CN113488648B - Preparation method of cuprous sulfide used as magnesium ion battery positive electrode material - Google Patents
Preparation method of cuprous sulfide used as magnesium ion battery positive electrode material Download PDFInfo
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- CN113488648B CN113488648B CN202110825476.9A CN202110825476A CN113488648B CN 113488648 B CN113488648 B CN 113488648B CN 202110825476 A CN202110825476 A CN 202110825476A CN 113488648 B CN113488648 B CN 113488648B
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- thiourea
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- nitrate trihydrate
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- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 title abstract description 13
- 229910001425 magnesium ion Inorganic materials 0.000 title abstract description 13
- 239000007774 positive electrode material Substances 0.000 title description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 30
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims description 17
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000002244 precipitate Substances 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 2
- 239000002689 soil Substances 0.000 claims description 2
- 239000010405 anode material Substances 0.000 abstract description 3
- 239000010406 cathode material Substances 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000011889 copper foil Substances 0.000 description 3
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 3
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 description 3
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 229910001416 lithium ion Inorganic materials 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 239000012621 metal-organic framework Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 239000002033 PVDF binder Substances 0.000 description 2
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000010277 constant-current charging Methods 0.000 description 2
- XRZJYOVMWCUNER-UHFFFAOYSA-L copper;sulfate;trihydrate Chemical compound O.O.O.[Cu+2].[O-]S([O-])(=O)=O XRZJYOVMWCUNER-UHFFFAOYSA-L 0.000 description 2
- 229940112669 cuprous oxide Drugs 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 238000007600 charging Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000009831 deintercalation Methods 0.000 description 1
- 238000001212 derivatisation Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 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
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Images
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
- H01M4/581—Chalcogenides or intercalation compounds thereof
- H01M4/5815—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—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
- H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
- H01M2004/028—Positive 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)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of cuprous sulfide used as a magnesium ion battery cathode material. The cuprous sulfide provided by the invention is used as a magnesium ion battery anode material, the battery cycle performance is excellent, and the battery specific capacity is high.
Description
Technical Field
The invention belongs to the technical field of batteries, and particularly relates to a preparation method of cuprous sulfide used as a magnesium ion battery positive electrode material.
Background
With the continuous development of human society, the consumption of energy is also greatly increased, the reserves of traditional non-renewable energy resources such as oil, coal, natural gas and the like are less and less, and serious environmental problems are caused, and the development of novel energy and storage devices is urgent (dynamics and finite element analysis of a megawatt wind turbine generator system transmission chain system under random wind load, which is a research result on the university of lakehou science university of ran, the study on the university of lakehou science, 2013, page 1, the 1 st section, lines 1 to 5, and the publication date 2014, 6 and 5).
The ion battery has the advantages of reusability, long service life and the like, and is widely concerned by the public. Lithium ion batteries are currently widely used ion batteries. However, lithium ion batteries have problems of poor safety, high price of lithium elements, and poor lithium resources ("typical safety problem research on lithium ion batteries for electric vehicles", new dawn, new promoter, 3 rd year 2020, 1 st to 2 th abstract page 119, 12 th to 31 th published day 2020; "research on foreign sodium ion batteries", liuchunna, power technology, 38 th volume 1 st, 12 th left column 1 st to 5 th page 12, and 12 th to 31 th published day 2014 ").
The magnesium ion battery has the following advantages: (1) potential safety hazards do not exist; (2) the magnesium resource is rich; (3) the theoretical volume specific capacity is high.
However, magnesium ions are divalent and strongly interact with the positive electrode active material, so that more energy is required for intercalation and deintercalation of magnesium ions. Therefore, the development of suitable cathode materials has become a key part of magnesium ion batteries.
The Weiqin Wang group produced carbon-coated cuprous sulfide composites by Metal Organic Framework (MOF) derivatization and vulcanization. The material is used for Mg 2+ /Li + The battery realizes 50 cycles at a current density of 150mAh/g (Metal oxide Framework (MOF) -Derived carbon-Derived cathode substrate on display reaction for Hybrid Mg 2+ /Li + batteries ", w.wang, et al, Journal of Power Sources,2020(445),227325.1, lines 1-8 of abstract, open 2020, 12 months and 31 days.
