CN108962621A - The core-shell structure compound and preparation method thereof of molte-salt synthesis preparation - Google Patents

The core-shell structure compound and preparation method thereof of molte-salt synthesis preparation Download PDF

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CN108962621A
CN108962621A CN201810776748.9A CN201810776748A CN108962621A CN 108962621 A CN108962621 A CN 108962621A CN 201810776748 A CN201810776748 A CN 201810776748A CN 108962621 A CN108962621 A CN 108962621A
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metallic compound
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salt
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CN108962621B (en
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王辉
曹苗苗
王荣方
武玉泰
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Jiaxing Qiyuan Network Information Technology Co ltd
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Qingdao University of Science and Technology
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H01G11/46—Metal oxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/22—Electrodes
    • H01G11/30—Electrodes characterised by their material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES OR LIGHT-SENSITIVE DEVICES, OF THE ELECTROLYTIC TYPE
    • H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
    • H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
    • H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/50—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese
    • H01M4/505—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of manganese of mixed oxides or hydroxides containing manganese for inserting or intercalating light metals, e.g. LiMn2O4 or LiMn2OxFy
    • 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/525—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron of mixed oxides or hydroxides containing iron, cobalt or nickel for inserting or intercalating light metals, e.g. LiNiO2, LiCoO2 or LiCoOxFy
    • 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 invention discloses a kind of core-shell structure compounds of molte-salt synthesis preparation, the compound includes the nucleome that metallic compound is constituted, and the shell that the metallic compound of package nucleome is constituted, the metallic compound include but is not limited to the carbide containing ion insertion, oxide, sulfide, selenides, antimonide, nitride or the phosphide prepared by fusion method.Specific preparation method is: transistion metal compound presoma decomposes at high temperature, releases gas and forms vacancy in the structure, and the metal salt under molten condition, which is embedded into vacancy, forms ion insertion, obtains the transistion metal compound of the structure with even porous.Preparation process is simple, non-environmental-pollution, and since product synthesizes at high temperature, crystallinity is high, and crystal structure is regular, and it is more excellent than the substance performance of single layer that the substance of core-shell structure can produce synergistic effect.

Description

The core-shell structure compound and preparation method thereof of molte-salt synthesis preparation
Technical field
The invention belongs to field of material technology, are related to a kind of method that core-shell structure compound is prepared in fuse salt, core Shell structure compound can be used for Faradic pseudo-capacitor, lithium electricity, the electrode material and enzyme-free glucose sensor of sodium electricity.
Background technique
As demand of the whole world to the energy increasingly increases, and people gradually increase the consciousness of environmental protection, in the past The energy will no longer adapt to requirement of the people to cleaning, efficient, safe, the economic energy, development cleaning green energy resource will be The most important thing developed now.Molte-salt synthesis is the new method of preparation nano material developed in recent years.Needed for this method Raw material is cheap and easy to get, preparation process is simple, cost is relatively low, product form is fine and yield is high, can effectively solve above-mentioned Problem.Supercapacitor had both reached the energy of battery as a kind of novel energy-storing equipment between traditional capacitor and battery Storage characteristics, and the power characteristic of capacitor is shown, energy density with higher, big power density can quickly fill Electric discharge, and the advantages that long cycle life.Transition metal element is the series of elements that the area d is in the periodic table of elements, valence There are unpaired electrons in layer track, therefore have the physicochemical property different from other elements.Transition metal oxide, which has, to be used as Electrode material is used as the purposes such as catalyst and gas sensitive.And transition metal oxide (such as Co3O4、CuO、NiO、MnO2Deng) Due to having extranuclear strucure similar with metal oxide containing precious metals, there is similar fake capacitance performance, and engage in trade than The electrode material of industry is more cheap and easy to get, and specific capacitance and energy density with higher and cheap, easy preparation etc. are excellent Point.
Currently, used method is mainly coprecipitation, hydro-thermal method, the methods of solution-gel method, these methods are usual In the case of step it is comparatively laborious, elapsed time is long, and the cost of substance needed for preparing is relatively high, and not environmentally.Ordinary circumstance The crystallinity that substance is formed under lower low-temperature condition is not high, and, method ratio high by the substance crystallization degree that high temperature melting molten salt process is formed It is relatively simple, it is environmentally protective, it is low in cost.
Summary of the invention
The object of the present invention is to provide a kind of methods that molte-salt synthesis prepares core-shell structure metallic compound.It solves common When method prepares transition metal oxide, existing technique is cumbersome, at high cost, the not high problem of crystallinity.
