrode in a charge-discharge process can be reduced.
Description
Technical Field
The application relates to the technical field of battery composite materials for potassium ions, in particular to a negative electrode material of a potassium ion battery and a preparation method thereof.
Background
The working principle of the potassium ion battery is similar to that of a lithium ion battery, and the potassium ion is utilized to realize charge and discharge in the process of inserting and extracting between the anode and the cathode. Compared with a lithium ion battery, the potassium ion battery has the following advantages: the potassium salt raw material is rich in reserve and low in price; (2) Due to the characteristics of potassium salt, low concentration electrolyte (electrolyte with the same concentration, potassium salt conductivity about 20% higher than lithium electrolyte) is allowed to be used; (3) The potassium ions do not form alloy with aluminum, the aluminum foil can be used as a current collector for the negative electrode, and the weight can be reduced by about 10 percent; (4) The sodium ion battery is allowed to discharge to zero volts due to the non-overdischarge characteristic of the potassium ion battery. Potassium ion compared with sodium ionHas a lower redox potential and thus has a higher voltage plateau and energy density. In addition, K + The weaker Lewis acidity accelerates the kinetics of ion transport and charge transfer at the electrolyte/active material interface. Although potassium ion batteries have such many advantages, they tend to exhibit lower capacity and poorer cycle performance due to the lack of suitable electrode materials to meet the deintercalation of potassium ions during charge and discharge. High capacity materials (e.g., silicon carbon, silicon oxide) typically have a short cycle life, while long cycle life materials (e.g., hard carbon, graphene) have a relatively low capacity, and therefore developing potassium ion electrode materials with high capacity, high stability is a significant challenge.
Due to the conversion reaction of transition metal sulfide and alkali metal ions and the process of removing and intercalating alkali metal in layered transition metal sulfide, the transition metal sulfide material has higher theoretical specific capacity than graphite, so that the transition metal sulfide material is widely applied to alkali metal ion batteries. Wherein the theoretical specific capacity of NixSy is 450-880 mA/g, but the theoretical specific capacity of NixSy is far from the theoretical specific capacity in practical application. The nano structure can increase the specific surface area of the electrode material, shorten the electron transmission and ion diffusion paths and improve the strain regulating capability of alkali metal ions in the deintercalation process, so that the electrochemical performance of the nano structure can be greatly improved. However, the nano material has higher surface energy, and is prone to agglomeration in the preparation and post-treatment process and the electrode preparation process, which deviates from the original purpose of preparing the nano material, so that the exploration of an effective strategy for inhibiting the agglomeration of the nano material is of great significance.
The patent application number is as follows: the Chinese patent document of CN201810835300.X discloses a preparation method of a nano nickel sulfide-graphene composite electrode material, which comprises the following preparation steps: (1) Placing a conductive substrate material into a graphene oxide solution, loading, and taking out and drying; (2) The graphene oxide/conductive substrate material prepared in the step (1) is used as a working electrode, a salt solution of nickel element is used as an electrolyte, a constant potential deposition method is adopted, the potential range is-1.2 to-1V, nano nickel hydroxide is deposited on the surface of the graphene oxide/conductive carbon base, and meanwhile, the graphene oxide is reduced, so that a nickel hydroxide-graphene composite material is obtained; (3) And (3) reacting the nickel hydroxide-graphene composite material with sodium sulfide to obtain the nano nickel sulfide-graphene composite material.
The patent application number is as follows: the Chinese patent application document of CN201910836150.9 discloses a preparation method of a high-performance nickel sulfide-graphene composite electrode material, which comprises the following steps: dispersing graphene oxide in deionized water, and obtaining uniformly dispersed graphene oxide solution through ultrasonic treatment; step two, dissolving nickel nitrate and thiourea into deionized water, continuously stirring until the nickel nitrate and the thiourea are completely dissolved, and then dropwise adding a potassium hydroxide solution to adjust the pH value to obtain a mixed solution; step three, adding the graphene oxide dispersion solution obtained in the step one into the mixed solution obtained in the step two, and fully stirring; step four, placing the mixed solution obtained in the step three in a microwave oven, and carrying out microwave rapid heating to obtain a sample; step five, collecting and transferring the sample obtained in the step four to a reaction kettle, and performing hydrothermal treatment to obtain a nickel sulfide-graphene product; and step six, centrifuging the nickel sulfide-graphene product obtained in the step five, washing the nickel sulfide-graphene product with deionized water for multiple times, and freeze-drying the nickel sulfide-graphene product to obtain the nickel sulfide-graphene composite material. The two methods are respectively used for preparing the required nickel sulfide-graphene composite material through the combination of electrodeposition, electric adsorption and solvothermal method, but the electrode produced through the method is not suitable for a potassium ion battery and is not beneficial to the deintercalation of potassium ions.
