CN107123810A - A kind of preparation method and applications based on nickel phosphide skeleton structure composite - Google Patents
A kind of preparation method and applications based on nickel phosphide skeleton structure composite Download PDFInfo
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- CN107123810A CN107123810A CN201710349416.8A CN201710349416A CN107123810A CN 107123810 A CN107123810 A CN 107123810A CN 201710349416 A CN201710349416 A CN 201710349416A CN 107123810 A CN107123810 A CN 107123810A
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- nickel phosphide
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- skeleton structure
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
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- 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
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- 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
- H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
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- 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 preparation method and application based on nickel phosphide skeleton structure composite, methods described step is as follows：（1）Ni metallo-organic framework materials are prepared using hydro-thermal reaction；（2）Dried Ni metallo-organic frameworks material is mixed with phosphorus source, is placed in tube furnace and calcines phosphatization, nickel phosphide frame structure material is obtained；（3）By step（2）The nickel phosphide frame structure material of acquisition is mixed with sublimed sulfur, after grinding is uniform, is being heated to melting and being subsequently cooled to room temperature, obtains being based on nickel phosphide skeleton structure composite.Composite prepared by the present invention possesses high electrical conductivity, the problem of can significantly improving traditional sulphur positive conductive difference in lithium-sulfur cell, and the strong bonding effect of nickel phosphide and sulphur can suppress the shuttle effect of many lithium sulfides, improve the cycle life of lithium-sulfur cell.
Description
Technical field
The invention belongs to technical field of energy material, it is related to a kind of preparation method and applications of composite, especially relates to
And a kind of preparation method and applications based on nickel phosphide skeleton structure composite.
Background technology
Lithium-sulfur cell be by negative pole of lithium metal, elemental sulfur for positive pole electrochemical cell of new generation.Elemental sulfur source is wide
It is general, cheap, environment-friendly, and its theoretical specific energy is up to 2600Wh/kg, is 5 times of existing lithium ion battery.Therefore
Lithium-sulfur cell is considered as the high-energy-density electrochemical energy storage system of new generation of great application potential.
But, the problem of lithium-sulfur cell still has many serious, such as：The utilization rate of elemental sulfur is low in electrode, circulate
Life-span is poor, high rate performance is poor, there is potential safety hazard, still governs its commercialized development.This be mainly due to it is following some：
（1）Elemental sulfur and discharging product lithium sulfide（Li2S）It is electronic body, therefore causes active material to be difficult to play its electricity completely
Chemism；（2）The many lithium sulfides of intermediate product of lithium-sulfur cell electric discharge are readily dissolved in ethers electrolyte and move to negative pole table
Face, many lithium sulfides and the negative pole Li of dissolving react, and cause while reduction negative electrode active material utilization rate and strong put certainly
Electricity；（3）Elemental sulfur volumetric expansion in charge and discharge process is serious（Volumetric expansion 80% or so）, easily make the active material in pole piece
Material departs from, the contact resistance between increase material, so as to cause decaying for performance.Problem above be also lithium-sulfur cell urgently
The problem of solution.
In order to solve the above problems and capture difficult point, people use different lithium-sulphur cell positive electrode preparation methods to suppress to wear
Shuttle effect, lifts the performance of lithium-sulfur cell.The result of study of recent years finds that polar material suppresses to shuttle with compound turn into of sulphur
Effect most efficient method.Compare over for the carbon material used, polar molecule（Metal oxide, metal sulfide etc.）
Can be with lithium-sulfur cell electric discharge intermediate product Li2Sn Very strong chemisorption is produced between (4≤n≤8), so as to suppress
Li2SnIt is dissolved into electrolyte.
