CN113066964A - Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof - Google Patents

Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof Download PDF

Info

Publication number
CN113066964A
CN113066964A CN202110277541.9A CN202110277541A CN113066964A CN 113066964 A CN113066964 A CN 113066964A CN 202110277541 A CN202110277541 A CN 202110277541A CN 113066964 A CN113066964 A CN 113066964A
Authority
CN
China
Prior art keywords
inlaid
double
carbon
hollow
metal phosphide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN202110277541.9A
Other languages
Chinese (zh)
Other versions
CN113066964B (en
Inventor
吴泽亮
王珺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanchang University
Original Assignee
Nanchang University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanchang University filed Critical Nanchang University
Priority to CN202110277541.9A priority Critical patent/CN113066964B/en
Publication of CN113066964A publication Critical patent/CN113066964A/en
Application granted granted Critical
Publication of CN113066964B publication Critical patent/CN113066964B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • 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
    • H01M4/5805—Phosphides
    • 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
    • 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 belongs to the technical field of lithium-sulfur batteries, and particularly relates to a double-metal phosphide-inlaid carbon hollow nano cage as well as a preparation method and an application thereof, wherein the double-metal phosphide-inlaid carbon hollow nano cage comprises the following steps: dispersing the nickel cobalt prussian blue derivative in a liquid medium to prepare a dispersion liquid, and adding dopamine hydrochloride into the dispersion liquid to prepare polydopamine-coated nickel cobalt prussian blue; calcining the polydopamine-coated nickel-cobalt Prussian blue derivative to prepare a carbon hollow nanocage with embedded nickel-cobalt double-metal particles; phosphine is used as a phosphating agent, and the carbon hollow nano cage inlaid with the bimetallic particles is phosphated in one step to prepare the carbon hollow nano cage inlaid with the bimetallic phosphide; preparing dispersion liquid from the double-metal phosphide-inlaid carbon hollow nano cage, carbon black and polyvinylidene fluoride, coating the dispersion liquid on a polypropylene diaphragm, and drying to obtain the multifunctional diaphragm; the invention obviously improves the comprehensive performance of the lithium-sulfur battery.

