CN110040705A - A method of preparing rich phosphorus phase phosphorized copper hollow nano-sphere - Google Patents
A method of preparing rich phosphorus phase phosphorized copper hollow nano-sphere Download PDFInfo
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- CN110040705A CN110040705A CN201910343200.XA CN201910343200A CN110040705A CN 110040705 A CN110040705 A CN 110040705A CN 201910343200 A CN201910343200 A CN 201910343200A CN 110040705 A CN110040705 A CN 110040705A
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- 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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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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Abstract
A method of preparing rich phosphorus phase phosphorized copper hollow nano-sphere.By Cu (CH under stirring3COO)2·H2O is dissolved in ethanol solution, and pyrroles is then added thereto and stirs to form dark blue solution A；Solution A is placed in reaction kettle and carries out solvent thermal reaction, after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；Presoma is placed in small porcelain boat, red phosphorus is placed in big porcelain boat, then small porcelain boat is inserted in big porcelain boat, and after sealing, phosphating reaction is carried out in vacuum tube furnace, and after reaction, the powder in small porcelain boat is rich phosphorus phase phosphorized copper hollow nano-sphere.Prepared rich phosphorus phase phosphorized copper hollow nano-sphere can be used as lithium ion battery or anode material of lithium-ion battery and electro catalytic electrode materials'use.While the phosphating reaction phosphorus that the present invention uses from outward appearance to inner essence is spread, oxide precursor is also being spread from inside to outside, and under the effect simultaneously of two kinds of processes, medicine ball is converted to hollow sphere.
Description
Technical field
The present invention relates to nano material and electrochemical fields, and in particular to a kind of to prepare rich phosphorus phase phosphorized copper hollow nano-sphere
Method.
Background technique
Transition metal phosphide has a wide range of applications in fields such as magnetics, optics and energy storages.It is direct by P-P
Bonding forms more phosphatization anion, and transition metal phosphide has the object phase of rich metal and the equal different phosphorus contents of rich phosphorus.In crowd
In more phosphides, rich phosphorus phase phosphorized copper (CuP2) it is that one kind potentially can be used for lithium/sodium-ion battery material, theoretical specific volume
Amount is up to 1281mAh g-1, there is very tempting application prospect.But with other using conversion reaction as the electrode material one of mechanism
Sample, there are huge volume changes during storing up lithium/sodium, and the volume of electrode material can be effectively relieved in hollow structure
Varying effect promotes its cyclical stability.
The thermodynamic condition as needed for the nucleating growth of rich phosphorus phase phosphorized copper is higher, prepares CuP at present2Having of method
Learn vapor deposition [Kloc C, Lux-Steiner M C, Keil M, et al.Growth and characterization of
CuP2single crystals[J].Journal of Crystal Growth,1990,106(4):635-642.].Ball-milling method
[Kim S O,Manthiram A.Phosphorus-Rich CuP2Embedded in Carbon Matrix as a High-
Performance Anode for Lithium-Ion Batteries[J].ACS Applied Materials&
Interfaces, 2017,9 (19): 16221.] and [Matsumoto K, Kaushik S, Hwang J, et al.High Rate
Capability and Cyclability of CuP2/C Composite Negative Electrode for Sodium
Secondary Battery Operating at Room to Intermediate Temperatures Using Ionic
Liquid[J].ChemElectroChem,2018.].But both methods can not all regulate and control the pattern of phosphorized copper, and
Energy consumption is high, is readily incorporated other miscellaneous phase substances.There are also consolidate growth method using shooting flow body fluid to prepare under high-temperature and high-pressure conditions
Phosphatization copper nano-wire [Li G A, Wang C Y, Chang W C, et al.Phosphorous-Rich Copper
Phosphide Nanowires for Field-Effect Transistors and Lithium-Ion Batteries.