Disclosure of Invention
In order to solve the technical problems, the application provides a negative electrode material of a potassium ion battery and a preparation method thereof. According to the application, dodecyl mercaptan is selected as a sulfur source, so that the distance between nano nickel sulfide on graphite is increased, and the speed of potassium ion deintercalation on the surface of an electrode is increased.
The specific technical scheme of the application is as follows:
the preparation method of the anode material of the potassium ion battery comprises the following steps:
s1: dissolving nickel acetylacetonate in a solvent to form a uniform first solution;
s2: dispersing graphene into the first solution to form a first turbid liquid;
s3: adding dodecyl mercaptan into the first turbid liquid, and uniformly mixing to obtain a precursor solution;
s4: the precursor solution is subjected to temperature rising, reaction, filtration, washing and drying in sequence to obtain the anode material of the potassium ion battery.
In the prior art, a constant potential deposition method is used for preparing a nickel sulfide-graphene material, the deposition amount in the electrodeposition process and the density of nickel sulfide on the surface of graphene cannot be controlled in the preparation process, and structural damage occurs in the protection and deintercalation process of potassium ions when the electrode is applied as a potassium ion battery, so that the function of the electrode is reduced; the nickel sulfide-graphene material is prepared by a simple and efficient microwave-assisted hydrothermal treatment method, a large amount of negative charges and functional groups on the surface of original graphene oxide are fully combined with nickel ions with positive charges through microwaves, and then thiourea is converted into the nickel sulfide-graphene material, and the quantity of the adsorbed nickel ions on the surface of the graphene oxide cannot be controlled in the electrostatic adsorption process of the method, so that the problems can occur when the nickel sulfide-graphene material is used as a potassium ion battery electrode.
In the technical scheme, dodecyl mercaptan is used as a sulfur source, nickel acetylacetonate is used as a nickel source, and nickel sulfide is loaded on the surface of graphene in a hot solvent by a one-step method to form a nickel sulfide-graphene composite material; in the preparation process, the steric hindrance of the dodecyl nickel sulfide can limit the density of nickel adsorbed on the surface of graphene, so that nickel sulfide formed on the surface of the graphene can have larger spacing, potassium ions can have a faster potassium ion deintercalation rate when being used as an electrode of a potassium ion battery, and meanwhile, due to the combination of one-dimensional nickel sulfide nano particles and two-dimensional graphene, the conductivity of the electrode is greatly improved, and meanwhile, the polarization of the electrode in the charge-discharge process can be reduced.
As a preferable mode of the above technical solution of the present application, dodecyl mercaptan is added in excess in step S3; in the scheme, excessive dodecyl mercaptan is added, because the inventor finds that the prepared nickel sulfide-graphene electrode material with a complex structure can adsorb a part of dodecyl mercaptan, the standing time required before the electrode prepared by the adsorbed nickel sulfide-graphene material is formed is shorter, and the assembly test efficiency of the potassium ion battery is higher.
As a preferable mode of the above technical scheme of the present application, the solvent in step S1 is selected from one of diphenyl ether, benzene, and ethanol.
As the optimization of the technical scheme, in the step S4, the reaction temperature is 200-300 ℃ and the reaction time is 1-2 hours.
As a preferable mode of the above-described aspect of the present application, in step S4, the solvent used for washing is selected from one of cyclohexane and n-hexane.
As a preferable mode of the technical scheme, in the step S4, the drying temperature is 30-50 ℃.
As the optimization of the technical scheme, in the step S1, ultrasound is firstly carried out in the dissolving process, and then stirring is carried out for 15-20 min at 20-30 ℃.
As the optimization of the technical scheme, in the step S2, the temperature of the dispersing process is 20-30 ℃ and the time is 15-60 min.
Another object of the present application is to provide a negative electrode material for a potassium ion battery, which can be prepared according to the above method.
