CN109768260A - A kind of two cobalts of phosphatization/carbon composite and its preparation method and application - Google Patents
A kind of two cobalts of phosphatization/carbon composite and its preparation method and application Download PDFInfo
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- CN109768260A CN109768260A CN201910063119.6A CN201910063119A CN109768260A CN 109768260 A CN109768260 A CN 109768260A CN 201910063119 A CN201910063119 A CN 201910063119A CN 109768260 A CN109768260 A CN 109768260A
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The present invention provides a kind of two cobalts of phosphatization/carbon composites and its preparation method and application.Two cobalts of the phosphatization/carbon composite provided by the invention includes carbon material substrate and the Co that is embedded in the carbon material substrate2P nanometer sheet.The preparation method includes: to carry out hydro-thermal reaction after (1) mixes cobalt source, phosphorus source and surfactant with water, obtain Co2P presoma；(2) by Co2After P presoma is mixed with organic carbon source solution, hydro-thermal reaction is carried out, Co is obtained2P/C composite material precursor；(3) by Co2P/C composite material precursor is calcined under protective atmosphere, obtains two cobalts of the phosphatization/carbon composite.Two cobalts of phosphatization provided by the invention/carbon composite good conductivity, specific capacity is high, high rate performance and good cycle.Preparation method raw material provided by the invention are cheap and easy to get, and preparation process is simple, and operation degree of controllability is strong.
Description
Technical field
The invention belongs to new energy materials field, it is related to a kind of electrode material more particularly to a kind of two cobalts of phosphatization/carbon is compound
Material and its preparation method and application.
Background technique
Since lithium ion battery has energy density big, light weight, small in size, good cycle, environmental-friendly and without note
Recall the advantages such as effect, is widely used in the every field such as electronic product, electric car and extensive energy storage.But lithium resource is on ground
Scarcity in shell and the problems such as being unevenly distributed, it is insufficient for people's demand growing to lithium ion battery, this serious system
About lithium ion battery is on a large scale applied.So new secondary battery that is abundant, low in cost, haveing excellent performance of exploiting natural resources,
Have become the new development trend in battery material field and research hotspot.
In recent years, sodium and kalium ion battery receive researchers and widely pay close attention to, it is considered to be replace lithium ion battery
As the ideal chose of next-generation accumulation power supply, because sodium, potassium and lithium belong to same major element, there is similar physical chemistry
Matter.It is resourceful simultaneously as sodium, potassium element are widely distributed, it is cheap the advantages that, more meet scale stored energy application
It is required that.Therefore, sodium ions to potassium ions battery also receives the extensive concern of numerous researchers as new type of energy storage device.
But since the radius of sodium and potassium ion is all bigger than lithium ion, to the electrode for capableing of free deintercalation sodium and potassium ion
The requirement of material is stringenter.When using traditional graphite cathode as when sodium-ion battery cathode, sodium ion is embedded in and abjection
When specific capacity it is lower, the serious development for restricting sodium-ion battery.Although the deintercalation potassium ion that traditional graphite cathode can be reversible,
But theoretical specific capacity is only 279mAh/g when as kalium ion battery cathode.Therefore, a kind of new sodium and potassium ion are researched and developed
Cell negative electrode material seems particularly significant.
Co2P has high theoretical specific capacity, high chemical stability, high conductivity, low as a kind of metal gap compound
The advantages that cost and smaller charge and discharge process polarization, have been widely used for the negative electrode material of lithium ion battery.However, simple
Co2There is repeatedly deintercalation process and be easy to make electrode volume variation gradually dusting failure in P material, become the chemical property of battery
Difference.
CN102347474A discloses a kind of large-capacity lithium ion battery cathode and preparation method thereof, including electrode base sheet,
The negative film of substrate surface, the negative film of substrate surface are phosphatization cobalt thin film；Preparation method be a. by metallic cobalt powder with
The mixing of red phosphorus powder, it is 1: 1~3 (molar ratios) that mixed proportion, which is metallic cobalt than red phosphorus powder, is uniformly mixed grinding, pulse is made in tabletting
Target used in laser deposition；B., target and substrate be put into vacuum deposition is intracavitary, and target and substrate distance 25-50mm, working gas are
Argon atmosphere, substrate temperature are 500-700 DEG C；C. the laser beam of laser is incident on the target of rotation after lens focus, warp
The particle of laser beam excitation is splashed on substrate.This method complex steps, the expensive equipment used, and the phosphatization cobalt prepared is thin
Film has that chemical property is to be improved, is not suitable for sodium ions to potassium ions battery.