The Juanbiao Wang team prepared cuprous sulfide by a template-free hydrothermal method, the cuprous sulfide material is used for a sodium ion battery, and the capacity of the cuprous sulfide material is 369mAh/g ('Cu') after 100 cycles under the current density of 0.2A/g 2 S hold spheres as an anode for high-rate sodium storage performance ", J.Wang, et al, Journal of electrochemical Chemistry,2020(874),114523.1, lines 1-6 of the Abstract, open dated 2020, 12, 31).
However, the above cuprous sulfide is used as a positive electrode material of a magnesium ion battery, and the battery cycle performance is not good.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of cuprous sulfide, which is used as a positive electrode material of a magnesium ion battery and has excellent battery cycle performance.
In order to achieve the purpose, the technical scheme of the invention is as follows:
the preparation method of cuprous sulfide is characterized by using copper nitrate trihydrate and polyvinylpyrrolidone as raw materials to synthesize cuprous oxide, and then reacting the cuprous oxide with thiourea in the presence of a small amount of oxygen.
Preferably, copper nitrate trihydrate and polyvinylpyrrolidone are dissolved in ethylene glycol, the reaction is carried out at 175 ℃ until the solution turns into copper red, thiourea is added, the reaction is continued until the solution turns into earth black, then the obtained solution is transferred to a reaction kettle which enables the volume of the solution in the reaction kettle to be 3/4-4/5 of the total volume, and the reaction is carried out for 24 hours at 160 ℃.
Preferably, the molar ratio of the copper nitrate trihydrate to the polyvinylpyrrolidone is between 532:1 and 534: 1.
Preferably, the amount of the ethylene glycol is such that the concentration of the copper nitrate trihydrate is between 0.078 and 0.082 mol/L.
Preferably, the thiourea is used in a molar ratio of copper nitrate trihydrate to thiourea of 1: 2.
Preferably, the preparation method of cuprous sulfide further comprises the following steps: and (3) centrifuging the solution obtained by reacting the thiourea in the presence of a small amount of oxygen with water and ethanol in sequence, removing supernatant, and drying the precipitate.
Preferably, the rotating speed in the centrifugation process is 6000rpm, and the centrifugation time is 5 min.
Preferably, the drying refers to vacuum drying at 60 ℃ for at least 12 h.
Preferably, the preparation method of cuprous sulfide comprises the following steps:
adding copper nitrate trihydrate and polyvinylpyrrolidone into ethylene glycol according to a molar ratio of 532:1-534:1, and stirring for 30min at room temperature until the copper nitrate trihydrate and the polyvinylpyrrolidone are completely dissolved; heating the solution to 175 ℃ in an oil bath, adding thiourea when the color of the solution becomes copper red, and continuously stirring until the solution becomes dark soil; transferring the obtained solution into a reaction kettle with the volume of the solution in the reaction kettle accounting for 3/4-4/5 of the total volume, heating to 160 ℃, preserving heat for 24 hours, and then cooling to room temperature;
taking the cooled solution, alternately centrifuging with water and ethanol for 3 times at 6000rpm for 5min each time, discarding the clear liquid, and drying the obtained precipitate in a vacuum drying oven at 60 deg.C for at least 12 h;
the dosage of the ethylene glycol is that the concentration of the copper nitrate trihydrate is 0.078-0.082 mol/L;
the dosage of the thiourea is that the molar ratio of the copper nitrate trihydrate to the thiourea is 1: 2.
The invention has the beneficial effects that:
the cuprous sulfide is used as a magnesium ion battery anode material, the battery cycle performance is excellent, the high service life of 850 cycles is realized under the current density of 560mA/g, and the coulombic efficiency is maintained to be more than 99%.
The cuprous sulfide is used as the anode material of the magnesium ion battery, and the specific capacity of the battery is high.
Drawings
FIG. 1 is an electron microscope (i.e., SEM) image of cuprous sulfide produced in example 1;
FIG. 2 is an elemental analysis (i.e., EDS) chart of cuprous sulfide obtained in example 1
FIG. 3 is an X-ray diffraction pattern (i.e., XRD) of the cuprous sulfide obtained in example 1, wherein the abscissa is the scanning angle and the ordinate is the diffraction intensity;
fig. 4 is a rate performance curve of an assembled battery of cuprous sulfide prepared in example 1, wherein the abscissa is cycle number and the ordinate is specific capacity of the battery;
FIG. 5 is a cyclic voltammogram of an assembled cell of cuprous sulfide made in example 1, with voltage on the abscissa and current on the ordinate;
fig. 6 is a graph of the cycling performance of an assembled battery of cuprous sulfide prepared in example 1, wherein the abscissa is the number of cycles and the ordinate is the specific capacity of the battery.