The content of the invention
, should it is an object of the invention to provide a kind of preparation method and applications based on nickel phosphide skeleton structure composite
Composite prepared by method possesses high electrical conductivity, can significantly improve traditional sulphur positive conductive difference in lithium-sulfur cell
Problem, and the strong bonding effect of nickel phosphide and sulphur can suppress the shuttle effect of many lithium sulfides, improve the circulation of lithium-sulfur cell
Life-span.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method based on nickel phosphide skeleton structure composite, comprises the following steps：
（1）Ni- metallo-organic framework materials are prepared using hydro-thermal reaction：10 ~ 20mmol nickel salt, 4 ~ 6mmol are matched somebody with somebody
Body, 200 ~ 300mL organic solvent, 4 ~ 6mL water, 4 ~ 6mL alcohol are configured to solution, and are transferred in reactor, 90 ~
200 DEG C of temperature carries out hydro-thermal reaction 6 ~ 24 hours, after reaction is cleaned, dried through centrifugation, methanol after terminating, obtains Ni-
Metallo-organic framework material.
In this step, the nickel salt is one kind in nickel sulfate, nickel nitrate, nickel acetate, nickel chloride；Part is equal benzene front three
One kind in acid, terephthalic acid (TPA), 2,5- dihydric para-phthalic acids；Organic solvent is N,N-dimethylformamide, N, N- bis-
One kind in ethyl formyl ammonia；Alcohol is one kind in methanol, ethanol, normal propyl alcohol, isopropanol.
（2）By dried Ni- metallo-organic frameworks material and phosphorus source according to 1:1 ~ 50 mass ratio is mixed, and is placed in pipe
In formula stove, phosphatization is calcined under conditions of 250 ~ 500 DEG C, 2 ~ 12 hours, inert gas shielding, nickel phosphide skeleton structure material is obtained
Material.
In this step, phosphorus source is one kind in potassium hypophosphite, sodium hypophosphite, ammonium hypophosphite, red phosphorus, white phosphorus, yellow phosphorus；
Inert gas is one kind in argon gas, nitrogen, helium.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:0.5 ~ 9 mass ratio mixing,
After grinding is uniform, it is heated to melting and being subsequently cooled to room under conditions of 120 ~ 250 DEG C, 5 ~ 24 hours, inert gas shielding
Temperature, obtains being based on nickel phosphide skeleton structure composite.
In this step, the inert gas is one kind in argon gas, nitrogen, helium.
The present invention has the advantages that：
（1）Ni- metallo-organic framework materials are prepared using hydro-thermal reaction, and by subsequent phosphating reaction by Ni- metals
Organic framework materials are converted into nickel phosphide frame structure material, during inversion of phases, and electrode keeps original porous spy
Point.
（2）Nickel phosphide frame structure material is to lithium-sulfur cell electric discharge intermediate product Li2Sn (4≤n≤8) have very strong change
Bonding action is learned, many lithium sulfides are adsorbed by chemical bond in charge and discharge process, so as to significantly inhibit the generation of shuttle effect.
（3）Nickel phosphide frame structure material has high electric conductivity, is effectively lifted by the recombination energy with sublimed sulfur
The overall electronic conductivity of compound, so as to strengthen the electro-chemical activity and reaction depth of lithium-sulphur cell positive electrode.
（4）Nickel phosphide frame structure material maintains the height similar to Ni- metallo-organic frameworks in preparation process
Specific surface area property, therefore in addition to improving electrochemical reaction active interface, additionally it is possible to abundant storage sulphur place is provided, so as to
During enough effectively suppression lithium-sulfur cell electric discharges the problem of volumetric expansion.
Brief description of the drawings
Scanning electron microscope (SEM) photographs of the Fig. 1 for the nickel phosphide frame structure material of the invention prepared under the conditions of 50000 times of amplifications；
Scanning electron microscope (SEM) photographs of the Fig. 2 for the nickel phosphide frame structure material of the invention prepared under the conditions of 5000 times of amplifications；
The X-ray diffraction spectrogram for the nickel phosphide frame structure material that Fig. 3 is prepared for the present invention；
Electric discharges of the Fig. 4 for the nickel phosphide skeleton structure composite of the invention prepared as lithium sulfur battery anode material in 0.1C is followed
Ring curve.