CN107403911A discloses a kind of graphene/transition metal phosphide/C-base composte material, preparation method and lithium
Ion battery negative electrode.Transition metal iron, cobalt or nickel and phosphorus shape in the graphene/transition metal phosphide/carbon composite
At compound.Using graphene as matrix in the composite material, received with the transition metal phosphide with good nanostructure
Rice grain is load, constructs graphene/transition metal phosphide composite material；Composite material is carried out using agraphitic carbon simultaneously
The modifications such as cladding, filling, connection, obtain graphene/transition metal phosphide/carbon ternary nano composite material.Although the program
Chemical property is fine, but composite material is needed using graphene, and cost of material is higher, and its preparation process is cumbersome.
CN106111171A discloses a kind of preparation method of the phosphatization cobalt of carbon-coating package, and this method is using cobalt salt and organic
Ligand is raw material, first metal-organic framework material of the synthesis containing cobalt, then in turn through high temperature pyrolysis, air oxidation and low temperature
Phosphatization has synthesized the phosphatization cobalt of carbon-coating package.Although program preparation cost relative moderate, its product are not used to battery
Pole piece can only be used as catalyst.
Therefore, it is simple to develop a kind of preparation method, conductivity is high, circulation and good rate capability, and be suitable for sodium/potassium from
The Co of sub- battery2P/C composite material is significant for this field.
Summary of the invention
Aiming at the above shortcomings existing in the prior art, the purpose of the present invention is to provide a kind of two cobalts of phosphatization/carbon is compound
Material and its preparation method and application.Two cobalts of phosphatization provided by the invention/carbon (Co2P/C) conductivity of composite material is high, specific volume
Amount is high, and circulation and good rate capability, raw material are cheap and easy to get, and preparation process is simple, and operation degree of controllability is strong.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the present invention provides a kind of two cobalts of phosphatization/carbon composite, two cobalts of phosphatization/carbon composite packet
The Co for including carbon material substrate and being embedded in the carbon material substrate2P nanometer sheet.
Co provided by the invention2The Co of P/C composite material2P nanometer sheet is embedded in carbon material substrate, alleviates phosphide
The volume change problem that grain generates during ion insertion and extraction, to improve the cyclical stability of composite material.On the other hand, carbon
Synergistic effect between phosphide improves the specific capacity and high rate performance of composite material.
In two cobalts of phosphatization/carbon composite provided by the invention, Co2P nanometer sheet is uniformly distributed in carbon material substrate, this
Help to be promoted the conductivity of the composite material.
It is used as currently preferred technical solution below, but not as the limitation to technical solution provided by the invention, leads to
Following preferred technical solution is crossed, can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the Co2P nanometer sheet is monodispersed Co2P nanometer sheet.
Preferably, the Co2The size of P nanometer sheet is 1-6 μm, such as 1 μm, 2 μm, 3 μm, 4 μm, 5 μm or 6 μm etc., but
It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.In the present invention, if Co2P
Nanometer sheet it is oversized, will lead to ion diffusion slow down；If Co2P nanometer sheet it is undersized, will lead to sheet-like particle powder
It is broken, influence the transmission of ion.Here, the size refers to Co2The side length of the longest edge of P nanometer sheet.
Preferably, the Co2P nanometer sheet with a thickness of 3-14nm, such as 3nm, 5nm, 7nm, 9nm, 10nm, 11nm,
12nm or 14nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.This
In invention, if Co2The thickness of P nanometer sheet is excessive, will lead to ion transmission path and becomes larger, and then ion diffusion is caused to slow down；
If Co2The thickness of P nanometer sheet is too small, easily leads to granule atomization, structure collapses.
Preferably, two cobalts of the phosphatization/carbon composite is layer structure.Layer structure can promote the composite material
Specific surface area, and be conducive to make pore structure more abundant.