Detailed Description
The examples are provided for better illustration of the present invention, but the present invention is not limited to the examples. Therefore, those skilled in the art should make insubstantial modifications and adaptations to the embodiments of the present invention in light of the above teachings and remain within the scope of the invention.
Example 1
The preparation method comprises the following specific preparation processes:
weighing 0.72g of polyvinylpyrrolidone (molecular weight of 40000) and 9.6mmol (2.319g) of copper sulfate trihydrate, measuring 120ml of ethylene glycol by using a measuring cylinder, dissolving 0.72g of polyvinylpyrrolidone and 2.319g) of copper sulfate trihydrate in 120ml of ethylene glycol, and magnetically stirring at room temperature for 30min until complete dissolution; placing the solution in a 200ml round-bottom flask, heating the solution to 175 ℃ in an oil bath, keeping the temperature for 15min, then enabling the solution to become copper red to generate Cu2O, quickly adding 19.2mmol (1.46g) of thiourea, and continuing stirring for five minutes, wherein the solution becomes black earth to indicate the conversion to Cu 2S;
transferring the obtained 120ml solution into a reaction kettle with the volume of 160ml, heating the reaction kettle to 160 ℃, preserving heat for 24 hours, and then cooling to room temperature;
taking the solution cooled to room temperature, alternately centrifuging with water and ethanol for 3 times (i.e. centrifuging with water and ethanol as washing solvent for 3 times respectively), maintaining the centrifugation rate at 6000rpm, centrifuging for 5min each time, discarding the supernatant to obtain tawny precipitate, and drying the precipitate in a vacuum drying oven at 60 deg.C for 12h to obtain the final product.
Performance detection
The cuprous sulfide prepared in example 1 was subjected to electron microscope scanning, elemental analysis, and X-ray diffraction, and the results are shown in fig. 1 to 3, respectively;
the element analysis method comprises the following specific steps: scanning by EDS under scanning electron microscope (SEM, JSM-7800F, JEOL, Japan), and calibrating to obtain element components and content at the position;
the specific method of X-ray diffraction is as follows: x-ray powder diffraction (XRD) testing was performed on a Rigaku diffractometer (D/MAX-2500X) at Cu K.alpha.radiation of 5-80 deg. to reveal Cu 2 The crystalline nature of S.
As can be seen from fig. 1, the cuprous sulfide produced in example 1 had a hollow structure.
As can be seen from fig. 2, the molecular weight ratio of copper to sulfur in the cuprous sulfide obtained in example 1 was 63.2:36.8, which was close to 2: 1.
As can be seen from FIG. 3, the cuprous sulfide and Cu sulfide obtained in example 1 2 The characteristic peak of the S PDF card is basically corresponding andthe characteristic peak of the synthesized material is strong, which indicates that the synthesized cuprous sulfide crystal form is complete.
Uniformly mixing 210mg of cuprous sulfide, 90mg of carbon black and 30mg of polyvinylidene fluoride (PVDF) prepared in example 1, dissolving the mixture in 1mLNMP, magnetically stirring at room temperature for 24 hours to prepare slurry, coating the slurry on copper foil (the coating thickness is 150 microns), then carrying out vacuum drying on the copper foil at 60 ℃ for 12 hours, punching the copper foil into a wafer with the diameter of 12mm as a positive electrode material, and then assembling the wafer, a polished metal pure magnesium sheet negative electrode, a glass fiber diaphragm, an OMBB electrolyte and a button battery case with model 2032 into a button battery (the water oxygen value is lower than 0.1 PPM); standing the assembled battery for 24h, and then carrying out cyclic voltammetry, rate capability and cyclic performance detection, wherein the results are respectively shown in FIGS. 4-6;
the cyclic voltammetry detection method comprises the following steps: the test voltage range is set to be 0.02V-2V at the electrochemical workstation (morning China, Shanghai) and the scanning speed is 0.0002V/s.
The rate performance detection method comprises the following steps: the blue-electricity LAND battery test system is set to carry out constant-current charging and discharging according to 200mA/g,400mA/g,560mA/g and 200mA/g, the discharging voltage is 0.02v, and the charging voltage is 2 v.
The cycle performance detection method comprises the following steps: 560mA/g, 0.02v of discharge voltage and 2v of charge voltage are set in a blue battery test system, constant-current charging and discharging are carried out, and the cycle number is set to 850 circles.