To achieve the goals above, the core-shell structure compound of molte-salt synthesis preparation of the present invention, the compound The shell that metallic compound including the nucleome that metallic compound is constituted, and package nucleome is constituted, the metallic compound packet It includes but is not limited by the carbide containing ion insertion of fusion method preparation, oxide, sulfide, selenides, antimonide, nitrogen Compound or phosphide.
A kind of scheme of the present invention, the preparation method of the core-shell structure compound of molte-salt synthesis preparation, specifically includes Following steps:
(1) preparation of nucleome metallic compound: transistion metal compound presoma and fuse salt are mixed, grinding, then High-temperature calcination is carried out, after cooling, washing, drying obtain the nucleome metallic compound containing ion insertion；
(2) preparation of shell metallic compound: by the resulting nucleome metallic compound of step (1) and transition metal compound Object presoma and fuse salt are by the processing such as grinding, then are calcined, and after cooling, wash, is dry, obtaining containing ion insertion Shell metallic compound；
Or the preparation of (2 ') shell metallic compound: by by the resulting nucleome metallic compound of step (1), at high temperature Fuse salt is melted in the salt bath to be formed and is chemically reacted, for example, Fe3O4+ urea → Fe2N3+…、CoP+K2Te → CoTe+ ..., Nucleome metallic compound surface layer is converted into the shell metallic compound containing ion insertion, then cooling, washing, drying；
Reaction temperature in the step (1), (2) and (2 ') is more than or equal to the decomposition temperature of transistion metal compound presoma High person in both degree and fuse salt fusing point.
Further, suitable nonionic surface active agent is added in step (1), (2) and the raw material of (2 '), reacts Raw material surfactant and transistion metal compound presoma and fuse salt or nucleome metallic compound, transistion metal compound Presoma and fuse salt or nucleome metallic compound and fuse salt react at high temperature together.
Further, transistion metal compound presoma of the present invention is that can chemically react at a temperature of certain Generate the substance of transition metal carbide, oxide, sulfide, selenides, antimonide, nitride or phosphide.Specifically, mistake Crossing metallic compound presoma is that labile transition metal salt or hydroxide can decompose at high temperature and generate transition gold Belong to oxide, including but not limited to nitrate, carbonate, oxalates or hydroxide, such as Ni (OH)2、CoCO3、Cu (CH3COO)2·H2O、Cu(OH)2、CuSO4·5H2O、Cu(NO3)2、Ni(NO3)2·6H2O、Co(NO3)2·6H2O、KMnO4、Ni (NO3)2、MnSO4、Mn(CH3COO)2、MoSO4、Mo(NO3)2、FeSO4、Fe(NO3)2And Na3VO3·2H2O etc., at this point, transition is golden The molar ratio for belonging to compounds precursors and fuse salt is 1:0.005~0.01.Transistion metal compound presoma is in certain temperature Under, by redox reaction or other reaction generate transition metal carbides, oxide, sulfide, selenides, antimonide, The substance of nitride or phosphide, such as Cu (CH3COO)2·H2O and glucose (Cu (CH3COO)2·H2O+ glucose → Cu2O +…)；Ni(NO3)2·6H2O and selenium powder (Ni (NO3)2·6H2O+ selenium powder → Ni3Se2+…)；Fe3O4With urea (Fe3O4+ urea →Fe2N3+…)；CoP and K2Te(CoP+K2Te → CoTe+ ...) etc..
Further, fuse salt of the present invention includes but is not limited to NaCl, NaOH, Na2SO4、K2SO4、NaNO3、 NaF、Na2S、Na2CO3、CH3COONa、HCOONa、Li2SO4、KOH、KCl、KNO3、K2CO3、NaF、CH3COOK or HCOOK.
Further, nonionic surface active agent of the present invention has high temperature resistance, including but not limited to NP- 5, NP-9, CO-630, alkyl phenol polyoxyethylene ether, nonylphenol polyoxyethylene ether or polyethylene glycol type nonionic surfactant.
Further, the present invention relates to the step of (1) and (2) in calcining, if air on calcination process without influence, can It is directly calcined in Muffle furnace and air tube furnace, if air has an impact to calcined product, such as avoids aoxidizing, needs to want sulphur Change, selenizing, phosphatization, nitridation etc., it is necessary to be carried out under gas shield.