Preferably, in two cobalts of the phosphatization/carbon composite, carbon material substrate and Co2The mass ratio of P nanometer sheet is 0.1:
1-0.5:1, such as 0.1:1,0.2:1,0.3:1,0.4:1 or 0.5:1 etc., it is not limited to cited numerical value, the numerical value
Other unlisted numerical value are equally applicable in range.In the present invention, if carbon material substrate and Co2The mass ratio mistake of P nanometer sheet
(i.e. Co greatly2P nanometer sheet is very few), the carbon-coating that will lead to cladding is blocked up, hinders the transmission of ion；If carbon material substrate and Co2P
Too small (the i.e. Co of the mass ratio of nanometer sheet2P nanometer sheet is excessive), the carbon-coating that will lead to cladding is excessively thin, and conductivity increases less, equally
Also it influences the transmission of ion and then influences chemical property
Preferably, the specific surface area of two cobalts of the phosphatization/carbon composite is 220-260m2g-1, such as 220m2g-1、
230m2g-1、240m2g-1、250m2g-1Or 260m2g-1Deng, it is not limited to cited numerical value, in the numberical range other
Unlisted numerical value is equally applicable.
Preferably, two cobalts of the phosphatization/carbon composite is porous material.
In the present invention, two cobalts of phosphatization/carbon composite is porous material, and pore structure is abundant, is conducive to ion and electronics
Fast transferring, active material volume change caused by ion insertion and extraction process can be effectively relieved in cyclic process, make structure
Stablize, improves the chemical property of material.
Preferably, the porosity of two cobalts of the phosphatization/carbon composite be 30%-60%, such as 30%, 35%, 40%,
50%, 55% or 60% etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With.
Preferably, the aperture of two cobalts of the phosphatization/carbon composite be 1-10nm, such as 1nm, 2nm, 3nm, 4nm, 5nm,
6nm, 7nm, 8nm, 9nm or 10nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Second aspect, the present invention provide a kind of two cobalts of phosphatization/carbon composite preparation method as described in relation to the first aspect, institute
State method the following steps are included:
(1) after mixing cobalt source, phosphorus source and surfactant with water, hydro-thermal reaction is carried out, Co is obtained2P presoma；
(2) by step (1) Co2After P presoma is mixed with organic carbon source solution, hydro-thermal reaction is carried out, Co is obtained2P/C
Composite material precursor；
(3) by step (2) Co2P/C composite material precursor is calcined under protective atmosphere, obtains the phosphorus
Change two cobalts/carbon composite.
Preparation method provided by the invention uses the Co of two one-step hydrothermals preparation2P/C composite material, raw material are inexpensively easy
, preparation process is simple, and operation degree of controllability is strong.The purpose of first step hydro-thermal reaction is to synthesize pure phase Co2P forerunner, second step
The purpose of hydro-thermal reaction is organic carbon source being evenly coated at Co2P particle surface.
As currently preferred technical solution, step (1) cobalt source is soluble cobalt.
Preferably, the soluble cobalt includes any one in cobalt nitrate, cobalt acetate or cobalt chloride or at least two
Combination.Here, the cobalt nitrate, cobalt acetate or cobalt chloride not only include pure material, also include its corresponding hydrate, such as
Cabaltous nitrate hexahydrate, four acetate hydrate cobalts or cobalt chloride hexahydrate etc..
Preferably, step (1) phosphorus source includes red phosphorus.
Preferably, the molar ratio of step (1) cobalt source and phosphorus source is 1:4.5-1:6.0, such as 1:4.5,1:5,1:5.5
Or 1:6 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (1) described surfactant includes cetyl trimethylammonium bromide (CTAB), polyvinyl pyrrole
In alkane (PVP) or neopelex (SDBS) any one or at least two combination.It is typical but be non-limited
Combination have the combination of CTAB and PVP, the combination of CTAB and SDBS, PVP and the combination of SDBS etc..
Preferably, in the hydro-thermal reaction system of step (1), the concentration of the surfactant is 1.43-4.29g/L, example
Such as 1.43g/L, 1.5g/L, 2.0g/L, 2.5g/L, 3.0g/L, 3.5g/L, 4.0g/L or 4.29g/L, it is not limited to institute
The numerical value enumerated, other interior unlisted numerical value of the numberical range are equally applicable.Here, the hydro-thermal reaction system refers to cobalt
Source, phosphorus source, the hydro-thermal reaction system of surfactant and water composition.
Preferably, step (1) the mixed method is to be stirred.
