CN107317008A - The preparation method and application of core-shell type carbon-clad metal phosphide nano-complex particle - Google Patents
The preparation method and application of core-shell type carbon-clad metal phosphide nano-complex particle Download PDFInfo
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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
- H01M4/362—Composites
- H01M4/366—Composites as layered products
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- 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
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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
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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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
- H01M4/133—Electrodes based on carbonaceous material, e.g. graphite-intercalation compounds or CFx
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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
- H01M4/136—Electrodes based on inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy
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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
- H01M4/36—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
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- 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 present invention provides a kind of preparation method of core-shell type carbon-clad metal phosphide nano-complex particle, and gained compound particle is applied in field of lithium ion battery as lithium ion battery negative material.The material and inert gas of a certain proportion of carbonaceous sources are added in direct-current arc metal nano powder production equipment is automatically controlled, evaporated metal raw material obtains carbon-clad metal nano particle presoma；Then it is put into high pressure sealing reactor and is heat-treated after presoma is mixed with red phosphorus powder, obtain carbon-clad metal phosphide nano composite material, using carbon coating nickel phosphide nano complex material as active material, makes lithium-ion electric pole piece.The advantage of the invention is that being used as presoma using the carbon-coating nickel nano-particle of fabricated in situ; low temperature phosphor obtains carbon coating nickel phosphide nano-complex particle; with higher Li insertion extraction capacity density and cyclical stability; low raw-material cost; technique is simple; can prepare with scale, suitable industrialization production requirements.
Description
Technical field
The invention belongs to nano material preparation technology and application field, it is related to a kind of core-shell type carbon-clad metal phosphide and receives
Rice compound particle preparation method and its as lithium ion battery negative material field of lithium ion battery application.
Background technology
Lithium ion battery (also referred to as lithium rechargeable battery or lithium-ions battery) have light weight, energy density it is big,
The advantages of voltage height, small volume, good cycle, memory-less effect, it is considered to be 21 century most have application prospect the energy it
One, and be widely used in traffic, communication and regenerative resource department.Have circulation time length due to graphite at present, it is a large amount of
In the presence of and be widely used negative material as commercial Li-ion battery the advantages of low cost, although carbon material is being made
To have preferable cycle performance in negative electrode of lithium ion battery material, but its low theoretical capacity (372mAh/g) can not meet
The today's society demand growing to the energy.Therefore, find and develop that a kind of energy density is high, with low cost, high charge-discharge
The material of the lithium ion battery negative material of speed and high circulation stability turns into current study hotspot to substitute graphite.
In recent years with the further investigation to lithium ion battery negative material, occur in that in succession different types of with storage lithium
The negative material of performance, such as metal simple-substance nano-particle, alloy nano particle, metal sulfide, metal nitride, transition gold
Belong to compound system of oxide, metal phosphide and these materials etc..Wherein, metal phosphide material is due to higher
The advantages of specific capacity, small electrode polarization and widely paid close attention to.Such as metal phosphide (MSx(M:Mn, Fe, Co, Ni, Cu etc.))
Series material, C.Wu et al. is reported in [Advanced Materials (2017 (29) 1604015)] to be closed using two-step method
Into the graphene Ni of three-dimensional core shell structure2P composites, as lithium ion cell electrode negative material, discharge first
During specific capacity be 875mAh/g, but after it is recycled to 10 times, its specific capacity is down to 500mAh/g.In order to further carry
High metal phosphide is used as the specific capacity and energy density of negative material, some new synthesis carbon-clad metal phosphide composite woods
Preparation method for material need to be studied further.