[J] .Acs Nano, 1936,10 (9): 8632.] and thermal decomposition parco-lubrizing prepares carbon coating CuP2Compound
[Shuangqiang C,Feixiang W,Laifa S,et al.Cross-Linking Hollow Carbon Sheet
Encapsulated CuP2Nanocomposites for High Energy Density Sodium Ion Batteries
[J] .ACS Nano, 2018,12 (7) 7018-7027] and electrochemical deposition method [Chandrasekar M S, Mitra S.Thin
copper phosphide films as conversion anode for lithium-ion battery
2013,92 (1): applications [J] .Electrochimica Acta 47-54.] prepares phosphatization Copper thin film.
Summary of the invention
The purpose of the present invention is to provide a kind of simple process, be easy to control and operate, be not necessarily to complex device, safety and
Stability is good, and process is environmentally protective and the side of the easy rich phosphorus phase phosphorized copper hollow nano-sphere of preparation for realizing industrial-scale production
Method.
In order to achieve the above objectives, the present invention adopts the following technical scheme:
1) by Cu (CH under stirring3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O be 0.5~
Cu (the CH of 3mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol
0.5 ‰~5 ‰ pyrroles, stirring form dark blue solution A；
2) solution A is placed in reaction kettle in 180~200 DEG C of progress solvent thermal reactions, after reaction by product nothing
Water-ethanol washing, then dry the presoma in freeze drying box；
3) presoma being placed in small porcelain boat for the molar ratio of 1:1~5 by presoma and red phosphorus, red phosphorus is placed in big porcelain boat,
Small porcelain boat is inserted in big porcelain boat again, is vacuumized after sealing in tube furnace in 400~800 DEG C of progress phosphating reactions, reaction
After, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
Step 1) the stirring uses magnetic agitation.
The packing ratio that the step 2) solution A is placed in reaction kettle is 70~80%.
Step 2) the reaction kettle is the stainless steel cauldron of polytetrafluoroethyllining lining.
The size of the small porcelain boat of step 3) is 3*6cm, and the size of big porcelain boat is 5*12cm.
Step 3) the vacuum degree is -0.1Mpa.
Step 3) the phosphating reaction time is 1~4h.
Prepared rich phosphorus phase phosphorized copper hollow nano-sphere can be used as lithium ion battery or anode material of lithium-ion battery with
And electro catalytic electrode materials'use.
Compared with prior art, the invention has the following beneficial technical effects:
1) present invention uses solvent-thermal method, and using ethyl alcohol as solvent, pyrroles produces as reducing agent and pattern controlling agent, control
The nucleating growth process of object is allowed to form the spherical morphology of nano particle composition.
2) after in green high-efficient preparing spherical Cu oxide presoma, the phosphorus of short time is carried out at low temperature
Change, red phosphorus distils to form active gaseous state phosphorus during this.By vapor transportation process in the porcelain boat of close joint, with solid copper
Oxide precursor is reacted, it from inside to outside, is converted to phosphorized copper while keeping the pattern of precursor by reaction.
3) importantly, while red phosphorus is from outward appearance to inner essence spread in the process, oxide precursor also from it is interior to
Under external diffusion, two kinds of processes while effect, medicine ball is converted to hollow sphere.
4) due to the requirement of present device and instrument is more simple and can produce more efficiently at out crystallinity preferably,
Partial size is smaller and is evenly distributed, the rich phosphorus phase phosphorized copper of purity is high.
5) present invention process is simple, is easy to control and operates, and safety and stability is good, and Yi Shixian industrially scalable is raw
It produces.Its technology of preparing is simple, is not necessarily to complex device, and process is environmentally protective.
Detailed description of the invention
Fig. 1 is the XRD diagram of rich phosphorus phase phosphorized copper hollow nano-sphere prepared by the embodiment of the present invention 5；
Fig. 2 is the SEM figure of rich phosphorus phase phosphorized copper hollow nano-sphere prepared by the embodiment of the present invention 5.
Specific embodiment
The invention will be described in further detail with reference to the accompanying drawings and embodiments.