Description

Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof
Technical Field
The invention belongs to the technical field of lithium-sulfur batteries, and particularly relates to a double-metal phosphide-inlaid carbon hollow nano cage and a preparation method and application thereof.
Background
The lithium-sulfur battery generally comprises four parts, namely a metal lithium cathode, a sulfur anode, an electrolyte and a diaphragm, is a high-energy-density battery system which realizes mutual conversion of electric energy and chemical energy by the fracture generation of a sulfur-sulfur bond, has the advantages of low cost, environmental friendliness and the like, and has theoretical specific capacity and energy density of 1675mAh h respectively-1And 2600Wh kg-1And is more than five times of the theoretical energy density of the lithium ion battery which is commercialized at present.
However, there are still some problems with lithium sulfur batteries:
(1) s and Li2S2/Li2S is an electronic insulating material, so that greater internal resistance can be generated in the charge-discharge cycle process of the battery, and the activity of the reaction is reduced; the method for solving the problem at present mainly compounds S and various carbon materials with good conductivity, which can greatly reduce the loading capacity of S to a certain extent; in addition, due to Li2Poor conductivity of S, and difficult complete conversion of S to Li on the electrode2S, and thus it is often difficult to obtain a theoretical specific capacity;
(2) due to S (2.03g cm)-3) And Li2S(1.66g cm-3) There is a density difference between them, and thus in a fully discharged state, sulfur will undergo a volume expansion of up to 80%, and severe volume expansion will cause exfoliation and failure of the electrode material, thereby causing a drastic deterioration in battery performance, while also limiting further applications of sulfur positive electrodes having a high loading;
(3) the working mechanism of the lithium-sulfur battery is a 'solid-liquid-solid' process, and polysulfide intermediates generally have good solubility in an organic solvent, so that a positive electrode material is continuously dissolved out into an electrolyte in a circulating process to cause irreversible capacity; in addition, S is superior to Li in solubility in organic solvent2S, resulting in a faster conversion of S to polysulfide than polysulfide to Li2Conversion of S, which further allows electricity to be generatedIncreasing the polysulfide content in the electrolyte; at the same time, polysulfide dissolved in the electrolyte is reduced to Li2S usually covers the surface of the positive electrode, which reduces the conductivity of the positive electrode;
(4) shuttle effect: since polysulfide can be well dissolved in the organic ether electrolyte, it can easily diffuse to the surface of the negative electrode, and thus directly react with the metal lithium sheet of the negative electrode, resulting in capacity loss, and Li generated by the reaction2S has poor conductivity and can also affect the cycling stability of the cathode to a certain degree; major research efforts are currently conducted to improve the conductivity of the positive electrode and inhibit the shuttle effect of the polar material, such as adding a large amount of conductive carbon material, polar metal compound, etc., while the energy density of the positive electrode is more or less reduced by the added sulfur host material of the positive electrode.
Therefore, in view of the above problems, further research is still needed on how to further improve the performance of the lithium sulfur battery.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a double-metal phosphide-inlaid carbon hollow nano cage and a preparation method and application thereof, the invention coats a polydopamine layer on the outer layer of a nickel-cobalt Prussian blue derivative, generates the hollow nickel-cobalt double-metal particle-inlaid carbon hollow nano cage at high temperature, prepares the nickel-cobalt double-metal phosphide-inlaid carbon hollow nano cage by a one-step phosphorization method, and coats the nickel-cobalt double-metal phosphide-inlaid carbon hollow nano cage on a polypropylene diaphragm (Celgard2500) for the first time to obtain a multifunctional diaphragm which is applied to a lithium-sulfur battery system so as to enhance the comprehensive performance of the lithium-sulfur battery system.
The present invention is thus achieved.
The first purpose of the invention is to provide a preparation method of a double-metal phosphide inlaid carbon hollow nano cage, which comprises the following steps:
s1 preparation of polydopamine-coated nickel cobalt Prussian blue compound (Ni-Co-PBA @ PDA)
Dispersing the nickel cobalt prussian blue derivative and dopamine hydrochloride in a liquid medium containing an initiator, and under the action of the initiator, carrying out self-polymerization on the dopamine on the surface of the nickel cobalt prussian blue derivative to generate poly-dopamine so as to prepare Ni-Co-PBA @ PDA;
s2 preparation of hollow carbon nanocage (Ni-Co @ C) embedded with nickel-cobalt double-metal particles
Calcining the Ni-Co-PBA @ PDA prepared in S1 at 400-700 ℃ in a protective gas atmosphere to obtain Ni-Co @ C;
s3 preparation of double-metal phosphide inlaid carbon hollow nanocage (Ni-Co-P @ C)
And (2) taking phosphine as a phosphating agent, and preparing the Ni-Co @ C prepared by S2 at 350-450 ℃ by adopting a one-step phosphating method.
Preferably, in S1, the initiator is a tris (hydroxymethyl) aminomethane buffer solution, the liquid medium is a mixed solution prepared from water and ethanol at a volume ratio of 0.5-2: 1, and the concentration of the initiator in the liquid medium is 5-15 mmol/L.
Preferably, in S2, the heating rate is 2-10 ℃/min, and the calcination time is 1-4 h.
Preferably, in S3, the heating rate is 2-10 ℃/min-1And the phosphating time is 1-4 h.