Embodiment
Technical scheme is further described with reference to embodiment, but is not limited thereto, it is every right
Technical solution of the present invention is modified or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, all should be contained
Cover in protection scope of the present invention.
Embodiment 1
（1）First by 15mmol nickel sulfate, 5mmol trimesic acid, 250mL N,N-dimethylformamide, 5mL
Water, 5mL methanol are configured to solution, and are transferred in reactor, carry out hydro-thermal under conditions of 90 DEG C and 6 hours in an oven
Reaction, reaction terminate obtained by product obtained by way of centrifugation, and using methanol clean, dry after, obtain Ni- metals
Organic framework materials.
（2）By dried Ni- metallo-organic frameworks material and potassium hypophosphite according to 1:1 mass ratio mixing, puts
In argon gas atmosphere tube furnace, phosphatization is calcined under conditions of 250 DEG C, 2 hours, nickel phosphide frame structure material is obtained.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:0.5 mass ratio mixing, grinds
After mill is uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 120 DEG C, 5 hours, argon gas protection, obtains nickel phosphide
Skeleton structure composite.
Embodiment 2
（1）First by 15mmol nickel nitrate, 5mmol 2,5- dihydric para-phthalic acids, 250mL N, N- diethyl formyls
Amine, 5mL water, 5mL isopropanol alcohol are configured to solution, and are transferred in reactor, in an oven at 180 DEG C and 12 hours
Under the conditions of carry out hydro-thermal reaction, the product obtained by reaction terminates is obtained by way of centrifugation, and is cleaned, dried using methanol
Afterwards, Ni- metallo-organic framework materials are obtained.
（2）By dried Ni- metallo-organic frameworks material and ammonium hypophosphite according to 1:20 mass ratio mixing, puts
In nitrogen atmosphere tube furnace, phosphatization is calcined under conditions of 350 DEG C, 12 hours, nickel phosphide frame structure material is obtained.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:4 mass ratio mixing, grinding
After uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 250 DEG C, 15 hours, nitrogen protection, obtains nickel phosphide bone
Frame structural composite material.
Embodiment 3
（1）First by 15mmol nickel chloride, 5mmol terephthalic acid (TPA), 250mL N,N-dimethylformamide, 5mL
Water, 5mL ethanol are configured to solution, and are transferred in reactor, enter water-filling under conditions of 150 DEG C and 24 hours in an oven
Thermal response, reaction terminate obtained by product obtained by way of centrifugation, and using methanol clean, dry after, obtain Ni- gold
Belong to organic framework materials.
（2）By dried Ni- metallo-organic frameworks material and white phosphorus according to 1:5 mass ratio mixing, is placed in helium
In gas atmosphere tube type stove, phosphatization is calcined under conditions of 500 DEG C, 6 hours, nickel phosphide frame structure material is obtained.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:9 mass ratio mixing, grinding
After uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 180 DEG C, 24 hours, helium protection, obtains nickel phosphide bone
Frame structural composite material.
Embodiment 4
（1）First by 15mmol nickel acetate, 5mmol trimesic acid, 250mL N, N- diethylformamides, 5mL
Water, 5mL normal propyl alcohol are configured to solution, and are transferred in reactor, are carried out in an oven under conditions of 120 DEG C and 18 hours
Hydro-thermal reaction, reaction terminate obtained by product obtained by way of centrifugation, and using methanol clean, dry after, obtain Ni-
Metallo-organic framework material.
（2）By dried Ni- metallo-organic frameworks material and sodium hypophosphite according to 1:50 mass ratio mixing, puts
In argon gas atmosphere tube furnace, phosphatization is calcined under conditions of 450 DEG C, 4 hours, nickel phosphide frame structure material is obtained.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:6 mass ratio mixing, grinding
After uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 210 DEG C, 10 hours, argon gas protection, obtains nickel phosphide bone
Frame structural composite material.