Further, it is of the present invention have core-shell structure compound can be used as supercapacitor, lithium ion battery, Electrode material in sodium-ion battery, can also act as enzyme-free glucose sensor.
Compared with prior art, the invention has the following advantages: (1) transistion metal compound presoma, in high temperature Lower decomposition releases gas and forms vacancy in the structure, and the metal salt under molten condition, which is embedded into vacancy, forms ion insertion, Obtain the transistion metal compound of the structure with even porous；(2) with the transition metal compound of the structure with even porous Based on object, by oxidation reaction or molte-salt synthesis, then its surface coats transistion metal compound, further improves material Chemical property；(3) preparation process is simple, non-environmental-pollution, and since product synthesizes at high temperature, crystallinity is high, crystal knot Structure is regular.(4) it is more excellent than the substance performance of single layer to can produce synergistic effect for the substance of core-shell structure.
Detailed description of the invention
Fig. 1 is porous C uO@MnO prepared by the present invention2Scheme with the SEM of CuO, left figure is the SEM of CuO, and right figure is CuO@ MnO2SEM figure it can be seen that CuO size be less than CuO@MnO2。
Fig. 2 is porous C uO@MnO prepared by the present invention2BET test curve
Fig. 3 is porous C uO@MnO prepared by the present invention2(with CuO and MnO obtained by conventional calcination2Compare) it is used as super electricity The test of the electrode material capacitive property of container.
Fig. 4 is CuO@MnO prepared by the present invention2As cyclic voltammetric of the enzyme-free glucose sensor in 0.1M NaOH Test chart.
Fig. 5 is CuO@MnO prepared by the present invention2As staircase curve of the enzyme-free glucose sensor in 0.1M NaOH.
Fig. 6 is CuO@MnO prepared by the present invention2As anti-interference survey of the enzyme-free glucose sensor in 0.1M NaOH Examination.
Fig. 7 is that the present invention is the fitting a straight line obtained by Fig. 5 staircase curve.
Fig. 8 is NiO@Co prepared by the present invention3O4The cyclical stability that positive electrode as lithium ion battery carries out is surveyed Examination.
Fig. 9 is NiO@Co prepared by the present invention3O4The cyclical stability that positive electrode as sodium ion electrode carries out is surveyed Examination.
Specific embodiment
It Porous transition metal compound of the invention is further detailed below by embodiment preparation and urges Changing activity can be described further.
Embodiment 1: porous C uO@MnO2Preparation
(1) 150mg (CH3COO) is weighed2·Cu·(H2O), 3g NaNO3, the alkyl phenol polyoxyethylene ether mixing of 150mg Grinding uniformly, is placed in tube furnace, is warming up to 350 DEG C of calcinings, keeps 2h, after it is cooled to room temperature, taking-up sample be placed in from In heart pipe, add distilled water centrifuge washing for several times, remove NaNO3,80 DEG C of dryings obtain presoma target product CuO.
(2) 50mg CuO and 50mg KMnO are weighed4With 3g Na2SO4It is ground, calcining keeps 2h at 300 DEG C, to it After being cooled to room temperature, takes out sample and be placed in centrifuge tube, add distilled water centrifuge washing for several times, remove Na2SO4, 80 DEG C of dryings obtain To target product CuO@MnO2。
Scheme from Fig. 1 SEM, it can be found that porous C uO@MnO obtained by the present embodiment2With the resulting presoma target of step (1) Product CuO is compared, and has loose porous structure, and as can be drawn from Figure 2, porous C uO@MnO2 has apparent pore-size distribution, Specific surface area reaches 59.160m2/g.From figure 3, it can be seen that porous C uO@MnO2Specific capacitance is about 145.3F.g-1, presoma Target product CuOSpecific capacitance 89.7F.g-1 , capacitive property improves 56Fg-1.Fig. 4-7 is manufactured in the present embodiment porous CuO@MnO2As the electrode material of enzyme-free glucose sensor, the performance test curve in 0.1M NaOH.4 circulation from figure Volt-ampere is as can be seen that porous C uO@MnO2There is oxidation catalysis to glucose.Fig. 5 chronoamperogram illustrates CuO@MnO2 After electrolyte is added in glucose solution, electric current is obviously increased rapidly.Fig. 7 is the fitting a straight line done by 5, it can be seen that The response concentration of glucose is 1-1000 μM.Fig. 6 is the test of glucose selective, under normal conditions can be there are many reproducibility object Matter exists simultaneously in sample, i.e., ascorbic acid (AA), carbohydrate and uric acid (UA), these compounds will interfere grape The detection of sugar.The physiological concentration of glucose is usually 3-8mM, higher than 10 times of chaff interferent.Successively add in 0.1M NaOH solution Enter 1.0mM glucose solution and 0.1mM chaff interferent, corresponding response current is as shown in fig. 6, voltage is+0.5V.Ascorbic acid and The response current of uric acid is the 4.49% and 2.71% of glucose respectively.As can be seen from the figure come, grape is glycoxidative be have it is bright Aobvious current-responsive, and chaff interferent does not have apparent current-responsive, illustrates CuO@MnO2Electrode is in alkaline medium to grape Sugar has high selectivity.In alkaline medium, CuO@MnO2Meeting surface enrichment negative electrical charge, simultaneously because chaff interferent (AA, UA) The deprotonation in alkaline medium and have negative electrical charge, therefore by negatively charged CuO@MnO2Repel, shows lower letter Number.