Preferably, in S3, in the process of the one-step phosphating method, the phosphating agent is obtained by directly introducing phosphine gas or decomposing sodium hypophosphite by heating at high temperature to generate phosphine gas, and the mass ratio of the sodium hypophosphite to Ni-Co @ C is 5-10: 1.
The second object of the present invention is to provide Ni-Co-P @ C prepared by the above-mentioned preparation method.
It is a third object of the present invention to provide a multifunctional separator (Ni-Co-P @ C/PP) obtained by coating the above Ni-Co-P @ C on a commercial polypropylene separator.
Preferably, the coating process specifically comprises: preparing a dispersion solution from the Ni-Co-P @ C, the carbon black and the polyvinylidene fluoride, coating the dispersion solution on a commercial polypropylene diaphragm, and drying to obtain the multifunctional diaphragm.
Preferably, the dispersing agent of the dispersion liquid is N-methyl pyrrolidone, Ni-Co-P @ C, and the mass ratio of carbon black to polyvinylidene fluoride is 7-8: 2-1: 1.
The fourth purpose of the invention is to provide the application of the Ni-Co-P @ C/PP in the lithium-sulfur battery.
Compared with the prior art, the invention has the advantages that:
(1) the poly dopamine layer is coated on the outer layer of the nickel cobalt Prussian blue derivative, the hollow carbon nanocage inlaid with nickel cobalt bimetallic particles is generated in situ at high temperature, and the hollow carbon nanocage inlaid with phosphide of the nickel cobalt bimetallic with a regular structure is prepared for the first time by a one-step phosphating method, and the structure of the hollow carbon nanocage is as follows: the nickel-cobalt double-metal phosphide hollow nanocage is of a cubic structure, the interior of the cube is of a hollow structure, the outer side of the hollow nanocage is wrapped by a polydopamine-derived carbon layer, and the inner side of the hollow nanocage is attached with embedded nickel-cobalt phosphide (capable of providing Ni-Co-P active sites);
(2) the nickel-cobalt double-metal phosphide hollow nanometer cage is coated on a polypropylene diaphragm for the first time to prepare a multifunctional diaphragm, and after the multifunctional diaphragm is used for preparing a lithium-sulfur battery, the performance of the lithium-sulfur battery can be improved, and the mechanism is as follows:
through the construction of the hollow structure, the volume expansion of the active substance in the charging and discharging process can be effectively relieved, and the stability of the battery structure is ensured; the attached Ni-Co-P active sites can effectively adsorb polysulfide, limit the polysulfide in the reaction process on the positive electrode side, simultaneously effectively promote catalytic conversion among the polysulfide, promote the conversion of long-chain liquid polysulfide to solid short-chain lithium sulfide, and inhibit the shuttle effect in the battery reaction, thereby improving the discharge specific capacity, the rate capability and the cycle performance of the battery; in addition, the bimetal phosphide has excellent conductivity, and is matched with the carbon layer on the outer side and the hollow structure in the inner part, so that the bimetal phosphide is more favorable for the rapid conduction of electrons and ions;
(3) the multifunctional diaphragm is used for the lithium-sulfur battery, the positive electrode and the negative electrode can be separated by the diaphragm, the short circuit phenomenon is avoided, the pore channel in the diaphragm is mainly responsible for transferring ions, the battery reaction circulation is promoted to continue, the electrochemical performance of the battery is obviously improved, and when the sulfur surface loading is 1.8mg cm-2Can be used at high current 5C (1C: 1672mA g)-1) Strip for packaging articlesThe discharge specific capacity is improved by 2.67 times compared with that of the common polypropylene diaphragm, the cyclic charge-discharge test can be carried out for 1000 circles under the current density of 0.5C, the average attenuation rate per circle is only 0.056 percent and is far less than 0.112 percent (731 circles) of the common polypropylene diaphragm battery, and the cyclic charge-discharge test is carried out under the conditions of different high-surface loading capacity (2.4-4.5 mg cm)-2) The high cycle stability is still maintained;
(4) the method for preparing the multifunctional diaphragm is simple, the raw materials are easy to obtain, and the multifunctional diaphragm is suitable for improving the performance of the lithium-sulfur battery.
Drawings
Figures 1, 2 and 3 are XRD, SEM and TEM, respectively, of nickel cobalt prussian blue prepared in example 1;
FIG. 4, FIG. 5 and FIG. 6 are XRD, SEM and TEM images, respectively, of Ni-Co @ C prepared in example 1;
FIG. 7, FIG. 8 and FIG. 9 are SEM and TEM images of Ni-Co-P @ C prepared in example 1, respectively;
fig. 10 is a cross-sectional SEM image of the multifunctional separator prepared in example 1;
fig. 11 is a mechanical folding test digital photograph of the multifunctional separator prepared in example 1;
FIG. 12 is a charge-discharge capacity-voltage curve at a rate of 0.1 to 5C for a lithium-sulfur battery assembled using the multifunctional separator prepared in example 1;
fig. 13 is a charge and discharge capacity-voltage curve at a rate of 5C for a lithium-sulfur battery assembled using the multifunctional separator prepared in example 1 and a general polypropylene separator;
FIG. 14 is a lithium sulfur battery assembled using the multifunctional separator prepared in example 1 and a general polypropylene separator (sulfur loading of 1.8mg cm)-2) A charge-discharge long cycle test chart under 0.5C multiplying power;
FIG. 15 shows lithium sulfur cells assembled using the multifunctional separator of example 1 at various sulfur loadings ranging from 2.4 to 3.5mg cm-2A long cycle test chart with the multiplying power of 0.5C;