The research of metal phosphide is mostly derived from lithium ion and combines to form compound L i with phosphorus3P, these phosphides have in itself
There is high specific capacity, but need to be combined with carbon to improve the conduction of carrier in charge and discharge process.Patent [CN
101304089A] disclose the preparation method of lithium ion battery negative material, i.e. nickel phosphide film a kind of.This method is using reaction
Property pulsed laser deposition, is made the target used in pulsed laser deposition, in argon gas gas by tabletting after phosphorus powder and nickel powder ground and mixed
Laser beam is incided on target after lens focus in atmosphere, and nickel phosphide film is arrived in deposition on substrate.The phosphatization that this method is obtained
Nickel (Ni2P) discharge capacity is 730mAh/g to electrode first, and 30 capacity of circulation are down to 400mAh/g, in order to further improve
The specific capacity of negative material, still needs to improve the preparation method of metal phosphide.Patent [CN 101556998A] discloses a kind of gold
Belong to phosphide as the preparation method of ion secondary battery cathode material lithium.This method by red phosphorus powder and metal dust in proportion
Mixing be put into ball grinder, ball milling 10-50 hours under hydrogen or argon gas atmosphere, by ball milling product under same atmosphere 400-
1000 DEG C of preroast 5-30 hours, last 100-600 DEG C of after baking 5-30 hours under hydrogen or argon gas atmosphere, this method is obtained
The material manufacturing cycle arrived is longer, consumes energy larger, preparation technology is more complicated, still needs to do further improvement.
For simple metal phosphide material, although with high lithium storage content, but be used as negative electrode active
Material, during lithium ion battery charge and discharge cycles, the deintercalation repeatedly of lithium easily makes electrode volume expansion gradually efflorescence failure,
The chemical property of electrode is set to be deteriorated, capacity reduction.And carbon material has very high hardness and intensity, carbon-clad metal phosphorus is constructed
Compound nano-powder, can effectively suppress volumetric expansion, improve material circulation performance.
The content of the invention
For prior art deficiency and Improvement requirement, it is multiple that the present invention provides a kind of core-shell type carbon-clad metal phosphide nanometer
The preparation method and technology of particle is closed, using the carbon-clad metal nano particle of fabricated in situ as presoma, by low temperature phosphor
Technique obtains carbon-clad metal phosphide nano-complex particle, and there is the nano-complex particle graphitization carbon ball to be shell, metal phosphorus
Compound is shell-caryogram nanostructured of core, improves Li insertion extraction capacity and cyclical stability：Effectively raise at big times
Specific capacity under the conditions of rate discharge and recharge；Under the protection of graphitized carbon shell, electrode material structure is effectively safeguarded, improves electrode
Stable circulation performance；Can obtain 2140mAh/g initial discharge capacities in lithium ion battery with nonaqueous electrolyte, 15 circulations with
1300mAh/g discharge capacity is remained in that afterwards.
In order to achieve the above object, the technical solution adopted by the present invention is:Core-shell type carbon-clad metal phosphide nanometer is multiple
Close the preparation method of particle, it is characterised in that comprise the following steps：
The first step, metal raw is added in the powder for automatically controlling direct-current arc metal nano powder production equipment generates room
Material, carbon source and inert gas, evaporated metal raw material obtain carbon covered metal nanoparticle precursor；
Second step, carbon covered metal nanoparticle precursor is mixed with red phosphorus powder under the conditions of anhydrous and oxygen-free and is put into high pressure
Seal in reactor, under inert gas shielding, after pyroreaction, be cooled to room temperature, obtain carbon-clad metal phosphide nanometer
Compound particle.
Raw metal is one or both of iron, manganese, cobalt, nickel, copper, zinc combination of the above in the first step, using block
Body or powder, raw metal are 20~80g, are placed on powder generation room anode.
When carbon source is gaseous state in the first step, the ratio of carbon source and inert gas is 1:5~4:1；When carbon source is liquid,
In carbon source and raw metal placing graphite crucible, graphite crucible is placed on powder generation room anode, every in powder generation room
Add the inert gas that 5~50ml carbon sources are passed through 0.01~0.03MPa；When carbon source is solid-state, carbon source and raw metal mixing pressure
It is placed on after block on powder generation room anode, carbon source is 1 with metal-powder mass ratio:3~5:1, adding inert gas volume is
0.01MPa~0.06MPa.
The gaseous carbon source be methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene in one kind or
Two or more mixing；Described liquid carbon source is the one or more combination of ethanol, methanol or propyl alcohol；Described solid-state carbon source is
One or more combination in carbon and its allotrope, glucose or polypyrrole PPy.
Inert gas is the one or more combination of argon gas, helium or neon in the first step.