In summary, the beneficial effects of the application are as follows:
1. according to the application, dodecyl mercaptan is used as a sulfur source, nickel acetylacetonate is used as a nickel source, and nickel sulfide is loaded on the surface of graphene in a hot solvent by a one-step method to form a nickel sulfide-graphene composite material; in the preparation process, the steric hindrance of the dodecyl nickel sulfide can limit the density of nickel adsorbed on the surface of graphene, so that nickel sulfide formed on the surface of the graphene can have larger spacing, potassium ions can have a faster potassium ion deintercalation rate when being used as an electrode of a potassium ion battery, and meanwhile, due to the combination of one-dimensional nickel sulfide nano particles and two-dimensional graphene, the conductivity of the electrode is greatly improved, and meanwhile, the polarization of the electrode in the charge and discharge processes can be reduced;
2. by adding excessive dodecyl mercaptan, a part of dodecyl mercaptan can be adsorbed by the nickel sulfide-graphene electrode material with a complex structure, the nickel sulfide-graphene material with the adsorbed dodecyl mercaptan can be immersed into electrolyte more quickly, the standing time required before formation is shorter, and the assembly test efficiency of the potassium ion battery is higher;
3. the electrode prepared by the electrode material has higher capacity and better cycle performance when being applied as a potassium ion battery, and has longer service life.
Drawings
FIG. 1 is a TEM image of a negative electrode material of a potassium ion battery of example 1;
FIG. 2 is an XRD pattern of button cells prepared from the electrode materials of example 1 and comparative example 1;
fig. 3 is an XPS diagram of a button cell prepared from the electrode material of example 1;
FIG. 4 is a CV curve of button cells prepared from the electrode materials of example 1 and comparative example 1;
fig. 5 is a cycle curve and charge and discharge curves of different cycles of the button cell prepared from the electrode material of example 1.
Detailed Description
The technical scheme of the present application will be clearly and completely described below with reference to the accompanying drawings and specific embodiments. It will be apparent that the described embodiments are only some, but not all, embodiments of the application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1: dissolving nickel acetylacetonate in a solvent to form a uniform first solution;
s2: dispersing graphene into the first solution to form a first turbid liquid;
s3: adding dodecyl mercaptan into the first turbid liquid, and uniformly mixing to obtain a precursor solution;
s4: and heating, reacting, filtering, washing and drying the precursor solution to obtain the anode material of the potassium ion battery.
Taking dodecyl mercaptan as a sulfur source, taking nickel acetylacetonate as a nickel source, and loading nickel sulfide on the surface of graphene in a hot solvent by a one-step method to form a nickel sulfide-graphene composite material; in the preparation process, the steric hindrance of the dodecyl nickel sulfide can limit the density of nickel adsorbed on the surface of graphene, so that nickel sulfide formed on the surface of the graphene can have larger spacing, potassium ions can have a faster potassium ion deintercalation rate when being used as an electrode of a potassium ion battery, and meanwhile, due to the combination of one-dimensional nickel sulfide nano particles and two-dimensional graphene, the conductivity of the electrode is greatly improved, and meanwhile, the polarization of the electrode in the charge-discharge process can be reduced.
The dodecyl mercaptan added in step S3 is excessive; according to the scheme, excessive dodecyl mercaptan is added, a part of dodecyl mercaptan can be adsorbed by the prepared nickel sulfide-graphene electrode material with a complex structure, and the electrode prepared by the nickel sulfide-graphene material after the dodecyl mercaptan is adsorbed can be soaked by electrolyte very quickly, so that a long time is not required to be kept still before formation, and the assembly test efficiency of the potassium ion battery is higher.
The solvent in the step S1 is selected from one of diphenyl ether, benzene, ethanol and the like; preferably, diphenyl ether is selected as the organic solvent of the application, which has good solubility to dodecyl mercaptan, and the adsorbed acting force of part of dodecyl mercaptan can be ensured to be larger than the acting force of solvent molecules to dodecyl mercaptan when the nickel sulfide-graphene material is prepared, so that the dodecyl mercaptan can be adsorbed and taken out of the solvent.
In the step S4, the reaction temperature is 200-300 ℃ and the reaction time is 1-2 hours; the formation, the particle size and the morphology of the nickel sulfide can be controlled by a solvothermal method, and the dispersibility of the product is good. Under solvothermal conditions, the properties of the solvent (density, viscosity, dispersion) are mutually influenced; under the condition of the experiment, the optimal temperature range of the reaction temperature is 230-240 ℃.
In step S4, the solvent used for washing is selected from one of cyclohexane and n-hexane; part of the residual solvent and some substances which are not firmly adhered are washed off.
In the step S4, the drying temperature is 30-50 ℃, and the drying is performed at a low temperature, so that the loss or danger of the adsorbed mercaptan is avoided.