FIG. 16 shows sulfur loading of 4.5mg cm for a lithium sulfur battery assembled using the multifunctional separator prepared in example 1-2Double, doubleLong cycle test plot with a rate of 0.2C.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The following test methods and detection methods, unless otherwise specified, are conventional methods; the starting materials and reagents are not specifically indicated and are commercially available.
Example 1
A preparation method of a multifunctional diaphragm of a lithium-sulfur battery comprises the following steps:
(1) preparation of nickel cobalt prussian blue derivative (Ni-Co-PBA): 1.75 g (20 mmol) of nickel nitrate hexahydrate and 2.65 g (75 mmol) of trisodium citrate are dissolved in 200 ml of deionized water to form solution A; dissolving 1.33 g of potassium cobalt cyanide in 200 ml of deionized water to form a solution B; then mixing the solution A and the solution B, and finishing the whole process in the stirring process; stirring for half an hour at room temperature, standing for 18 hours, then washing by centrifugation, collecting light blue precipitate, and drying in vacuum to obtain the nickel cobalt Prussian blue derivative.
(2) Dopamine hydrochloride-coated nickel cobalt prussian blue derivative (Ni-Co-PBA @ PDA): dispersing 200 mg of the prepared Ni-Co-PBA powder in 60 ml of a mixed solution of ethanol and deionized water containing 10 mmol per liter of tris (hydroxymethyl) aminomethane buffer solution, wherein the volume ratio of water to ethanol is 1: 1; after ultrasonic dispersion, 200 mg of dopamine hydrochloride is added into the mixed solution, stirred for 12 hours, filtered, washed and dried to obtain solid powder.
(3) Preparation of carbon layer-wrapped bimetallic hollow nanocages (Ni-Co @ C): 0.5 g of Ni-Co-PBA @ PDA powder is put into a quartz boat and calcined in a tube furnace in argon atmosphere, the calcination temperature is 600 ℃, and the heating rate is 5 ℃/min-1The calcination time is 2 h.
(4) Preparation of bimetallic hollow phosphide nanocages (Ni-Co-P @ C): 0.1 g of Ni-Co @ C and 1 g of phosphorous monohydrateSodium acid is respectively placed in two quartz boats, the boat carrying sodium hypophosphite is placed at the upstream of a heating pipe, argon is used as carrier gas to ensure that phosphine gas generated by decomposition in the high-temperature process can flow through the surface of Ni-Co @ C, the phosphating temperature is 400 ℃, the phosphating time is 2h, and the heating rate is 5 ℃/min-1And cooling, washing and drying to obtain Ni-Co-P @ C powder.
(5) Preparation of multifunctional separator (Ni-Co-P @ C/PP): the prepared bimetallic hollow nano cage (Ni-Co-P @ C), carbon black and polyvinylidene fluoride are ground and mixed according to the mass ratio of 8:1:1, then are dispersed in an N-methyl pyrrolidone solution, and after stirring for 8 hours, a coating machine is used for coating the slurry on a commercial polypropylene diaphragm (Celgard2500), and then after drying, the disc with the diameter of 19 mm is cut.
Example 2
A preparation method of a multifunctional diaphragm of a lithium-sulfur battery comprises the following steps:
(1) preparation of nickel cobalt prussian blue derivative (Ni-Co-PBA): dissolving 0.35 g of nickel nitrate hexahydrate and 0.53 g of trisodium citrate in 200 ml of deionized water to form solution A; 0.266 g of potassium cobalt cyanide was dissolved in 200 ml of deionized water to form solution B; then mixing the solution A and the solution B, and finishing the whole process in the stirring process; stirring for half an hour at room temperature, standing for 18 hours, then washing by centrifugation, collecting light blue precipitate, and drying in vacuum to obtain the nickel cobalt Prussian blue derivative.
(2) Dopamine hydrochloride-coated nickel cobalt prussian blue derivative (Ni-Co-PBA @ PDA): dispersing 200 mg of the prepared Ni-Co-PBA powder in 60 ml of a mixed solution of ethanol and deionized water containing 15mmol/l of tris (hydroxymethyl) aminomethane buffer, wherein the volume ratio of water to ethanol is 2: 1; after ultrasonic dispersion, 200 mg of dopamine hydrochloride is added into the mixed solution, stirred for 12 hours, filtered, washed and dried to obtain solid powder.
(3) Preparation of carbon layer-wrapped bimetallic hollow nanocages (Ni-Co @ C): 0.5 g of Ni-Co-PBA @ PDA powder is put into a quartz boat and calcined in a tube furnace in argon atmosphere, the calcination temperature is 400 ℃, and the heating speed is increasedThe rate is 2 ℃/min-1The calcination time is 4 h.
(4) Preparation of bimetallic hollow phosphide nanocages (Ni-Co-P @ C): respectively placing 0.1 g of Ni-Co @ C and 1 g of sodium hypophosphite monohydrate in two quartz boats, placing the boats carrying the sodium hypophosphite at the upstream of a heating pipe, taking argon as carrier gas to ensure that phosphine gas generated by decomposition in the high-temperature process can flow through the surface of the Ni-Co @ C, the phosphating temperature is 350 ℃, the phosphating time is 4h, and the heating rate is 2 ℃/min-1And cooling, washing and drying to obtain Ni-Co-P @ C powder.
(5) Preparation of multifunctional separator (Ni-Co-P @ C/PP): the prepared bimetallic hollow nano cage (Ni-Co-P @ C), carbon black and polyvinylidene fluoride are ground and mixed according to the mass ratio of 7:2:1, then are dispersed in an N-methyl pyrrolidone solution, and after stirring for 8 hours, a coating machine is used for coating the slurry on a commercial polypropylene diaphragm (Celgard2500), and then after drying, the disc with the diameter of 19 mm is cut.
Example 3
A preparation method of a multifunctional diaphragm of a lithium-sulfur battery comprises the following steps:
(1) preparation of nickel cobalt prussian blue derivative (Ni-Co-PBA): dissolving 1.75 g of nickel nitrate hexahydrate and 2.65 g of trisodium citrate in 200 ml of deionized water to form solution A; dissolving 1.33 g of potassium cobalt cyanide in 200 ml of deionized water to form a solution B; then mixing the solution A and the solution B, and finishing the whole process in the stirring process; stirring for half an hour at room temperature, standing for 18 hours, then washing by centrifugation, collecting light blue precipitate, and drying in vacuum to obtain the nickel cobalt Prussian blue derivative.