As currently preferred technical solution, the temperature of step (1) described hydro-thermal reaction is 140-220 DEG C, such as 140
DEG C, 150 DEG C, 160 DEG C, 170 DEG C, 180 DEG C, 190 DEG C, 200 DEG C, 210 DEG C or 220 DEG C etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the time of step (1) described hydro-thermal reaction be 15-60h, such as 15h, 20h, 25h, 30h, 35h, 40h,
45h, 50h, 55h or 60h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
It is applicable in.
Preferably, step (1) described hydro-thermal reaction carries out in the stainless steel autoclave for having teflon lining.
Preferably, step (1) further include: to the Co2P presoma is washed and is dried.
Preferably, the washing methods is first to use salt acid elution, then with water and ethanol washing.For example, with salt acid elution two
Deionized water and ethanol wash are used for several times again after secondary.
Preferably, the concentration of the hydrochloric acid be 1-3mol/L, such as 1mol/L, 1.5mol/L, 2mol/L, 2.5mol/L or
3mol/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As currently preferred technical solution, in step (2), the organic carbon source includes glucose, sucrose or lemon
In acid any one or at least two combination.It is typical but be non-limiting combination and have: the combination of dextrose and saccharose, Portugal
The combination etc. of the combination of grape sugar and citric acid, sucrose and citric acid.
Preferably, in step (2) the organic carbon source solution, the concentration of organic carbon source is 0.05-0.5mol/L, such as
0.05mol/L, 0.1mol/L, 0.2mol/L, 0.3mol/L, 0.4mol/L or 0.5mol/L etc., it is not limited to cited
Numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, in step (2), the Co2The mass ratio of P presoma and organic carbon source is 1:0.15-1:0.55, example
Such as 1:0.15,1:0.25,1:0.35,1:0.45 or 1:0.55, it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable.Here, the Co2The quality of P presoma is Co2The quality of P presoma dry powder, i.e., it is dry
Quality after dry.
As the preferred technical solution of this law name, the temperature of step (2) described hydro-thermal reaction is 160-200 DEG C, such as 160
DEG C, 170 DEG C, 180 DEG C, 190 DEG C or 200 DEG C etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value it is equally applicable.
Preferably, the time of step (2) described hydro-thermal reaction be 2-5h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h or
5h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (2) described hydro-thermal reaction carries out in the stainless steel autoclave for having teflon lining.
As currently preferred technical solution, step (3) described protective atmosphere includes argon gas.
Preferably, the temperature of step (3) described calcining be 500-700 DEG C, such as 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C or
700 DEG C etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the time of step (3) described calcining be 2-6h, such as 2h, 2.5h, 3h, 3.5h, 4h, 4.5h, 5h,
5.5h or 6h etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the heating rate of step (3) described calcining be 1-10 DEG C/min, such as 1 DEG C/min, 2 DEG C/min, 3 DEG C/
Min, 4 DEG C/min, 5 DEG C/min, 6 DEG C/min, 7 DEG C/min, 8 DEG C/min, 9 DEG C/min or 10 DEG C/min etc., it is not limited to
Cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
As the further preferred technical solution of preparation method of the present invention, the described method comprises the following steps:
(1) after mixing soluble cobalt, red phosphorus and surfactant with water, in the stainless steel high pressure for having teflon lining
Hydro-thermal reaction is carried out in kettle, the temperature of hydro-thermal reaction is 140-220 DEG C, the hydro-thermal reaction time 15-60h, to hydro-thermal reaction
Product first uses 1-3mol/L salt acid elution, then with water and ethanol washing, finally dries, obtain Co2P presoma；
Wherein, soluble cobalt and the molar ratio of red phosphorus are 1:4.5-1:6.0；In hydro-thermal reaction system, the surface is living
Property agent concentration be 1.43-4.29g/L；
(2) by step (1) Co2After P presoma is mixed with the organic carbon source solution of 0.05-0.5mol/L, there is spy
Hydro-thermal reaction is carried out in the stainless steel autoclave of fluon lining, the temperature of hydro-thermal reaction is 160-200 DEG C, and the hydro-thermal reaction time is
2-5h obtains Co2P/C composite material precursor；
Wherein, the Co2The mass ratio of P presoma and organic carbon source is 1:0.15-1:0.55；
(3) by step (2) Co2P/C composite material precursor is under an argon atmosphere with the heating speed of 1-10 DEG C/min
Rate is warming up to 500-700 DEG C and is calcined, calcination time 2-6h, obtains two cobalts of the phosphatization/carbon composite.