In the step S1, ultrasound is firstly carried out in the dissolution process, and then stirring is carried out for 15-20 min at 20-30 ℃ to promote the dissolution and dispersion of the nickel acetylacetonate crystals in the solvent.
In the step S2, the temperature in the dispersing process is 20-30 ℃ and the time is 15-60 min, so that the dispersion of dodecyl mercaptan is promoted.
The application also aims to provide a cathode material of the potassium ion battery, which can be prepared by the method, and the electrode prepared by the electrode material has higher capacity and better cycle performance and longer service life when being applied as a potassium ion battery.
Example 1
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 0.13 g nickel acetylacetonate in a 50 mL container, then adding 10 mL diphenyl ether, carrying out ultrasonic treatment for 10 min, and then stirring at 25 ℃ for 20min to form a uniform green solution;
s2, dispersing 10 mg graphene into the first solution to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 3 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 235 ℃ for 1.5-h, filtering, washing with cyclohexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
The inventors carried out morphology characterization on the anode material of the potassium ion battery obtained in the embodiment, and as shown in fig. 1, it can be seen from a Transmission Electron Microscope (TEM) image that nickel sulfide nanorods are uniformly supported on graphene, wherein the diameter of the nickel sulfide nanorods is 3-5 nm.
Meanwhile, phase analysis is performed on the anode material of the potassium ion battery obtained in the embodiment, and fig. 2 shows X-ray diffraction (XRD) patterns of S1 and graphene respectively, so that it can be seen from the figure that S1 has both a characteristic peak of graphene and a characteristic peak of nickel sulfide, that is, S1 is a composite of graphene and nickel sulfide. To further demonstrate the sulfide content of S1, we performed X-ray photoelectron spectroscopy (XPS) test on S14, as shown in FIG. 3, which shows that S1 has Ni at the same time 2+ And Ni 3+ S is S 2- In a form consistent with XRD results.
Example 2
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 0.13 g nickel acetylacetonate in a 50 mL container, then adding 10 mL diphenyl ether, carrying out ultrasonic treatment for 10 min, and then stirring at 25 ℃ for 20min to form a uniform green solution;
s2, dispersing 10 mg graphene into the first solution to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 3 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 230 ℃ for 1.5-h, filtering, washing with cyclohexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
Example 3
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 0.13 g nickel acetylacetonate in a 50 mL container, then adding 10 mL diphenyl ether, carrying out ultrasonic treatment for 10 min, and then stirring at 25 ℃ for 20min to form a uniform green solution;
s2, dispersing 10 mg graphene into the first solution to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 3 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 240 ℃ for 1.5-h, filtering, washing with cyclohexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
Example 4
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 0.13 g nickel acetylacetonate in a 50 mL container, then adding 10 mL diphenyl ether, carrying out ultrasonic treatment for 10 min, and then stirring at 25 ℃ for 20min to form a uniform green solution;
s2, dispersing 10 mg graphene into the first solution to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 3 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 235 ℃ for 1.5-h, filtering, washing with a normal hexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
Example 5
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 0.13 g nickel acetylacetonate in a 50 mL container, adding 10 mL ethanol, performing ultrasonic treatment for 10 min, and stirring at 25 ℃ for 20min to form a uniform green solution;
s2, dispersing 10 mg graphene into the first solution to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 3 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 235 ℃ for 1.5-h, filtering, washing with cyclohexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
Example 6
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 0.13 g nickel acetylacetonate in a 50 mL container, then adding 10 mL diphenyl ether, carrying out ultrasonic treatment for 10 min, and then stirring at 25 ℃ for 20min to form a uniform green solution;
s2, dispersing 10 mg graphene into the first solution to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 2.5 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 235 ℃ for 1.5-h, filtering, washing with cyclohexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
Comparative example 1
The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1, weighing 10 mL diphenyl ether in a 50 mL container;
s2, dispersing 10 mg graphene into the dimethyl ether to form a first turbid liquid; then stirring at 25deg.C for 30 min
S3, rapidly adding 3 mL dodecyl mercaptan into the solution, and stirring at 25 ℃ for 40 min to obtain a precursor solution;
s4, reacting the precursor solution at 235 ℃ for 1.5-h, filtering, washing with cyclohexane solvent for 3-5 times, and drying the obtained black solid at 40 ℃ to obtain the potassium ion battery anode material.