The scanning electron microscope (SEM) photograph such as Fig. 1 of nickel phosphide frame structure material manufactured in the present embodiment under the conditions of 50000 times of amplifications
Shown, the scanning electron microscope (SEM) photograph under the conditions of 5000 times of amplifications is as shown in Figure 2；X-ray diffraction spectrogram is as shown in Figure 3.
When nickel phosphide skeleton structure composite manufactured in the present embodiment is used as into lithium sulfur battery anode material, lithium-sulfur cell
Positive electrode is as shown in Figure 4 in 0.1C discharge cycles curve.
Embodiment 5
（1）First by 15mmol nickel acetate, 5mmol 2,5- dihydric para-phthalic acids, 250mL N, N- diethyl formyls
Amine, 5mL water, 5mL isopropanol are configured to solution, and are transferred in reactor, in an oven in 200 DEG C and the bar of 6 hours
Hydro-thermal reaction is carried out under part, the product obtained by reaction terminates is obtained by way of centrifugation, and cleaned, dried using methanol
Afterwards, Ni- metallo-organic framework materials are obtained.
（2）By dried Ni- metallo-organic frameworks material and red phosphorus according to 1:2 mass ratio mixing, is placed in helium
In gas atmosphere tube type stove, phosphatization is calcined under conditions of 500 DEG C, 8 hours, nickel phosphide frame structure material is obtained.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:2 mass ratio mixing, grinding
After uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 150 DEG C, 20 hours, helium protection, obtains nickel phosphide bone
Frame structural composite material.
Embodiment 6
（1）First by 15mmol nickel chloride, 5mmol terephthalic acid (TPA), 250mL N,N-dimethylformamide, 5mL
Water, 5mL normal propyl alcohol are configured to solution, and are transferred in reactor, are carried out in an oven under conditions of 180 DEG C and 12 hours
Hydro-thermal reaction, reaction terminate obtained by product obtained by way of centrifugation, and using methanol clean, dry after, obtain Ni-
Metallo-organic framework material.
（2）By dried Ni- metallo-organic frameworks material and yellow phosphorus according to 1:10 mass ratio mixing, is placed in nitrogen
In gas atmosphere tube type stove, phosphatization is calcined under conditions of 450 DEG C, 2 hours, nickel phosphide frame structure material is obtained.
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:1 mass ratio mixing, grinding
After uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 180 DEG C, 5 hours, nitrogen protection, obtains nickel phosphide bone
Frame structural composite material.
Claims (9)
1. a kind of preparation method based on nickel phosphide skeleton structure composite, it is characterised in that methods described step is as follows：
（1）Ni- metallo-organic framework materials are prepared using hydro-thermal reaction；
（2）By dried Ni- metallo-organic frameworks material and phosphorus source according to 1:1 ~ 50 mass ratio is mixed, and is placed in tube furnace
In, phosphatization is calcined under conditions of 250 ~ 500 DEG C, 2 ~ 12 hours, inert gas shielding, nickel phosphide frame structure material is obtained；
（3）By step（2）The nickel phosphide frame structure material of acquisition is with sublimed sulfur according to 1:0.5 ~ 9 mass ratio mixing, grinding
After uniform, it is heated to melting and being subsequently cooled to room temperature under conditions of 120 ~ 250 DEG C, 5 ~ 24 hours, inert gas shielding, obtains
To based on nickel phosphide skeleton structure composite.
2. the preparation method according to claim 1 based on nickel phosphide skeleton structure composite, it is characterised in that described
Step（1）Comprise the following steps that：
10 ~ 20mmol nickel salt, 4 ~ 6mmol part, 200 ~ 300mL organic solvent, 4 ~ 6mL water, 4 ~ 6mL alcohol are matched somebody with somebody
Be set to solution, and be transferred in reactor, hydro-thermal reaction 6 ~ 24 hours is carried out in 90 ~ 200 DEG C of temperature, reaction passed through after terminating from
After heart separation, methanol cleaning, drying, Ni- metallo-organic framework materials are obtained.
3. the preparation method according to claim 2 based on nickel phosphide skeleton structure composite, it is characterised in that described
Nickel salt is one kind in nickel sulfate, nickel nitrate, nickel acetate, nickel chloride.
4. the preparation method according to claim 2 based on nickel phosphide skeleton structure composite, it is characterised in that described
Part is one kind in trimesic acid, terephthalic acid (TPA), 2,5- dihydric para-phthalic acids.
5. the preparation method according to claim 1 based on nickel phosphide skeleton structure composite, it is characterised in that described
Organic solvent is one kind in N,N-dimethylformamide, N, N- diethyl formyl ammonia.
6. the preparation side of the lithium sulfur battery anode material according to claim 1 based on nickel phosphide skeleton structure composite
Method, it is characterised in that the alcohol is one kind in methanol, ethanol, normal propyl alcohol, isopropanol.
7. the preparation method according to claim 1 based on nickel phosphide skeleton structure composite, it is characterised in that described
Phosphorus source is one kind in potassium hypophosphite, sodium hypophosphite, ammonium hypophosphite, red phosphorus, white phosphorus, yellow phosphorus.
8. the preparation method according to claim 1 based on nickel phosphide skeleton structure composite, it is characterised in that described
Inert gas is one kind in argon gas, nitrogen, helium.
9. a kind of claim 1-8 any claims methods described prepare based on nickel phosphide skeleton structure composite in lithium
Application in sulphur cell positive electrode.
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Cited By (6)
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| CN108493403A (en) * | 2018-05-17 | 2018-09-04 | 中山大学 | A kind of synthetic method of self-supporting sodium-ion battery cathode |
| CN108493426A (en) * | 2018-04-13 | 2018-09-04 | 西北大学 | A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery |
| CN109055975A (en) * | 2018-08-01 | 2018-12-21 | 北京工业大学 | One kind preparing porous Ni based on two-dimensional metallic organic backbone template2The method of P/C electrode |
| CN109546116A (en) * | 2018-11-19 | 2019-03-29 | 肇庆市华师大光电产业研究院 | A kind of lithium sulfur battery anode material, preparation method and application |
| CN109686933A (en) * | 2018-12-12 | 2019-04-26 | 电子科技大学 | It is a kind of using carbon cloth as the preparation method of the lithium-sulfur cell self-supporting positive electrode of substrate |
| CN112604717A (en) * | 2020-12-29 | 2021-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of quantum dot iron-based metal organic framework composite material |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108493426A (en) * | 2018-04-13 | 2018-09-04 | 西北大学 | A kind of preparation method of carbon coating nickel phosphide composite material nanometer particle and its application in preparing sodium-ion battery |
| CN108493403A (en) * | 2018-05-17 | 2018-09-04 | 中山大学 | A kind of synthetic method of self-supporting sodium-ion battery cathode |
| CN108493403B (en) * | 2018-05-17 | 2020-10-27 | 中山大学 | Synthesis method of self-supporting sodium ion battery cathode |
| CN109055975A (en) * | 2018-08-01 | 2018-12-21 | 北京工业大学 | One kind preparing porous Ni based on two-dimensional metallic organic backbone template2The method of P/C electrode |
| CN109546116A (en) * | 2018-11-19 | 2019-03-29 | 肇庆市华师大光电产业研究院 | A kind of lithium sulfur battery anode material, preparation method and application |
| CN109546116B (en) * | 2018-11-19 | 2022-02-22 | 肇庆市华师大光电产业研究院 | Lithium-sulfur battery positive electrode material, preparation method and application |
| CN109686933A (en) * | 2018-12-12 | 2019-04-26 | 电子科技大学 | It is a kind of using carbon cloth as the preparation method of the lithium-sulfur cell self-supporting positive electrode of substrate |
| CN112604717A (en) * | 2020-12-29 | 2021-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of quantum dot iron-based metal organic framework composite material |
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