(2) Dopamine hydrochloride-coated nickel cobalt prussian blue derivative (Ni-Co-PBA @ PDA): dispersing 200 mg of the prepared Ni-Co-PBA powder in 60 ml of a mixed solution of ethanol and deionized water containing 5mmol per liter of tris (hydroxymethyl) aminomethane buffer solution, wherein the volume ratio of water to ethanol is 1: 2; after ultrasonic dispersion, 200 mg of dopamine hydrochloride is added into the mixed solution, stirred for 12 hours, filtered, washed and dried to obtain solid powder.
(3)Preparation of carbon layer-wrapped bimetallic hollow nanocages (Ni-Co @ C): 0.5 g of Ni-Co-PBA @ PDA powder is put into a quartz boat and calcined in a tube furnace in argon atmosphere, the calcination temperature is 700 ℃, the heating rate is 10 ℃/min-1The calcination time is 1 h.
(4) Preparation of bimetallic hollow phosphide nanocages (Ni-Co-P @ C): respectively placing 0.1 g of Ni-Co @ C and 1 g of sodium hypophosphite monohydrate in two quartz boats, placing the boats carrying the sodium hypophosphite at the upstream of a heating pipe, taking argon as carrier gas to ensure that phosphine gas generated by decomposition in the high-temperature process can flow through the surface of the Ni-Co @ C, the phosphating temperature is 450 ℃, the phosphating time is 1h, and the heating rate is 10 ℃/min-1And cooling, washing and drying to obtain Ni-Co-P @ C powder.
(5) Preparation of multifunctional separator (Ni-Co-P @ C/PP): the prepared bimetallic hollow nano cage (Ni-Co-P @ C), carbon black and polyvinylidene fluoride are ground and mixed according to the mass ratio of 8:1:1, then are dispersed in an N-methyl pyrrolidone solution, and after stirring for 8 hours, a coating machine is used for coating the slurry on a commercial polypropylene diaphragm (Celgard2500), and then after drying, the disc with the diameter of 19 mm is cut.
The properties of the materials prepared in the above examples 1 to 3 are similar, and the structure of the materials is characterized by taking the example 1 as an example, and the specific characteristics can be seen in fig. 1 to 11.
Fig. 1, 2 and 3 are XRD, SEM and TEM analyses of Ni-Co-PBA, respectively, and through peak type comparison, a nickel cobalt prussian blue derivative was successfully synthesized, and the shape was cubic, the inside was solid, and the particle size was uniform.
Fig. 4, 5 and 6 are XRD, SEM and TEM analyses of Ni — Co @ C, respectively, from which it is clear that after calcination, a nickel-cobalt alloy is formed, and from fig. 5, after calcination, the cubic structure is maintained, and from TEM, after calcination, the interior is hollow and the exterior is coated with a carbon layer of about 15 nm.
Fig. 7, 8 and 9 show XRD, SEM and TEM images of Ni-Co-P @ C, respectively. Compared with a PDF card, the diffraction peak of Ni-Co-P is successfully obtained, and the appearance before and after phosphorization is not changed as can be seen from SEM and TEM results.
From the SEM image of Ni-Co-P @ C/PP in FIG. 10, it can be seen that the multifunctional phosphide layer had a thickness of about 3.2 microns and a unit area loading of about 0.4mg cm-2. FIG. 11 is a mechanical folding test digital photo of Ni-Co-P @ C/PP, and it can be seen from the digital photo of FIG. 11 that when the diaphragm is subjected to a mechanical test, Ni-Co-P @ C is better adhered to the diaphragm, and after being folded, the Ni-Co-P @ C does not fall off and has a uniform surface.
The performances of the materials prepared in the above examples 1-3 are similar, and the following materials are used for preparing a lithium-sulfur battery and detecting the battery performance by taking the example 1 as an example, and the specific preparation method is as follows:
the exterior of the lithium-sulfur battery button battery (CR2032) consists of stainless steel positive and negative motor shells. The electrolyte is DME/DOL solution of 1M lithium bis (trifluoromethane) sulfonimide containing 2 wt% of lithium nitrate, and is prepared by tabletting in a glove box in an argon atmosphere.
The results are shown in fig. 12-16, in which fig. 12 is a charge and discharge capacity-voltage curve of the lithium-sulfur battery assembled by using the multifunctional separator at a rate of 0.1-5C, and the prepared battery is subjected to standing stabilization, and then to rate and cycle charge and discharge tests, and shows 1412.6,1093.9,961.3,906.1,821.5 and 654.5mAh g at current densities of 0.1, 0.2, 0.5, 1, 2, 5C-1The specific discharge capacity (fig. 12) of the lithium sulfur battery is improved by 2.67 times compared with that of the common polypropylene diaphragm (fig. 13 is a charge-discharge capacity-voltage curve of the lithium sulfur battery assembled by the multifunctional diaphragm and the common polypropylene diaphragm under the multiplying power of 5C), and 414.8mAh g can be still maintained after repeated charge-discharge circulation reaches 1000 circles under the current density of 0.5C-1The specific discharge capacity of (a) was 0.056%, which is much lower than 0.112% (731 cycles) of a battery using a general polypropylene separator (fig. 14 is a lithium sulfur battery assembled using a multifunctional separator and a general polypropylene separator (sulfur loading is 1.8mg cm)-2) Charge-discharge long cycle test pattern at 0.5C rate); at the same time, the method is also researched under the condition of high sulfur loading capacity, and the sulfur loading is between 2.4 and 4.5mg cm-2A cycle test was performed within the range of (1) (FIGS. 15 to 16); the high cycling stability is still maintained at different high areal loadings.