Comparative example 2
60mg of graphene oxide is dispersed in deionized water, and a uniformly dispersed graphene oxide solution is obtained through ultrasonic treatment. Secondly, dissolving nickel nitrate and thiourea in deionized water, continuously stirring until the nickel nitrate and the thiourea are completely dissolved, then dropwise adding potassium hydroxide solution to adjust the pH value, and magnetically stirring for a long time to obtain a mixed solution. And adding graphene oxide solutions with different concentrations into the mixed solution, continuously stirring and carrying out ultrasonic treatment to obtain graphene oxide suspension. Transferring the obtained mixed solution into a microwave oven for microwave rapid heating for 4-8min to obtain black sticky matter, and then performing hydrothermal treatment on the black sticky matter at the reaction temperature of 110-150 ℃ for 6-8h. And collecting the nickel sulfide-graphene composite, performing centrifugal washing for a plurality of times, and finally performing freeze drying to obtain the nickel sulfide-graphene composite powder.
For example 1, example 7 and comparative 1, the inventors performed the following tests:
phase analysis was performed on S2, and as shown in fig. 2, XRD results showed that S2 had distinct graphene characteristic peaks. A potassium ion button cell was prepared using S2 according to w (S2): w (PVDF): w (SP) =85:10:5, preparing electrode slurry, coating and drying by a scraper to obtain an electrode plate, wherein the diameter of the electrode plate is 12 mm, the load capacity is about 2.0 mg, assembling the electrode plate with potassium metal to form a CR2032 button cell, and testing the electrochemical performance of the CR2032 button cell.
Firstly, performing Cyclic Voltammetry (CV) test on batteries prepared from S1 and S2 materials, as shown in FIG. 4, it can be seen from CV curve that S1 can generate complex reaction on the electrode surface to form SEI film due to first charge and discharge, so that the first circle can show different peak number and peak position from the last three circles, and the peak position of the next 3 circles can be seen from the curve to basically coincide, thus demonstrating excellent reversibility; fig. b shows two small peaks around 0.5V as graphene oxide peaks, illustrating the remaining 4 peak positions in fig. a as two pairs of redox peaks of nickel sulfide; the cyclic test of the S1 battery is carried out, the test current is 100 mA/g, as shown in fig. 5, the capacity of the battery is still kept at about 520 mAh/g after 200 cycles, almost no attenuation is caused, and the coulomb efficiency is always kept above 98%; FIG. 5b is a charge-discharge curve for different cycles, from which it can be seen that the specific capacity of the other cycles is substantially unchanged except the first cycle specific capacity; in addition, the charge-discharge platform corresponds to the CV curve oxidation-reduction peak, and the platform is hardly changed along with the increase of the number of circles of circulation, which indicates that the material has good structural stability.
The application and its embodiments have been described above schematically, without limitation, and the actual construction is not limited to this, as it is shown in the drawings, which are only one of the embodiments of the application. Therefore, if one of ordinary skill in the art is informed by this disclosure, a structural manner and an embodiment similar to the technical scheme are not creatively devised without departing from the gist of the present application, and all the structural manners and the embodiments belong to the protection scope of the present application.
Claims (7)
1. The preparation method of the anode material of the potassium ion battery comprises the following steps:
s1: dissolving nickel acetylacetonate in a solvent to form a uniform first solution;
s2: dispersing graphene into the first solution to form a first turbid liquid;
s3: adding dodecyl mercaptan into the first turbid liquid, and uniformly mixing to obtain a precursor solution;
s4: the precursor solution is subjected to temperature rising, reaction, filtration, washing and drying in sequence to obtain a potassium ion battery anode material;
the solvent in the step S1 is selected from one of diphenyl ether, benzene and ethanol;
the dodecyl mercaptan added in step S3 is in excess.
2. The method for preparing the anode material of the potassium ion battery according to claim 1, wherein in the step S4, the reaction temperature is 200-300 ℃ and the reaction time is 1-2 hours.
3. The method according to claim 1, wherein in step S4, the solvent used for washing is selected from one of cyclohexane and n-hexane.
4. The method for preparing a negative electrode material of a potassium ion battery according to claim 1, wherein in step S4, the drying temperature is 30-50 ℃.
5. The method for preparing the negative electrode material of the potassium ion battery according to claim 1, wherein in the step S1, ultrasound is performed first in the dissolution process, and then stirring is performed at 20-30 ℃ for 15-20 min.
6. The method for preparing the negative electrode material of the potassium ion battery according to claim 1, wherein in the step S2, the temperature of the dispersing process is 20-30 ℃ and the time is 15-60 min.
7. The negative electrode material of the potassium ion battery is characterized by being prepared by the method according to any one of claims 1-6.
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