As can be seen from fig. 4, the reduction peak gradually moves toward a high potential, and the oxidation peak moves toward a low potential, which indicates that the polarization of the battery gradually decreases and the current gradually increases.
As shown in FIG. 5, the specific capacity of the battery is maintained at 250mAh/g under the current density of 200mA/g, the specific capacity of the battery is reduced to below 200mAh/g after the current density is increased to 560mA/g, but the specific capacity is increased back to the level of about 250mAh/g when the current density is reduced to 200mA/g again. Thus, the assembled battery is proved to have excellent rate performance.
As can be seen from fig. 6, the current density 560mA/g test the cycle performance test of the battery 850 cycles after the first 60 cycles of battery activation, the battery first reached a level with a peak value close to 200mAh/g and then the capacity gradually decreased and stabilized at a level of 130 mAh/g.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (8)
1. The preparation method of cuprous sulfide is characterized by dissolving copper nitrate trihydrate and polyvinylpyrrolidone in ethylene glycol, reacting at 175 ℃ until the solution turns into copper red, then adding thiourea, continuing to react until the solution turns into earth black, then transferring the obtained solution to a reaction kettle with the volume of the solution in the reaction kettle accounting for 3/4-4/5 of the total volume, and reacting at 160 ℃ for 24 hours.
2. The method according to claim 1, wherein the molar ratio of copper nitrate trihydrate to polyvinylpyrrolidone is 532:1 to 534: 1.
3. The method according to claim 1, wherein the ethylene glycol is used in such an amount that the concentration of copper nitrate trihydrate is 0.078 to 0.082 mol/L.
4. The method according to claim 1, wherein the thiourea is used in a molar ratio of 1:2 of copper nitrate trihydrate to thiourea.
5. The method of any one of claims 1 to 4, further comprising the steps of: and (3) centrifuging the solution obtained by reacting the thiourea in the presence of a small amount of oxygen with water and ethanol in sequence, removing supernatant, and drying the precipitate.
6. The method according to claim 5, wherein the rotation speed during centrifugation is 6000rpm, and the time for each centrifugation is 5 min.
7. The method according to claim 5, wherein the drying is carried out at 60 ℃ for at least 12 hours under vacuum.
8. The method of claim 1, comprising the steps of:
adding copper nitrate trihydrate and polyvinylpyrrolidone into ethylene glycol according to a molar ratio of 532:1-534:1, and stirring for 30min at room temperature until the copper nitrate trihydrate and the polyvinylpyrrolidone are completely dissolved; heating the solution to 175 ℃ in an oil bath, adding thiourea when the color of the solution becomes copper red, and continuously stirring until the solution becomes dark soil; transferring the obtained solution into a reaction kettle with the volume of the solution in the reaction kettle accounting for 3/4-4/5 of the total volume, heating to 160 ℃, preserving heat for 24 hours, and then cooling to room temperature;
taking the cooled solution, alternately centrifuging with water and ethanol for 3 times at 6000rpm for 5min each time, discarding the clear liquid, and drying the obtained precipitate in a vacuum drying oven at 60 deg.C for at least 12 h;
the dosage of the ethylene glycol is that the concentration of the copper nitrate trihydrate is 0.078-0.082 mol/L;
the dosage of the thiourea is that the molar ratio of the copper nitrate trihydrate to the thiourea is 1: 2.
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Inventor after: Wu Liang Inventor after: Zhong Zhiyong Inventor after: Chen Yanning Inventor after: Wu Jiahao Inventor after: Chen Yonghua Inventor after: Yao Wenhui Inventor after: Huang Guangsheng Inventor after: Pan Fusheng Inventor before: Wu Liang Inventor before: Zhong Zhiyong Inventor before: Chen Yanning Inventor before: Wu Jiahao Inventor before: Chen Yonghua Inventor before: Yao Wenhui Inventor before: Huang Guangsheng Inventor before: Pan Fusheng |
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Effective date of registration: 20231130 Address after: Room 103, Building 2, International Maker Port Park, No. 130 Xiazhongdukou, Shapingba Street, Shapingba District, Chongqing, 400000 Patentee after: Chongqing Magnesium Energy Storage Technology Co.,Ltd. Address before: 400 000 No. 174 Zhengjie, Shapingba District, Chongqing Patentee before: Chongqing University |