The mass ratio of carbon covered metal nanoparticle precursor and red phosphorus powder is 1 in the second step:1~1:3；Described
Anhydrous and oxygen-free is that water content is less than thousand a ten thousandths in two steps, and oxygen content is less than thousand a ten thousandths.
Inert gas is the one or more combination of argon gas, helium, neon or nitrogen, inert gas body in the second step
Product is 0.01MPa~0.08MPa；The vacuum heating conditions are 500~800 DEG C, react 1~4h.
A kind of application of carbon-clad metal phosphide nano-complex particle, it is characterised in that by carbon-clad metal phosphide
Nano-complex particle is applied in lithium-ion electric pole piece is prepared, and is comprised the following steps：It is nano combined in carbon-clad metal phosphide
Conductive agent and binding agent are added in particle, is dispersed in solvent and obtains electrode material；Electrode material is applied to and led
The single or double of electrojet device, after solvent is removed under vacuum heating conditions, different sizes are prepared according to battery specifications
Electrode slice.
Described carbon-clad metal phosphide nano-complex particle and the mass percent of binding agent are (50~90):10；
Described conductive agent is carbon black conductive agent (acetylene black, Super P, Super S, 350G, carbon fiber (VGCF), CNT
(CNTs), Ketjen black (Ket jen black EC300J, Ket jen black EC300JD)) etc.), graphite agent (KS-
6th, SFG-6 etc.) or graphene in one or more combination, the mass percent of conductive agent is less than 40；Described binding agent gathers
Vinylidene chloride (PVDF), polytetrafluoroethylene (PTFE) (PTFE), sodium carboxymethylcellulose (CMC), butadiene-styrene rubber (SBR) or polyvinyl alcohol
(PVA) one or more combination.
Described solvent is 1-METHYLPYRROLIDONE (NMP), dinethylformamide (DMF) or deionized water；Described
Conductive current collector is iron foil, nickel foil, aluminium foil, copper foil, foam copper, nickel foam, foamed aluminium or foamed iron.
Beneficial effects of the present invention are:
(1) preparation process is simple, and low raw-material cost does not produce harmful substance, can be with industrialized production；
(2) prepare during carbon-clad metal phosphide nano-complex particle, the presence of carbon shell can suppress metallic element
Oxidation, effectively prevent the reunion of nano-particle in heat treatment process；
(3) in heat treatment process, carbon shell provides the diffusion admittance that phosphorus atoms enter in core, makes phosphorus atoms and kernel gold
Category reaction generation metal phosphide, ultimately form by shell of carbon, metal phosphide for core core-shell type nano structure；
(4) presence of graphitized carbon shell provides lithium ion exchanged passage, and carbon shell has very high intensity, effectively suppresses
The volumetric expansion of metal phosphide, it is to avoid metal phosphide nano-particle because of Li insertion extraction process and caused by efflorescence and failure；
(5) phosphide has height ratio capacity in itself, and compound L i has been combined to form with lithium3P, graphitized carbon shell material is provided
More avtive spots are combined with lithium ion, form LiC6Mutually and with good circulation characteristic.Based on the advantage of two kinds of materials, institute
The nano material of synthesis has the comprehensive advantage such as height ratio capacity and high circulation stability.
Brief description of the drawings
Fig. 1 is X-ray diffraction (XRD) collection of illustrative plates for the carbon coating nickel phosphide nano-complex particle that embodiment 1 is synthesized.
Fig. 2 is the Raman spectrum (Raman) for the carbon coating nickel phosphide nano-complex particle that embodiment 1 is synthesized.
Fig. 3 is charge and discharge of the carbon coating nickel phosphide nano-complex particle of the synthesis of embodiment 1 under 300mA/g current density
Electric curve.
Fig. 4 is circulation of the carbon coating nickel phosphide nano-complex particle of the synthesis of embodiment 1 under 300mA/g current density
Stability curve.
Embodiment
The present invention is further illustrated with reference to the accompanying drawings and detailed description.
Embodiment 1
Generated in the present embodiment using equipment to automatically control direct-current arc metal nano powder production equipment by powder
Room, powder granularity grading room, powder dust trapping chamber, powder handling room, vacuum system, gas-circulating system, Hydraulic Power Transmission System, water
Cooling system and programming Control system composition；Negative electrode and anode are installed in powder generation room, and locular wall is generated and outside through powder
Hydraulic drive and the connection of programming Control system；When preparing powder, anode is charged material into, the gap with negative electrode formation 10-30mm,
Whole equipment is vacuumized, and leads to cooling water.It is passed through after active gases and condensed gas, startup power supply and starting the arc device, in negative electrode and sun
Electric arc is formed between pole, material starts evaporative condenser and forms nano-powder particle, and specific method is：
Take 40g nickel blocks to be put on the powder generation room anode for automatically control direct-current arc metal nano powder production equipment to steam
Hair, while it is 3 to be passed through ratio:4 methane and argon gas, obtains carbon-coating nickel nanoparticle precursor；By this presoma in gloves
1 is pressed in case (ensureing anhydrous and oxygen-free environment):2 mass ratioes are put after being mixed with red phosphorus powder into high pressure sealing reactor, instead
Answer kettle to be heated to 600 DEG C of progress heat treatment 3h under the protection of 0.05MPa argon gas, be cooled to room temperature, obtain carbon coating nickel phosphide and receive
Nano composite material.The XRD for the carbon coating nickel phosphide nano composite material that embodiment 1 is obtained is as shown in Figure 1.The diffraction maximum in figure
Determine to mainly contain nickel phosphide and on a small quantity the elemental nickel phase of non-phosphatization in the composite.
Embodiment 2
Obtained carbon-clad metal phosphide nano composite material in above-described embodiment 1 is fabricated to lithium-ion electric pole piece.
Wherein the carbon coating nickel phosphide nano composite material of electrode slice in mass ratio 80%, 10% Ketjen black and 10% poly- inclined difluoro
Ethene (PVDF) binding agent is well mixed, and adds appropriate 1-METHYLPYRROLIDONE (NMP) dissolving, slurry is coated on copper current collector
Electrode is made；This experimental electrode 100 DEG C of dry 12h in vacuum drying oven, battery is assembled in high-purity argon gas atmosphere glove box.Its
Middle electrolyte is 1mol/L LiPF6Solution, solvent is volume ratio 1:1 ethylene carbonate (EC) and diethyl carbonate (DC).With
Polypropylene is barrier film, is that lithium piece is assembled into CR2025 button cells to electrode.
The lithium ion battery negative electrode using carbon coating nickel phosphide nano composite material as active material is made in the present invention,
At room temperature in the range of 0.01~3V, charge and discharge test is carried out to battery with 300mA/g current densities, the initial of 2140mAh/g is obtained
Specific discharge capacity, still keeps 1300mAh/g specific discharge capacity, stable cycle performance after 15 circulations.
The Raman spectrum (Raman) for the carbon coating nickel phosphide nano composite material that embodiment one is obtained is as shown in Figure 2.By scheming
The relative intensity at middle D peaks and G peaks can determine the carbon coated in the material containing a large amount of defects.
Fig. 3 and Fig. 4 are respectively at room temperature in the range of 0.01~3V, bent with the discharge and recharge that 300mA/g current density is carried out
Line and stable circulation performance curve.As seen from the figure, carbon coating phosphatization nickel composite material produced by the present invention is used as lithium ion battery
During negative material, with the first discharge specific capacity close to 2140mAh/g, Fig. 4 shows that its cycle performance is highly stable.The 15th
After secondary circulation, its reversible specific capacity remains at 1300mAh/g.
Embodiment 3
Each step of the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle described in the present embodiment
In the same manner as in Example 1, different technical parameters are：
Take 20g nickel powders and 15g carbon dusts uniformly after mixing, be pressed into block and be put into and automatically control direct-current arc metal nano powder
Evaporated on the anode of body production equipment powder generation room, while being passed through 0.06MPa helium, obtain carbon-coating nickel nano-particle forerunner
Body；This presoma is pressed 1 in glove box:3 mass ratioes are put after being mixed with red phosphorus powder into sealing reactor, reactor
800 DEG C of progress heat treatment 1h are heated under the protection of 0.01MPa nitrogen, room temperature is cooled to, carbon coating nickel phosphide nanometer are obtained multiple
Condensation material.
Embodiment 4
Obtained carbon-clad metal phosphide nano composite material in above-described embodiment 3 is fabricated to lithium-ion electric pole piece.
Wherein the carbon coating nickel phosphide nano composite material of electrode slice in mass ratio 50%, 40% CNT and 10% butylbenzene rubber
Glue (SBR) binding agent is well mixed, and adds appropriate dinethylformamide (DMF) dissolving, slurry is coated on copper current collector and made
Obtain electrode.
Embodiment 5
Each step of the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle described in the present embodiment
In the same manner as in Example 1, different technical parameters are：
Take 80g nickel powders to be put into graphite crucible, add 20~40ml ethanol, graphite crucible is put into and automatically controls direct current
Evaporated on the anode of the powder generation room of electric arc metal nano powder production equipment, while being passed through 0.01MPa neons obtains carbon bag
Cover nickel nano particle presoma；This presoma is pressed 1 in glove box:1 mass ratio puts paramount after being mixed with red phosphorus powder
In means of press seals reactor, reactor is heated to 500 DEG C of progress heat treatment 4h under the protection of 0.08MPa helium, is cooled to room temperature, obtains
To carbon coating nickel phosphide nano composite material.
Embodiment 6
Obtained carbon-clad metal phosphide nano composite material in above-described embodiment 5 is fabricated to lithium-ion electric pole piece.
Wherein carbon coating nickel phosphide nano composite material, 10% acetylene black and 20% polyvinyl alcohol of electrode slice in mass ratio 70%
(PVA) binding agent is well mixed, and is added appropriate amount of deionized water dissolving, slurry is coated on copper current collector electrode is made.
Claims (10)
1. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle, it is characterised in that comprise the following steps：
The first step, automatically control direct-current arc metal nano powder production equipment powder generate room in add raw metal,
Carbon source and inert gas, evaporated metal raw material obtain carbon covered metal nanoparticle precursor；
Second step, carbon covered metal nanoparticle precursor is mixed with red phosphorus powder under the conditions of anhydrous and oxygen-free and is put into high pressure sealing
In reactor, under inert gas shielding, after pyroreaction, room temperature is cooled to, carbon-clad metal phosphide is obtained nano combined
Particle.
2. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle according to claim 1, its feature
Be, raw metal is one or both of iron, manganese, cobalt, nickel, copper, zinc combination of the above in the first step, using block or
Powder, raw metal is 20~80g, is placed on powder generation room anode.
3. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle according to claim 1, its feature
It is, when carbon source is gaseous state in the first step, the ratio of carbon source and inert gas is 1:5~4:1；When carbon source is liquid, carbon
In source and raw metal placing graphite crucible, graphite crucible is placed on powder generation room anode, is often added in powder generation room
Enter the inert gas that 5~50ml carbon sources are passed through 0.01~0.03MPa；When carbon source is solid-state, carbon source and raw metal mixing briquetting
After be placed on powder generation room anode, carbon source and metal-powder mass ratio are 1:3~5:1, adding inert gas volume is
0.01MPa~0.06MPa.
4. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle according to claim 3, its feature
It is, the gaseous carbon source is one or both of methane, ethane, acetylene, ethene, propylene, propine, propane, butane, butylene
It is mixed above；Described liquid carbon source is the one or more combination of ethanol, methanol or propyl alcohol；Described solid-state carbon source be carbon and
One or more combination in its allotrope, glucose or polypyrrole PPy.
5. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle according to claim 1, its feature
It is, inert gas is the one or more combination of argon gas, helium or neon in the first step.
6. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle according to claim 1, its feature
It is, the mass ratio of carbon covered metal nanoparticle precursor and red phosphorus powder is 1 in the second step:3~1:1；Described second
Anhydrous and oxygen-free is that water content is less than thousand a ten thousandths in step, and oxygen content is less than thousand a ten thousandths.
7. the preparation method of core-shell type carbon-clad metal phosphide nano-complex particle according to claim 1, its feature
It is, inert gas is the one or more combination of argon gas, helium, neon or nitrogen, inert gas volume in the second step
For 0.01MPa~0.08MPa；The vacuum heating conditions are 500~800 DEG C, react 1~4h.
8. a kind of application according to any described carbon-clad metal phosphide nano-complex particles of claim 1-7, its feature
It is, carbon-clad metal phosphide nano-complex particle is applied in lithium-ion electric pole piece is prepared, comprised the following steps：In carbon
Addition conductive agent and binding agent in metal phosphide nano-complex particle are coated, is dispersed in solvent and obtains electrode material
Material；Electrode material is applied to the single or double of conductive current collector, after solvent is removed under vacuum heating conditions, according to electricity
Pond specification prepares various sizes of electrode slice.
9. the application of carbon-clad metal phosphide nano-complex particle according to claim 8, it is characterised in that described
The mass percent of carbon-clad metal phosphide nano-complex particle and binding agent is (50~90):10；The conductive agent is charcoal
The one or more combination of black conductive agent, graphite agent or graphene, the mass percent of conductive agent is less than 40；Described is viscous
Knot agent is one or more of groups of polyvinylidene chloride, polytetrafluoroethylene (PTFE), sodium carboxymethylcellulose, butadiene-styrene rubber or polyvinyl alcohol
Close.
10. the application of carbon-clad metal phosphide nano-complex particle according to claim 8, it is characterised in that described
Solvent be 1-METHYLPYRROLIDONE, dinethylformamide or deionized water；Described conductive current collector be iron foil, nickel foil,
Aluminium foil, copper foil, foam copper, nickel foam, foamed aluminium or foamed iron.
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| CN108878164A (en) * | 2018-06-20 | 2018-11-23 | 中国地质大学（北京） | For supercapacitor or the phosphorus nickel combination electrode material of lithium battery and preparation method thereof |
| CN109865524A (en) * | 2017-12-05 | 2019-06-11 | 中国科学院大连化学物理研究所 | A kind of carbon support transition metal phosphide produces hydrogen elctro-catalyst and preparation method thereof |
| CN110952112A (en) * | 2019-12-24 | 2020-04-03 | 济南大学 | Graphene outer layer @ nickel phosphide interlayer @ nickel inner layer framework composite material and preparation method and application thereof |
| CN111112602A (en) * | 2019-12-26 | 2020-05-08 | 华侨大学 | Aluminum oxide-carbon composite coated copper powder, preparation method and application |
| 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 |
| CN111564610A (en) * | 2020-04-03 | 2020-08-21 | 华南师范大学 | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof |
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| 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 |
| 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 |
| CN111564610A (en) * | 2020-04-03 | 2020-08-21 | 华南师范大学 | Carbon-coated cuprous phosphide-copper composite particle modified by carbon nanotube and preparation method and application thereof |
| CN113299492A (en) * | 2021-06-07 | 2021-08-24 | 北京工业大学 | MOF-derived porous metal phosphide nanosheet array and application thereof |
| CN113299492B (en) * | 2021-06-07 | 2022-05-27 | 北京工业大学 | MOF-derived porous metal phosphide nanosheet array and application thereof |
| CN113422031A (en) * | 2021-07-01 | 2021-09-21 | 大连理工大学 | Preparation method and application of carbon-coated zinc diphosphide composite material prepared by three-step method |
| CN113422031B (en) * | 2021-07-01 | 2022-04-12 | 大连理工大学 | Preparation method and application of carbon-coated zinc diphosphide composite material prepared by three-step method |
| CN113725436A (en) * | 2021-08-31 | 2021-11-30 | 江苏科技大学 | Phosphorus-based composite material and preparation method thereof, sodium ion secondary battery cathode and secondary battery |
| CN113839026A (en) * | 2021-10-18 | 2021-12-24 | 苏州大学 | Lithium ion battery cathode composite material and preparation method thereof |
| CN113839026B (en) * | 2021-10-18 | 2023-03-24 | 苏州大学 | Lithium ion battery cathode composite material and preparation method thereof |
| CN114203458A (en) * | 2021-11-23 | 2022-03-18 | 湖北大学 | Conductive polymer coated nickel phosphide nanowire and preparation method and application thereof |
| CN114203458B (en) * | 2021-11-23 | 2023-10-03 | 湖北大学 | Nickel phosphide nanowire coated by conductive polymer and preparation method and application thereof |
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