Embodiment 1:
1) by Cu (CH under magnetic agitation3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O is
Cu (the CH of 0.5mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol
0.5 ‰ pyrroles, stirring form dark blue solution A；
2) solution A is placed in the stainless steel cauldron of polytetrafluoroethyllining lining by 70% packing ratio and is carried out in 200 DEG C
Solvent thermal reaction after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；
3) presoma is placed in the small porcelain boat of 3*6cm for 1:1 molar ratio by presoma and red phosphorus, red phosphorus is placed in 5*12cm
Big porcelain boat in, then small porcelain boat is inserted in big porcelain boat, in 400 in the tube furnace that vacuum degree is -0.1Mpa after sealing
DEG C phosphating reaction 1h, after reaction, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
Embodiment 2:
1) by Cu (CH under magnetic agitation3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O is
Cu (the CH of 1mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol 2 ‰
Pyrroles, stirring form dark blue solution A；
2) solution A is placed in the stainless steel cauldron of polytetrafluoroethyllining lining by 75% packing ratio and is carried out in 190 DEG C
Solvent thermal reaction after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；
3) presoma is placed in the small porcelain boat of 3*6cm for 1:2 molar ratio by presoma and red phosphorus, red phosphorus is placed in 5*12cm
Big porcelain boat in, then small porcelain boat is inserted in big porcelain boat, in 500 in the tube furnace that vacuum degree is -0.1Mpa after sealing
DEG C phosphating reaction 2h, after reaction, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
Embodiment 3:
1) by Cu (CH under magnetic agitation3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O is
Cu (the CH of 2mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol 3 ‰
Pyrroles, stirring form dark blue solution A；
2) solution A is placed in the stainless steel cauldron of polytetrafluoroethyllining lining by 80% packing ratio and is carried out in 180 DEG C
Solvent thermal reaction after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；
3) presoma is placed in the small porcelain boat of 3*6cm for 1:4 molar ratio by presoma and red phosphorus, red phosphorus is placed in 5*12cm
Big porcelain boat in, then small porcelain boat is inserted in big porcelain boat, in 800 in the tube furnace that vacuum degree is -0.1Mpa after sealing
DEG C phosphating reaction 4h, after reaction, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
Embodiment 4:
1) by Cu (CH under magnetic agitation3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O is
Cu (the CH of 3mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol 5 ‰
Pyrroles, stirring form dark blue solution A；
2) solution A is placed in the stainless steel cauldron of polytetrafluoroethyllining lining by 78% packing ratio and is carried out in 180 DEG C
Solvent thermal reaction after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；
3) presoma is placed in the small porcelain boat of 3*6cm for 1:3 molar ratio by presoma and red phosphorus, red phosphorus is placed in 5*12cm
Big porcelain boat in, then small porcelain boat is inserted in big porcelain boat, in 600 in the tube furnace that vacuum degree is -0.1Mpa after sealing
DEG C phosphating reaction 3h, after reaction, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
Embodiment 5:
1) by Cu (CH under magnetic agitation3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O is
Cu (the CH of 1mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol 5 ‰
Pyrroles, stirring form dark blue solution A；
2) solution A is placed in the stainless steel cauldron of polytetrafluoroethyllining lining by 70% packing ratio and is carried out in 180 DEG C
Solvent thermal reaction after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；
3) presoma is placed in the small porcelain boat of 3*6cm for 1:5 molar ratio by presoma and red phosphorus, red phosphorus is placed in 5*12cm
Big porcelain boat in, then small porcelain boat is inserted in big porcelain boat, in 500 in the tube furnace that vacuum degree is -0.1Mpa after sealing
DEG C phosphating reaction 3h, after reaction, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
It can be seen from figure 1 that the diffraction maximum of material prepared complies with standard card 76-1190, corresponding object well
It is mutually CuP2, diffraction maximum peak shape is sharp, and crystallinity is good.
Figure it is seen that prepared CuP2Material is the spherical pattern of nanometer, and nanometer bulb diameter is about 150-
180nm can be seen that from the nanosphere of rupture, be internally hollow.Additionally a small amount of nano wire exists.
Embodiment 6:
1) by Cu (CH under magnetic agitation3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O is
Cu (the CH of 1mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol 1 ‰
Pyrroles, stirring form dark blue solution A；
2) solution A is placed in the stainless steel cauldron of polytetrafluoroethyllining lining by 70% packing ratio and is carried out in 200 DEG C
Solvent thermal reaction after reaction washs product with dehydrated alcohol, then dry the presoma in freeze drying box；
3) presoma is placed in the small porcelain boat of 3*6cm for 1:5 molar ratio by presoma and red phosphorus, red phosphorus is placed in 5*12cm
Big porcelain boat in, then small porcelain boat is inserted in big porcelain boat, in 400 in the tube furnace that vacuum degree is -0.1Mpa after sealing
DEG C phosphating reaction 4h, after reaction, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
Claims (7)
1. a kind of method for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that the following steps are included:
1) by Cu (CH under stirring3COO)2·H2O, which is dissolved in ethanol solution, obtains Cu (CH3COO)2·H2The concentration of O be 0.5~
Cu (the CH of 3mol/L3COO)2·H2Then Cu (CH is added in O ethanol solution thereto3COO)2·H2O volumes of aqueous ethanol
0.5 ‰~5 ‰ pyrroles, stirring form dark blue solution A；
2) solution A is placed in poly- reaction kettle in 180~200 DEG C of progress solvent thermal reactions, after reaction by product with anhydrous
Ethanol washing, then dry the presoma in freeze drying box；
3) presoma is placed in small porcelain boat for the molar ratio of 1:1~5 by presoma and red phosphorus, red phosphorus is placed in big porcelain boat, then will
Small porcelain boat is inserted in big porcelain boat, is vacuumized after sealing in 400~800 DEG C of progress phosphating reactions in tube furnace, reaction terminates
Afterwards, the powder in small porcelain boat is phosphorus phase phosphorized copper hollow nano-sphere.
2. the method according to claim 1 for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that: the step
1) stirring uses magnetic agitation.
3. the method according to claim 1 for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that: the step
2) it is 70~80% that solution A, which is placed in the packing ratio of reaction kettle,.
4. the method according to claim 1 for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that: the step
2) reaction kettle is the stainless steel cauldron of polytetrafluoroethyllining lining.
5. the method according to claim 1 for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that: the step
3) size of small porcelain boat is 3*6cm, and the size of big porcelain boat is 5*12cm.
6. the method according to claim 1 for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that: the step
3) vacuum degree is -0.1Mpa.
7. the method according to claim 1 for preparing rich phosphorus phase phosphorized copper hollow nano-sphere, it is characterised in that: the step
3) the phosphating reaction time is 1~4h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707321A (en) * | 2019-10-23 | 2020-01-17 | 合肥国轩高科动力能源有限公司 | Copper-coated hollow nickel phosphide material and preparation method and application thereof |
| CN111313006A (en) * | 2020-03-03 | 2020-06-19 | 顺德职业技术学院 | Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof |
| WO2024098957A1 (en) * | 2022-11-10 | 2024-05-16 | 东江环保股份有限公司 | Preparation method and use of nano copper phosphide |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110707321A (en) * | 2019-10-23 | 2020-01-17 | 合肥国轩高科动力能源有限公司 | Copper-coated hollow nickel phosphide material and preparation method and application thereof |
| CN111313006A (en) * | 2020-03-03 | 2020-06-19 | 顺德职业技术学院 | Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof |
| CN111313006B (en) * | 2020-03-03 | 2022-05-10 | 顺德职业技术学院 | Phosphorus-copper negative electrode material for lithium ion battery and preparation method thereof |
| WO2024098957A1 (en) * | 2022-11-10 | 2024-05-16 | 东江环保股份有限公司 | Preparation method and use of nano copper phosphide |
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