The preparation of embodiment 2:CuO@NiO
Cu(OH)2Preparation: 20mL 0.1M NaOH is added dropwise to 20mL 0.05M CuCl2, stirring at normal temperature 5min, Centrifuge washing, 60 DEG C of dryings obtain transistion metal compound presoma Cu (OH)2。
(1) 150mg Cu (OH) is weighed2, 3g NaNO3It is uniform with the octadecylamine mixed grinding of 150mg, it is placed in tube furnace, 350 DEG C of calcinings are warming up to, 2h is kept, after it is cooled to room temperature, sample is taken out and is placed in centrifuge tube, add distilled water centrifuge washing For several times, NaNO is removed3, 80 DEG C of dryings obtain presoma target product CuO.
(2) 50mg CuO, 50mg Ni (NO are weighed3)2·6H2O, 5g Na2SO4Mixed grinding is uniform, is placed in tubular type, rises Temperature keeps 2h, after it is cooled to room temperature, takes out sample and be placed in centrifuge tube, add distilled water centrifuge washing number to 300 DEG C of calcinings It is secondary, remove Na2SO4, 80 DEG C of dryings obtain target product CuO@NiO.
After measured, present invention gained CuO@NiO has loose compared with presoma target product CuO prepared by step (1) Porous structure, capacitive property improve 67Fg-1.The response concentration of the response of glucose is 1-800 μM.
Embodiment 3: porous NiO@Co3O4Preparation
(1) 150mgNi (NO is weighed3)2·6H2O, 3gNaNO3It is uniform with the CO-630 mixed grinding of 150mg, it is placed in tubular type In furnace, be warming up to 500 DEG C of calcinings, keep 2h, after it is cooled to room temperature, takes out sample and be placed in centrifuge tube, add distilled water from The heart washs for several times, removes NaNO3, 80 DEG C of dryings obtain presoma target product NiO.
(2) 50mgNiO, 50mgCo (NO are weighed3)2·6H2O, 5gLiNO3Mixed grinding is uniform, is placed in tube furnace, rises Temperature keeps 2h, after it is cooled to room temperature, takes out sample and be placed in centrifuge tube, add distilled water centrifuge washing number to 300 DEG C of calcinings It is secondary, remove LiNO3, 80 DEG C of dryings obtain presoma target product NiO@Co4O3.Here fuse salt have certain reduction or Person's oxidation also plays the effect to form (Li/Na) intercalation.
After measured, present invention gained NiO@Co3O4Compared with the NiO of step (1) preparation, capacitor has reached 580F g-1.The response concentration of the response of glucose is 1-1200 μM.Stable circulation is carried out using it as the positive electrode of lithium ion battery Property test when, current density be 50mA/g when, the capacitance of lithium electricity reaches 580Fg-1。
The positive electrode of NiO@prepared by the present embodiment 3 as li-ion electrode, in 1mol/m3LiPF6Ethylene carbonate (EC) in the mixed solvent of ethyl methyl carbonate (EMC) and dimethyl carbonate (DMC) (volume ratio 1:1:1) carries out stable circulation Property test, charging and discharging currents density be 50mA/g when, capacitor reaches 478mAh/g.
NiO@Co manufactured in the present embodiment3O4As sodium ion electrode positive electrode, fiberglass packing is used as separator electricity Solution liquid is 1.0M NaClO4, tested in PC=100vol% and 5%FEC, be 30mA/g's in charging and discharging currents density When, capacitance reaches 580mAh/g.
Embodiment 4: porous C u2O@Cu2The preparation of S
Weigh 150mgCu (CH3COO)2·H2O, 100mg glucose, 3gNaNO3, the polyoxyethylene of the alkyl phenol of 150mg Ether mixed grinding is uniform, is placed in tube furnace, in N2In the state of protection, 350 DEG C of calcinings are warming up to, keep 2h；To its cooling To room temperature, takes out sample and be placed in centrifuge tube, add distilled water centrifuge washing for several times, remove NaNO3,80 DEG C of dryings, before obtaining Drive body target product Cu2O。
Obtained Cu2O takes out 50mg and KCl and places a porcelain boat, another places the sulphur powder of 28.75mg here Cu2The molar ratio of O and the substance of sulphur powder is 1:2.3), in N2Protection under be heated to 450 DEG C of two hours of calcining, then cool down KCl salt is removed to room temperature, obtains Cu2O@Cu2S。
Embodiment 5, porous Fe C@Ni3Se2
(1) 150mgFeCl is weighed3·6H2The CO-630 mixed grinding of O, 3gNaCl and 150mg are uniform, are placed in tube furnace It is passed through N2, 810 DEG C of calcinings are warming up to, 2h is kept, after it is cooled to room temperature, sample is taken out and is placed in centrifuge tube, add distilled water Centrifuge washing for several times, removes NaCl, and 80 DEG C of dryings obtain presoma target product FeC.
(2) 50mgFeC, 50mgNi (NO are weighed3)2·6H2O, 32mg selenium powder, 5gKNO3Mixed grinding is uniform, is placed in tubular type In furnace, 450 DEG C of calcinings are warming up to, keep 1.5h, after it is cooled to room temperature, sample is taken out and is placed in centrifuge tube, add distilled water Centrifuge washing for several times, removes KNO3, 80 DEG C of dryings obtain presoma target product FeC@Ni3Se2。
Embodiment 6, porous Fe3O4@Fe2N3
(1) 150mgFeCl is weighed3·6H2The NP-9 mixed grinding of O, 3gKCl and 150mg are uniform, are warming up to 810 DEG C and forge It burns, keeps 2h, after it is cooled to room temperature, takes out sample and be placed in centrifuge tube, add distilled water centrifuge washing for several times, remove KCl, 100 DEG C of dryings obtain presoma target product Fe3O4。
(2) 50mgFe is weighed3O4, 200mg urea, 3gKNO3Mixed grinding is abundant, is placed in tube furnace, is passed through N2Heating It to 520 DEG C of calcining a period of times, is cooled to room temperature to it, takes out sample and be placed in centrifuge tube, add distilled water centrifuge washing for several times, Remove KNO3, 80 DEG C of dryings obtain presoma target product Fe3O4@Fe2N3。
Embodiment 7, porous C oP@CoTe
(1) 150mgCo (NO is weighed3)2·6H2O, 150mgPCl3, 3gNaNO3It is uniform with 150mgNP-5 mixed grinding, it sets In tube furnace, under Ar gas shielded, be warming up to 520 DEG C of calcinings, keep 2h, after it is cooled to room temperature, take out sample be placed in from In heart pipe, add distilled water centrifuge washing for several times, removes NaNO3, 80 DEG C of dryings obtain presoma target product CoP.
(2) 45mg presoma CoP, 20mgK are weighed2Te, 3gLiNO3Mixed grinding is abundant, is placed in tube furnace, is passed through N2 500 DEG C are heated to after it is cooled to room temperature, sample is taken out and is placed in centrifuge tube, add distilled water centrifuge washing for several times, remove LiNO3, 80 DEG C of dryings obtain target product CoP@CoTe.

Claims (7)

1. the core-shell structure compound of molte-salt synthesis preparation, which is characterized in that the compound includes what metallic compound was constituted Nucleome, and the shell that the metallic compound of nucleome is constituted is wrapped up, the metallic compound includes but is not limited to pass through fusion method The carbide containing ion insertion, oxide, sulfide, selenides, antimonide, nitride or the phosphide of preparation.