In conclusion, when the multifunctional diaphragm prepared by the invention is used for the lithium-sulfur battery, the diaphragm can separate the anode and the cathode, so that the short circuit phenomenon is avoided, the pore channel in the diaphragm is mainly responsible for transferring ions, the circulation of the battery reaction is promoted to continue, the electrochemical performance of the battery is obviously improved, and when the loading capacity on the sulfur surface is 1.8mg cm-2Can be used at high current 5C (1C: 1672mA g)-1) The battery can be stably charged and discharged under the condition, compared with the common polypropylene diaphragm, the discharge specific capacity is improved by 2.67 times, the battery can be circularly charged and discharged under the current density of 0.5C for 1000 circles, the average attenuation rate per circle is only 0.056 percent and is far less than 0.112 percent (731 circles) of the common polypropylene diaphragm battery, and under the conditions of different high surface loading capacity (2.4-4.5 mg cm)-2) The high cycle stability is still maintained, and the mechanism is as follows: the hollow nano-cage of the nickel-cobalt double-metal phosphide prepared by the method is of a cubic structure, the interior of the cube is of a hollow structure, the outer side of the hollow nano-cage is wrapped by a layer of carbon layer derived from polydopamine, and the inner side of the hollow nano-cage is attached with the inlaid nickel-cobalt phosphide (capable of providing Ni-Co-P active sites), so that the volume expansion of an active substance in the charging and discharging process can be effectively relieved through the construction of the hollow structure, and the stability of the battery structure is ensured; the attached Ni-Co-P active sites can effectively adsorb polysulfide, limit the polysulfide in the reaction process on the positive electrode side, simultaneously effectively promote catalytic conversion among the polysulfide, promote the conversion of long-chain liquid polysulfide to solid short-chain lithium sulfide, and inhibit the shuttle effect in the battery reaction, thereby improving the discharge specific capacity, the rate capability and the cycle performance of the battery; in addition, the bimetal phosphide has excellent conductivity, and is matched with the carbon layer on the outer side and the hollow structure in the inner side, so that the bimetal phosphide is more favorable for quick conduction of electrons and ions.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a double-metal phosphide-inlaid carbon hollow nano cage is characterized by comprising the following steps:
s1 preparation of polydopamine-coated nickel cobalt Prussian blue compound
Dispersing the nickel cobalt prussian blue derivative and dopamine hydrochloride in a liquid medium containing an initiator, and under the action of the initiator, carrying out self-polymerization on the dopamine on the surface of the nickel cobalt prussian blue derivative to generate polydopamine so as to prepare a polydopamine-coated nickel cobalt prussian blue compound;
s2 preparation of hollow carbon nanocage embedded with nickel-cobalt double-metal particles
Calcining the polydopamine-coated nickel-cobalt Prussian blue compound prepared in S1 at 400-700 ℃ in a protective gas atmosphere to prepare a carbon hollow nano cage with embedded nickel-cobalt double metal particles;
s3 preparation of double-metal phosphide inlaid carbon hollow nanocage
And (2) taking phosphine as a phosphating agent, and preparing the hollow carbon nanocage inlaid with the nickel-cobalt double-metal particles prepared by S2 at 350-450 ℃ by adopting a one-step phosphating method.
2. The method for preparing a double metal phosphide-inlaid carbon hollow nanocage as claimed in claim 1, wherein in S1, the initiator is tris (hydroxymethyl) aminomethane buffer solution, the liquid medium is a mixed solution prepared from water and ethanol in a volume ratio of 0.5-2: 1, and the concentration of the initiator in the liquid medium is 5-15 mmol/L.
3. The method for preparing a hollow carbon nanocage with a dual metal phosphide mosaic as claimed in claim 1, wherein in S2, the temperature rise rate is 2-10 ℃/min and the calcination time is 1-4 h.
4. The dual metal phosphide damascene of claim 1The preparation method of the carbon hollow nano cage is characterized in that in S3, the heating rate is 2-10 ℃/min-1And the phosphating time is 1-4 h.
5. The method for preparing the hollow carbon nanocage with the dual metal phosphide inlaid structure as recited in claim 1, wherein in the step of the one-step phosphating process in S3, the phosphating agent is obtained by directly introducing phosphine gas or decomposing sodium hypophosphite by high-temperature heating to generate phosphine gas, and the mass ratio of the sodium hypophosphite to the nickel-cobalt dual metal particle inlaid carbon hollow nanocage is 5-10: 1.
6. The double metal phosphide-inlaid carbon hollow nanocage prepared by the preparation method according to any one of claims 1 to 5.
7. A multifunctional membrane prepared by coating the double metal phosphide-inlaid carbon hollow nanocage of claim 6 on a commercial polypropylene membrane.
8. The multifunctional membrane according to claim 7, characterized in that the process of coating is in particular: preparing a dispersion of the dual metal phosphide-inlaid carbon hollow nanocage of claim 6, carbon black and polyvinylidene fluoride, and then coating the dispersion on a commercial polypropylene separator, and drying to obtain a multifunctional separator.
9. The multifunctional membrane as claimed in claim 8, wherein the dispersant of the dispersion is N-methylpyrrolidone, and the mass ratio of the double metal phosphide-inlaid carbon hollow nanocages to the carbon black to the polyvinylidene fluoride is 7-8: 2-1: 1.
10. Use of the multifunctional separator according to any one of claims 7 to 9 in a lithium-sulfur battery.
CN202110277541.9A 2021-03-15 2021-03-15 Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof Active CN113066964B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110277541.9A CN113066964B (en) 2021-03-15 2021-03-15 Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110277541.9A CN113066964B (en) 2021-03-15 2021-03-15 Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof

Publications (2)

Publication Number Publication Date
CN113066964A true CN113066964A (en) 2021-07-02
CN113066964B CN113066964B (en) 2022-04-19

Family

ID=76560600

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110277541.9A Active CN113066964B (en) 2021-03-15 2021-03-15 Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof

Country Status (1)

Country Link
CN (1) CN113066964B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113782728A (en) * 2021-09-15 2021-12-10 浙江王点科技有限公司 Preparation method and application of cobalt Prussian blue analogue/carbon nano tube composite material
CN114371201A (en) * 2022-01-07 2022-04-19 四川大学 Reusable glucose sensor and preparation method and application thereof
CN114944474A (en) * 2022-05-18 2022-08-26 电子科技大学 Preparation method of CoSe-dispersed hierarchical porous carbon material for lithium-sulfur battery

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106450200A (en) * 2016-10-25 2017-02-22 福建师范大学 Cos@carbon nano-cage as well as preparation method and application thereof
CN109395752A (en) * 2018-06-20 2019-03-01 长沙理工大学 A kind of self-supporting double-metal phosphide Ni2P-Cu3P composite material and preparation method
CN109935819A (en) * 2019-04-02 2019-06-25 江西理工大学 A kind of preparation method of the negative electrode material for lithium ion battery
CN109999861A (en) * 2019-03-06 2019-07-12 江苏大学 A kind of nickel cobalt double-metal phosphide elctro-catalyst and its synthetic method and application
CN110745799A (en) * 2019-10-25 2020-02-04 苏州大学 Iron phosphide nanocube modified graphene/carbon nanotube composite aerogel material, preparation method thereof and lithium-sulfur battery
CN111715248A (en) * 2020-06-22 2020-09-29 陕西科技大学 Cathode catalyst for hollow nano electrolyzed water and preparation method thereof
CN111889128A (en) * 2020-07-29 2020-11-06 淮安新能源材料技术研究院 Preparation method of cage-shaped ferronickel bimetallic phosphide loaded nitrogen-doped porous carbon material
CN112151804A (en) * 2020-09-27 2020-12-29 广州大学 Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106450200A (en) * 2016-10-25 2017-02-22 福建师范大学 Cos@carbon nano-cage as well as preparation method and application thereof
CN109395752A (en) * 2018-06-20 2019-03-01 长沙理工大学 A kind of self-supporting double-metal phosphide Ni2P-Cu3P composite material and preparation method
CN109999861A (en) * 2019-03-06 2019-07-12 江苏大学 A kind of nickel cobalt double-metal phosphide elctro-catalyst and its synthetic method and application
CN109935819A (en) * 2019-04-02 2019-06-25 江西理工大学 A kind of preparation method of the negative electrode material for lithium ion battery
CN110745799A (en) * 2019-10-25 2020-02-04 苏州大学 Iron phosphide nanocube modified graphene/carbon nanotube composite aerogel material, preparation method thereof and lithium-sulfur battery
CN111715248A (en) * 2020-06-22 2020-09-29 陕西科技大学 Cathode catalyst for hollow nano electrolyzed water and preparation method thereof
CN111889128A (en) * 2020-07-29 2020-11-06 淮安新能源材料技术研究院 Preparation method of cage-shaped ferronickel bimetallic phosphide loaded nitrogen-doped porous carbon material
CN112151804A (en) * 2020-09-27 2020-12-29 广州大学 Prussian blue analogue-based carbon-coated transition metal oxide and preparation method and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
邢锦娟等: "Co-MOFs材料在锂离子电池负极材料中的应用研究进展", 《化学研究》 *
陈嘉卉等: "中空核壳结构Ni_(1.2)Co_(0.8)P@N-C钠离子电池负极材料的制备及拉曼研究", 《电化学》 *