The third aspect, the present invention provide a kind of two cobalts of phosphatization/carbon composite purposes as described in relation to the first aspect, the phosphorus
Change two cobalts/carbon composite as negative electrode material for sodium-ion battery or kalium ion battery.
Two cobalts of phosphatization/carbon composite provided by the invention is applied shows excellent follow in sodium ions to potassium ions battery
Ring and high rate performance, have broad application prospects.
Compared with prior art, the invention has the following advantages:
(1) two cobalts of phosphatization provided by the invention/carbon composite good conductivity, specific capacity is high, high rate performance and cyclicity
Can be good, negative electrode material is particularly suitable for application as sodium-ion battery or kalium ion battery.Two cobalts of phosphatization/carbon provided by the invention
Composite material is used for sodium-ion battery, and 50mA/g initial charge specific capacity is up to 366.7mAh/g, 500mA/g specific discharge capacity
Up to 301.2mAh/g, conductivity is up to 6.8 × 10-4Capacity retention ratio after lower 50 charge and discharge cycles of S/m, 50mA/g is reachable
80.1%；Two cobalts of phosphatization/carbon composite provided by the invention is used for kalium ion battery, and 50mA/g initial charge specific capacity can
Up to 297.2mAh/g, 500mA/g specific discharge capacity is up to 285.3mAh/g, and conductivity is up to 5.2 × 10-450 under S/m, 50mA/g
Capacity retention ratio after secondary charge and discharge cycles is up to 70.2%；
(2) preparation method provided by the invention uses the Co of two one-step hydrothermals preparation2P/C composite material, raw material are cheap
It is easy to get, preparation process is simple, and operation degree of controllability is strong, is adapted for industrialization large-scale production.
Detailed description of the invention
Fig. 1 is Co prepared by the embodiment of the present invention 12The XRD diagram of P/C composite material；
Fig. 2 is Co prepared by the embodiment of the present invention 12The SEM of P/C composite material schemes；
Fig. 3 is Co prepared by the embodiment of the present invention 12P/C composite material is as anode material of lithium-ion battery, in voltage zone
Between for 0.01~3.0V, current density be 50mA/g under conditions of cycle performance test chart；
Fig. 4 is Co prepared by the embodiment of the present invention 22P/C composite material is as kalium ion battery negative electrode material, in voltage zone
Between for 0.01~3.0V, current density be 50mA/g under conditions of cycle performance test chart.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this
Invention protection scope is subject to claims.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1
The present embodiment is prepared as follows Co2P/C composite material:
(1) by the Co (NO of 0.6112g3)2·6H2O, the ctab surface activating agent of the red phosphorus of 0.3577g and 0.05g are added
Into 35mL deionized water, magnetic agitation is carried out.Obtained suspension is transferred to the stainless steel autoclave of 50mL teflon lining
In, 210 DEG C are put in baking oven, 48h is reacted, obtains Co2P presoma.Washed twice afterwards with the hydrochloric acid of 3mol/L, after use deionization
Water and ethanol wash for several times, it is dry to be placed in drying box.
Wherein, Co (NO3)2·6H2The molar ratio of O and red phosphorus is about 1:5.5, in the suspension system of hydro-thermal reaction
The concentration of surfactant (CTAB) is 1.43g/L.
(2) Co for then taking 1g dry2P presoma is added in the glucose solution of 0.048mol/L, after be transferred to 50mL
In the stainless steel autoclave of teflon lining, 180 DEG C are put in baking oven, 3h is reacted, obtains Co2P/C composite material precursor.
Wherein, the Co2The mass ratio of P presoma and organic carbon source (glucose) is 1:0.3.
(3) under protection of argon gas by presoma, 550 DEG C are risen to the heating rate of 5 DEG C/min, keeps the temperature 3h, obtained described
Co2P/C composite material.
To Co manufactured in the present embodiment2P/C composite material carries out surface structure table using scanning electron microscope (SEM)
Sign carries out Pore Characterization using full-automatic multi-functional gas absorption instrument, and result is as follows.
Co manufactured in the present embodiment2P/C composite material includes carbon material substrate and is embedded in the carbon material substrate
Monodispersed Co2P nanometer sheet, carbon material substrate and Co2The mass ratio of P nanometer sheet is 0.25:1；The Co2The ruler of P nanometer sheet
Very little is 1-3 μm, with a thickness of 3-11nm；The Co2P/C composite material is layer structure porous material, and specific surface area is
256m2g-1, porosity 50%, aperture 1-4nm.