2. a kind of preparation method of the core-shell structure compound of molte-salt synthesis preparation described in claim 1, which is characterized in that tool Body the following steps are included:
(1) preparation of nucleome metallic compound: transistion metal compound presoma and fuse salt are mixed, then grinding carries out High-temperature calcination, after cooling, washing, drying obtain the nucleome metallic compound containing ion insertion；
(2) preparation of shell metallic compound: before the resulting nucleome metallic compound of step (1) and transistion metal compound It drives body and fuse salt passes through the processing such as grinding, then calcined, after cooling, washing, drying obtain the shell containing ion insertion Metallic compound；
Or the preparation of (2 ') shell metallic compound: by by the resulting nucleome metallic compound of step (1), under high temperature, molten Melt salt and melt in the salt bath to be formed and chemically reacted, nucleome metallic compound surface layer is converted into the shell containing ion insertion Metallic compound, then cooling, washing, drying；
Reaction temperature in the step (1), (2) and (2 ') be more than or equal to transistion metal compound presoma decomposition temperature and High person in fuse salt fusing point the two.
3. the preparation method of the core-shell structure compound of molte-salt synthesis preparation according to claim 1, which is characterized in that Nonionic surface active agent is added in step (1), (2) and the raw material of (2 ').
4. the preparation method of the core-shell structure compound of molte-salt synthesis preparation according to claim 1, which is characterized in that mistake Crossing metallic compound presoma is that chemical reaction can occur at a temperature of certain to generate transition metal carbide, oxide, vulcanization Object, selenides, antimonide, nitride or phosphide substance.
5. the preparation method of the core-shell structure compound of molte-salt synthesis preparation according to claim 1, which is characterized in that molten Melting salt includes but is not limited to NaCl, NaOH, Na2SO4、K2SO4、NaNO3、NaF、Na2S、Na2CO3、CH3COONa、HCOONa、 Li2SO4、KOH、KCl、KNO3、K2CO3、NaF、CH3COOK or HCOOK.
6. the preparation method of the core-shell structure compound of molte-salt synthesis preparation according to claim 5, which is characterized in that non- Ionic surfactant have high temperature resistance, including but not limited to NP-5, NP-9, CO-630, alkyl phenol polyoxyethylene ether, Nonylphenol polyoxyethylene ether or polyethylene glycol type nonionic surfactant.
7. the preparation method of the core-shell structure compound of molte-salt synthesis preparation according to claim 1, which is characterized in that tool There is core-shell structure compound to can be used as supercapacitor, lithium ion battery, the electrode material in sodium-ion battery, can also use Make enzyme-free glucose sensor.
CN201810776748.9A 2018-07-13 2018-07-13 Core-shell structure compound prepared by molten salt method and preparation method thereof Active CN108962621B (en)

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CN110474036A (en) * 2019-08-29 2019-11-19 桑顿新能源科技(长沙)有限公司 Anode material of lithium battery and preparation method thereof, lithium battery anode, lithium battery and power supply unit
CN112117448A (en) * 2020-09-24 2020-12-22 毛小林 Hollow nano core-shell structure compound prepared in ionic liquid and preparation method thereof
CN112225221A (en) * 2020-06-05 2021-01-15 上海大学 I-MAX phase material with core-shell structure and preparation method thereof
CN112591752A (en) * 2020-12-30 2021-04-02 松山湖材料实验室 Rapid preparation of V by molten salt chemical reaction2AlC powder preparation method and powder application thereof
CN117673331A (en) * 2024-01-31 2024-03-08 帕瓦(长沙)新能源科技有限公司 Positive electrode material coating material and preparation method thereof, modified positive electrode material and preparation method thereof, and sodium ion battery

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110247030A (en) * 2019-05-23 2019-09-17 天津大学 Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures
CN110247030B (en) * 2019-05-23 2022-05-10 天津大学 Method for preparing three-dimensional porous microspheres surrounded by nitrogen/sulfur co-doped carbon nanosheets embedded with metal/carbon yolk shell structures
CN110474036A (en) * 2019-08-29 2019-11-19 桑顿新能源科技(长沙)有限公司 Anode material of lithium battery and preparation method thereof, lithium battery anode, lithium battery and power supply unit
CN112225221A (en) * 2020-06-05 2021-01-15 上海大学 I-MAX phase material with core-shell structure and preparation method thereof
CN112117448A (en) * 2020-09-24 2020-12-22 毛小林 Hollow nano core-shell structure compound prepared in ionic liquid and preparation method thereof
CN112591752A (en) * 2020-12-30 2021-04-02 松山湖材料实验室 Rapid preparation of V by molten salt chemical reaction2AlC powder preparation method and powder application thereof
CN117673331A (en) * 2024-01-31 2024-03-08 帕瓦(长沙)新能源科技有限公司 Positive electrode material coating material and preparation method thereof, modified positive electrode material and preparation method thereof, and sodium ion battery

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