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113782728A (en) * 2021-09-15 2021-12-10 浙江王点科技有限公司 Preparation method and application of cobalt Prussian blue analogue/carbon nano tube composite material
CN114371201A (en) * 2022-01-07 2022-04-19 四川大学 Reusable glucose sensor and preparation method and application thereof
CN114371201B (en) * 2022-01-07 2022-09-27 四川大学 Reusable glucose sensor and preparation method and application thereof
CN114944474A (en) * 2022-05-18 2022-08-26 电子科技大学 Preparation method of CoSe-dispersed hierarchical porous carbon material for lithium-sulfur battery

Also Published As

Publication number Publication date
CN113066964B (en) 2022-04-19

Similar Documents

Publication Publication Date Title
Wu et al. Implanting nickel and cobalt phosphide into well-defined carbon nanocages: A synergistic adsorption-electrocatalysis separator mediator for durable high-power Li-S batteries
CN110104630B (en) Porous carbon composite material for battery diaphragm and preparation method and application thereof
CN109755545B (en) Porous carbon material and preparation method thereof, porous carbon/sulfur composite material, battery positive electrode material, lithium-sulfur battery and application thereof
Lim et al. Experimental study on sodiation of amorphous silicon for use as sodium-ion battery anode
CN113066964B (en) Double-metal phosphide-inlaid carbon hollow nano cage and preparation method and application thereof
Sennu et al. Marine algae inspired pre-treated SnO2 nanorods bundle as negative electrode for Li-ion capacitor and battery: an approach beyond intercalation
Tang et al. Novel MnO/carbon composite anode material with multi-modal pore structure for high performance lithium-ion batteries
JP5534363B2 (en) Composite nanoporous electrode material, production method thereof, and lithium ion secondary battery
CN111362254A (en) Preparation method and application of nitrogen-doped carbon nanotube-loaded phosphorus-doped cobaltosic oxide composite material
CN104870087A (en) Process for producing a carbon-supported nickel-cobalt-oxide catalyst and its use in rechargeable electrochemical metal-oxygen cells
CN103545113B (en) A kind of lithium ion hybrid super capacitor
KR101484503B1 (en) Cathode Catalyst for Lithium-Air Battery, Method of Manufacturing the Same, and Lithium-Air Battery Comprising the Same
KR20180114151A (en) Immobilized selenium, its preparation, and use of immobilized selenium in a rechargeable battery
JP2022508931A (en) A functional separation membrane with a catalyst site introduced, a manufacturing method thereof, and a lithium secondary battery containing the same.
CN104617249A (en) Barium sulfate composite diaphragm as well as preparation method and lithium ion battery
CN111554905B (en) Preparation method, product and application of zinc oxide-based carbon composite nano material
Priyadarshini et al. Investigation of various cobalt concentrations on LiV2O5 as cathode materials with tunable high rate capability and operating voltage in Li-ion batteries
CN113264519A (en) Modified carbon nanotube and preparation method thereof, negative electrode material, negative electrode plate and lithium ion battery
JP7286764B2 (en) Catalyst for positive electrode material for lithium secondary battery, and lithium secondary battery containing the same
CN111584841B (en) Composite material, preparation method thereof and water-based lithium ion battery
CN111354940B (en) Metal-coated two-dimensional silicon material and preparation method and application thereof
JP7190030B2 (en) Negative electrode active material and electrochemical device and electronic equipment using the same
WO2018195837A1 (en) Metal-sulfur battery and preparation method therefor
Duan et al. Enhancing the polysulfide redox conversion by a heterogeneous CoP-Co3S4 electrocatalyst for Li-S batteries
CN108063253A (en) Graphene and preparation method thereof, the Anode and battery containing graphene

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant