CN105655585B - A kind of single-phase skutterudite structure NiP3Preparation method - Google Patents
A kind of single-phase skutterudite structure NiP3Preparation method Download PDFInfo
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- CN105655585B CN105655585B CN201610169416.5A CN201610169416A CN105655585B CN 105655585 B CN105655585 B CN 105655585B CN 201610169416 A CN201610169416 A CN 201610169416A CN 105655585 B CN105655585 B CN 105655585B
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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
- H01M4/36—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
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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
- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
- H01M4/139—Processes of manufacture
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
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- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N10/00—Thermoelectric devices comprising a junction of dissimilar materials, i.e. devices exhibiting Seebeck or Peltier effects
- H10N10/80—Constructional details
- H10N10/85—Thermoelectric active materials
- H10N10/851—Thermoelectric active materials comprising inorganic compositions
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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
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of single-phase skutterudite structure NiP3Preparation method, belong to the transition metal phosphide material technical field of high phosphorus.This method includes：By nickel sulfide, red phosphorus powder according to nickel, phosphorus atoms than 1:4~1:5 mixing, under 670~700 DEG C of temperature, vacuum condition be sintered 80~100h to get.The present invention prepares the NiP of single-phase skutterudite structure using nickel sulfide and red phosphorus as raw material3, simple for process, easy to operate, raw material is cheap and easy to get and cost is relatively low, suitable for large-scale production and application.The NiP of synthesis3It is not only good thermoelectric material and more potential novel lithium battery cathode material.
Description
Technical field
The present invention relates to a kind of single-phase skutterudite structure NiP3Preparation method, belong to the transition metal phosphide material of high phosphorus
Expect technical field.
Background technology
The transition metal phosphide NiP of high phosphorus3It can be stabilized, have similar to CoAs in water3Crystal structure, again
Name skutterudite section bar material, is found by Norway scientist Skutterudite and for the first time with its naming.NiP3Material is generally all
With cubic crystal structure, single nickle atom is closely surrounded by six neighbouring phosphorus atoms, and the phosphorus atoms composition octahedral of periphery
Body structure, special electronic structure, electron transport and the heat that the particularity of the structure is caged crystal structure and is consequently formed
Transport feature, it has also become more potential thermoelectric material and ion cathode material lithium.Many scientists to preparation method into
Research is gone, the method for wherein S.Boyanov nickel powders and red phosphorus powder direct sintering has prepared about 20 μm of granular size, pattern
Single NiP3, but the pattern of the powder is random, it is limited as influence of the lithium cell cathode material to chemical property.It
Afterwards, nickel powder and red phosphorus are put into ball mill by J.Fullenwarth propositions synthesizes NiP in argon gas atmosphere3, this method and S.
Boyanov direct sinterings prepare NiP3Method it is similar, can control NiP3Granular size is at 1 μm hereinafter, still to the requirement of equipment
Higher, it is of high cost and not easy to operate.The NiP that above two method is prepared3Pattern is all controlled by nickel powder pattern, and majority is in micro-
Meter level is other, and is influenced by Ni-P systems feature, easily forms the Ni of low phosphorus content3P、Ni2P-compound.
Invention content
The object of the present invention is to provide a kind of single-phase skutterudite structure NiP3Preparation method, this method is simple, easy to operate,
And cost is relatively low.
In order to achieve the goal above, the technical solution adopted in the present invention is：
Single-phase skutterudite structure NiP3Preparation method, include the following steps：Nickel sulfide, red phosphorus powder is former according to nickel, phosphorus
Sub- ratio 1:4~1:5 mixing, under 670~700 DEG C of temperature, vacuum condition be sintered 80~100h to get.
Commercial goods can be used in the nickel sulfide, can be also prepared by hydro-thermal method.Hydro-thermal method prepares the behaviour of nickel sulfide
As：By nickel source, sulphur source according to nickel, sulphur atom than 1:1~1:2 are added to the water, and mixing is after 120~200 DEG C of temperature, closed item
Under part 6~12h of insulation reaction to get.
Nickel acetate, six water nickel chlorides, nickel sulfate etc. can be used in the nickel source.
Sodium thiosulfate, thioacetamide etc. can be used in the sulphur source.
The vacuum degree of the vacuum condition is 1.0 × 10-3~15 × 10-3Pa。
Beneficial effects of the present invention：
The present invention prepares the NiP of single-phase skutterudite structure using nickel sulfide and red phosphorus as raw material3, it is simple for process, easy to operate,
Raw material is cheap and easy to get and cost is relatively low, suitable for large-scale production and application.The NiP of synthesis3Good thermoelectric material is not only,
It is more potential novel lithium battery cathode material.
Description of the drawings
Fig. 1 prepares NiP for embodiment 13SEM figure；
Fig. 2 prepares NiP for comparative example3SEM figure；
Fig. 3 prepares NiP for Examples 1 to 3 and comparative example3XRD spectrum.
Specific embodiment
Following embodiments are only described in further detail the present invention, but do not form any limitation of the invention.
Embodiment 1
Single-phase skutterudite structure NiP in the present embodiment3Preparation method include the following steps：
1) hydro-thermal method prepares nickel sulfide (NiS)
Using nickel acetate, sodium thiosulfate as nickel source and sulphur source, according to nickel, sulphur atom than 1:1 by 0.75g nickel acetates and
0.372g sodium thiosulfate is separately added into 30mL deionized waters, and magnetic agitation 30min respectively, later mixes two solution,
It is transferred to after magnetic agitation 20min in 100mL reaction kettles；The good reaction kettle of fit sealing is placed in baking oven, at 200 DEG C of temperature
Insulation reaction 12h, reaction finish taking-up reaction solution, cooled to room temperature；The reaction solution of cooling is placed in a centrifuge centrifugation,
Precipitation is taken to be cleaned 3 times with deionized water and ethyl alcohol successively, is placed in pumping and filtering device and filters, dry 6h, obtains black at 70 DEG C
The nickel sulfide of color；
2) high temperature sintering prepares the transition metal phosphide NiP of high phosphorus3
According to nickel, phosphorus atoms than 1:4 is mixed by the nickel sulfide in step 1) and red phosphorus (red phosphorus grinds 1h, dry 10h in advance)
Close, be placed in quartz ampoule, vacuumize and do tube sealing processing (in quartz ampoule vacuum degree be 1.0 × 10-3Pa, the quartz ampoule sealed
Pipe range about 10cm)；Quartz ampoule is placed in Muffle furnace, the high temperature sintering at 670 DEG C of temperature, 3 DEG C/min of heating rate, during heat preservation
Between 100h, it is air-cooled later to obtain gray product, by this product CS2Cleaning 2 times removes the sulphur being mingled with and the white phosphorus of conversion, most
Gray product NiP is obtained eventually3。
Embodiment 2
Single-phase skutterudite structure NiP in the present embodiment3Preparation method include the following steps：
1) hydro-thermal method prepares nickel sulfide (NiS)
Using six water nickel chlorides, thioacetamide as nickel source and sulphur source, by quality be 0.713g six water nickel chlorides and
The thioacetamide of 0.676g is separately added into 30mL deionized waters, is transferred to after being sufficiently stirred in 100mL reaction kettles；It will fastening
The reaction kettle being sealed is placed in baking oven, and the insulation reaction 12h at 170 DEG C of temperature, reaction finishes taking-up reaction solution, natural cooling
To room temperature；The reaction solution of cooling is placed in a centrifuge centrifugation, precipitation is taken to be cleaned 3 times with deionized water and ethyl alcohol successively, is filtered,
Dry 6h, obtains the nickel sulfide of black at 70 DEG C；
2) high temperature sintering prepares the transition metal phosphide NiP of high phosphorus3
According to nickel, phosphorus atoms than 1:4.5 by the nickel sulfide in step 1) and red phosphorus (red phosphorus grinds 1h, dry 10h in advance)
Mixing, be placed in quartz ampoule, vacuumize and do tube sealing processing (in quartz ampoule vacuum degree be 1.0 × 10-3Pa, the quartz sealed
Pipe pipe range about 10cm)；Quartz ampoule is placed in Muffle furnace, the high temperature sintering at 700 DEG C of temperature, 3 DEG C/min of heating rate, heat preservation
Time 80h, it is air-cooled later to obtain gray product, by this product CS2Cleaning 2 times removes the sulphur being mingled with and the white phosphorus of conversion, most
Gray product NiP is obtained eventually3。
Embodiment 3
Single-phase skutterudite structure NiP in the present embodiment3Preparation method substantially with embodiment 1, differ only in using city
The nickel sulfide sold.
Embodiment 4
Single-phase skutterudite structure NiP in the present embodiment3Preparation method substantially with embodiment 2, difference lies in step 1)
Nickel, sulphur atom ratio are 1:2,120 DEG C, soaking time 6h of hydrothermal temperature, nickel, phosphorus atoms ratio are 1 in step 2):5, quartz ampoule
Middle vacuum degree is 15 × 10-3Pa。
Comparative example
NiP in this comparative example3Preparation method be：
By dried metal nickel powder (100nm, 99.9%) and red phosphorus powder (100 mesh, 99%) with molar ratio 1:3 ratio
Example mixing, be placed in sealing vitreosil pipe in, vacuumize and do tube sealing processing (in quartz ampoule vacuum degree be 1.0 × 10- 3Pa, the quartz ampoule pipe range about 10cm sealed)；Quartz ampoule is placed in Muffle furnace, the high temperature sintering at 700 DEG C of temperature, heating speed
Rate 3 DEG C/min, soaking time 80h, it is air-cooled later to obtain product, by this product CS2Cleaning 2 times removes the sulphur being mingled with and turns
The white phosphorus of change obtains grey black NiP3。
Test example
1st, SEM scanning electron microscope analysis
NiP prepared by Example 1 and comparative example3Carry out SEM scanning electron microscope analysis, the result is shown in Figure 1 and Fig. 2.From Fig. 1
As can be seen that NiP prepared by embodiment 13Particle is in not specification shape, and particle is more tiny (large specific surface area), and surface is thick
It is rough.Figure it is seen that NiP prepared by comparative example3Particle is in spherical, 10 μm or so of diameter.In comparison, fine particle
NiP3Chemical property is more preferably.
2nd, X-ray diffraction analysis
NiP prepared by Example 1~3 and comparative example3X-ray diffraction analysis is carried out, as a result sees Fig. 3.It can from Fig. 3
Go out, NiP prepared by Examples 1 to 33It matches with standard diagram (PDF073-1242), more single, the substantially free of impurities of object phase,
Illustrate the NiP prepared3For single-phase material, and NiP prepared by comparative example3There is micro NiP2Impurity, product is not single, NiP3It is pure
It spends impacted.
Claims (5)
1. single-phase skutterudite structure NiP3Preparation method, it is characterised in that：Include the following steps：By nickel sulfide, red phosphorus powder according to
Nickel, phosphorus atoms are than 1:4~1:5 mixing, under 670~700 DEG C of temperature, vacuum condition be sintered 80~100h to get.
2. preparation method according to claim 1, it is characterised in that：The preparation method of the nickel sulfide is：By nickel source, sulphur
Source is according to nickel, sulphur atom than 1:1~1:2 are added to the water, and mixing is after 120~200 DEG C of temperature, under confined conditions insulation reaction 6
~12h to get.
3. preparation method according to claim 2, it is characterised in that：The nickel source is nickel acetate, six water nickel chlorides or sulphur
Sour nickel.
4. preparation method according to claim 2, it is characterised in that：The sulphur source is sodium thiosulfate or thioacetyl
Amine.
5. preparation method according to claim 1, it is characterised in that：The vacuum degree of the vacuum condition is 1.0 × 10-3~
15×10-3Pa。
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Inventor after: Hu Junhua Inventor after: Liu Panpan Inventor after: Cao Guoqin Inventor after: Wang Peng Inventor after: Shao Guosheng Inventor after: Mao Jing Inventor before: Song Angang Inventor before: Hu Junhua Inventor before: Liu Panpan Inventor before: Mao Jing Inventor before: Wang Peng Inventor before: Shao Guosheng |
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