Co manufactured in the present embodiment2The electrochemical property test of P/C composite material the results are shown in Table 1 and table 2.
Fig. 1 is Co manufactured in the present embodiment2X-ray powder diffraction (XRD) figure of P/C composite material, the bright gained of the chart
Product be pure Co2P, diffraction maximum position match with JCPDS No.32-0306 standard diagram, without any other miscellaneous phase, knot
Brilliant degree is high.
Fig. 2 is Co manufactured in the present embodiment2The SEM of P/C composite material schemes, and is learnt by the map analysis, product Co2P/C has
Layer structure, the size of nanometer sheet is 1-3 μm, with a thickness of 3-11nm.
Fig. 3 is Co manufactured in the present embodiment2P/C composite material (prepares sodium ion electricity as anode material of lithium-ion battery
The specific method in pond is referring to electrochemical property test part) voltage range is 0.01~3.0V, current density is 50mA/g's
Under the conditions of cycle performance test chart, it can be seen from this figure that at 25 DEG C, with the current density of 50mA/g in 0.01-3.0V
Between carry out charge and discharge cycles, Co manufactured in the present embodiment2The discharge capacity for the first time of P/C composite material is 783.5mAh/g, is filled
Capacitance is 586.7mAh/g, and reversible specific capacity is 463.8mAh/g after 50 circles, it is shown that excellent stable circulation performance.
Embodiment 2
The present embodiment is prepared as follows Co2P/C composite material:
(1) by the Co (NO of 0.6112g3)2·6H2O, the ctab surface activating agent of the red phosphorus of 0.2927g and 0.1g are added to
In 35mL deionized water, magnetic agitation is carried out.Obtained suspension is transferred in the stainless steel autoclave of 50mL teflon lining,
150 DEG C are put in baking oven, 60h is reacted, obtains Co2P presoma.Washed twice afterwards with the hydrochloric acid of 2mol/L, after use deionized water
For several times with ethanol wash, it is dry to be placed in drying box.
Wherein, Co (NO3)2·6H2The molar ratio of O and red phosphorus is 1:4.5, for table in the suspension system of hydro-thermal reaction
The concentration of face activating agent (CTAB) is 2.85g/L.
(2) Co for then taking 1g dry2P presoma is added in the glucose solution of 0.04mol/L, after be transferred to 50mL spy
In the stainless steel autoclave of fluon lining, 190 DEG C are put in baking oven, 4h is reacted, obtains Co2P/C composite material precursor.
Wherein, the Co2The mass ratio of P presoma and organic carbon source (glucose) is 1:0.25.
(3) by Co2P/C composite material precursor rises to 600 DEG C under protection of argon gas, with the heating rate of 3 DEG C/min, protects
Warm 2h obtains the Co2P/C composite material.
Structural characterization is carried out according to the method for embodiment 1, as a result Co manufactured in the present embodiment2P/C composite material packet
The monodispersed Co for including carbon material substrate and being embedded in the carbon material substrate2P nanometer sheet, carbon material substrate and Co2P receives
The mass ratio of rice piece is 0.2:1；The Co2The size of P nanometer sheet is 2-4 μm, with a thickness of 5-10nm；The Co2P/C composite wood
Material is layer structure porous material, specific surface area 252m2g-1, porosity 60%, aperture 2-5nm.
Co manufactured in the present embodiment2The electrochemical property test of P/C composite material the results are shown in Table 1 and table 2.
Fig. 4 is Co manufactured in the present embodiment2P/C composite material (prepares potassium ion electricity as kalium ion battery negative electrode material
The specific method in pond is referring to electrochemical property test part) voltage range is 0.01~3.0V, current density is 50mA/g's
Under the conditions of cycle performance test chart, it can be seen from this figure that at 25 DEG C, with the current density of 50mA/g in 0.01-3.0V
Between carry out charge and discharge cycles, Co2The discharge capacity for the first time of P/C composite material is 627.9mAh/g, and charging capacity is
473.5mAh/g, 50 circle after reversible specific capacity be 374.4mAh/g, it is shown that excellent stable circulation performance.
Embodiment 3
The present embodiment is prepared as follows Co2P/C composite material:
(1) by the Co (NO of 0.6112g3)2·6H2O, the SDBS surfactant of the red phosphorus of 0.3902g and 0.15g are added
Into 35mL deionized water, magnetic agitation is carried out.Obtained suspension is transferred to the stainless steel autoclave of 50mL teflon lining
In, 220 DEG C are put in baking oven, 30h is reacted, obtains Co2P presoma.Washed twice afterwards with the hydrochloric acid of 1mol/L, after use deionization
Water and ethanol wash for several times, it is dry to be placed in drying box.
Wherein, Co (NO3)2·6H2The molar ratio of O and red phosphorus is 1:6, for surface in the suspension system of hydro-thermal reaction
The concentration of activating agent (SDBS) is 4.29g/L.
(2) Co for then taking 1g dry2P presoma is added in the glucose solution of 0.08mol/L, after be transferred to 50mL spy
In the stainless steel autoclave of fluon lining, 200 DEG C are put in baking oven, 2h is reacted, obtains Co2P/C composite material precursor.
Wherein, the Co2The mass ratio of P presoma and organic carbon source (glucose) is 1:0.55.
(3) by Co2P/C composite material precursor rises to 700 DEG C under protection of argon gas, with the heating rate of 10 DEG C/min,
3h is kept the temperature, the Co is obtained2P/C composite material.
Structural characterization is carried out according to the method for embodiment 1, as a result Co manufactured in the present embodiment2P/C composite material packet
The monodispersed Co for including carbon material substrate and being embedded in the carbon material substrate2P nanometer sheet, carbon material substrate and Co2P receives
The mass ratio of rice piece is 0.47:1；The Co2The size of P nanometer sheet is 3-6 μm, with a thickness of 6-14nm；The Co2P/C composite wood
Material is layer structure porous material, specific surface area 249m2g-1, porosity 60%, aperture 3-10nm.
Co manufactured in the present embodiment2The electrochemical property test of P/C composite material the results are shown in Table 1 and table 2.
Embodiment 4
The present embodiment is prepared as follows Co2P/C composite material:
(1) by the Co (NO of 0.6112g3)2·6H2O, the PVP surfactant of the red phosphorus of 0.3252g and 0.14g are added to
In 35mL deionized water, magnetic agitation is carried out.Obtained suspension is transferred in the stainless steel autoclave of 50mL teflon lining,
170 DEG C are put in baking oven, 48h is reacted, obtains Co2P forerunner.Washed twice afterwards with the hydrochloric acid of 3mol/L, afterwards with deionized water and
Ethanol wash for several times, it is dry to be placed in drying box.
Wherein, Co (NO3)2·6H2The molar ratio of O and red phosphorus is 1:5, for surface in the suspension system of hydro-thermal reaction
The concentration of activating agent (PVP) is 4g/L.
(2) Co for then taking 1g dry2P presoma is added in the glucose solution of 0.06mol/L, after be transferred to 50mL spy
In the stainless steel autoclave of fluon lining, 180 DEG C are put in baking oven, 5h is reacted, obtains Co2P/C composite material precursor.
Wherein, the Co2The mass ratio of P presoma and organic carbon source (glucose) is 1:0.4.
(3) by Co2P/C composite material precursor rises to 650 DEG C under protection of argon gas, with the heating rate of 10 DEG C/min,
4h is kept the temperature, the Co is obtained2P/C composite material.
Structural characterization is carried out according to the method for embodiment 1, as a result Co manufactured in the present embodiment2P/C composite material packet
The monodispersed Co for including carbon material substrate and being embedded in the carbon material substrate2P nanometer sheet, carbon material substrate and Co2P receives
The mass ratio of rice piece is 0.32:1；The Co2The size of P nanometer sheet is 1-4 μm, with a thickness of 3-14nm；The Co2P/C composite wood
Material is layer structure porous material, specific surface area 247m2g-1, porosity 30%, aperture 2-5nm.
Co manufactured in the present embodiment2The electrochemical property test of P/C composite material the results are shown in Table 1 and table 2.
Embodiment 5
The present embodiment is prepared as follows Co2P/C composite material:
(1) by CoCl2·6H2O, red phosphorus and ctab surface activating agent are added in 35mL deionized water, are carried out magnetic force and are stirred
It mixes.Obtained suspension is transferred in the stainless steel autoclave of 50mL teflon lining, is put in baking oven 140 DEG C, reacts 15h,
Obtain Co2P presoma.It is washed twice afterwards with the hydrochloric acid of 3mol/L, afterwards for several times with deionized water and ethanol wash, is placed in drying box
It is dry.
Wherein, CoCl2·6H2The molar ratio of O and red phosphorus is about 1:5.5, for surface in the suspension system of hydro-thermal reaction
The concentration of activating agent (CTAB) is 3g/L.
(2) Co for then taking 1g dry2P presoma is added in the sucrose solution of 0.03mol/L, after be transferred to 50mL Teflon
In the stainless steel autoclave of grand lining, 160 DEG C are put in baking oven, 5h is reacted, obtains Co2P/C composite material precursor.
Wherein, the Co2The mass ratio of P presoma and organic carbon source (sucrose) is 1:0.15.
(3) under protection of argon gas by presoma, 500 DEG C are risen to the heating rate of 1 DEG C/min, keeps the temperature 6h, obtained described
Co2P/C composite material.
Structural characterization is carried out according to the method for embodiment 1, as a result Co manufactured in the present embodiment2P/C composite material packet
The monodispersed Co for including carbon material substrate and being embedded in the carbon material substrate2P nanometer sheet, carbon material substrate and Co2P receives
The mass ratio of rice piece is 0.14:1；The Co2The size of P nanometer sheet is 2-6 μm, with a thickness of 3-7nm；The Co2P/C composite wood
Material is layer structure porous material, specific surface area 257m2g-1, porosity 40%, aperture 3-6nm.
Co manufactured in the present embodiment2The electrochemical property test of P/C composite material the results are shown in Table 1 and table 2.
Comparative example 1
This comparative example prepares Co2Referring to embodiment 1, difference is the method for P/C composite material, in step (2), without
Hydro-thermal reaction, directly to dry Co2The presoma that P presoma obtains after mixing with glucose solution carries out forging for step (3)
It burns, i.e., without second of hydro-thermal reaction, dinectly bruning packet carbon.
The Co of method preparation by this comparative example2P/C composite material, its shortcoming is that, uneven, the meeting of carbon-coating cladding
Influence the transmission of ion.
The Co of this comparative example preparation2The electrochemical property test of P/C composite material the results are shown in Table 1 and table 2.
Comparative example 2
The method of negative electrode material is prepared referring to embodiment 1, difference is, without the operation of step (2), directly to step
(1) Co obtained2P presoma carries out the calcination operation of step (3).
The negative electrode material of this comparative example preparation is Co2P, not carbonaceous material substrate, this cathode material of this comparative example preparation
The negative electrode material prepared relative to embodiment is expected its shortcoming is that material electric conductivity is low, hinders the diffusion velocity of ion.
The electrochemical property test of the negative electrode material of this comparative example preparation the results are shown in Table 1 and table 2.
Electrochemical property test
Using four probe resistance rate tester testing conductivities.
Production prepared by each embodiment and comparative example is tested for the property at sodium-ion battery or kalium ion battery.
The method for being fabricated to sodium-ion battery are as follows: 0.06g is added in the product for weighing 0.21g embodiment or comparative example preparation
Acetylene black make conductive agent and the Kynoar (PVDF) of 0.03g makees binder, suitable N- methyl-is added after being fully ground
Pyrrolidones (NMP) solvent is coated on copper foil after sizing mixing uniformly, and vacuum drying backlash is at round negative electrode tab, with metallic sodium piece
To electrode, electrolyte is 1M NaClO4/DEC/EC (DEC and EC molar ratio is 1:1), and diaphragm is Whatman glass fibre,
CR2032 button cell is assembled into glove box full of argon gas.
The method for being fabricated to kalium ion battery are as follows: 0.12g is added in the product for weighing 0.28g embodiment or comparative example preparation
Acetylene black make conductive agent and the Kynoar (PVDF) of 0.04g makees binder, suitable N- methyl-is added after being fully ground
Pyrrolidones (NMP) solvent is coated on copper foil after sizing mixing uniformly, and vacuum drying backlash is at round negative electrode tab, with metallic potassium piece
To electrode, electrolyte is 1M KPF6/DEC/EC (DEC and EC molar ratio is 1:1), and diaphragm is Whatman glass fibre, is being filled
CR2032 button cell is assembled into the glove box of full argon gas.
It is carried out between 0.01-3.0V at 25 DEG C with the current density of 50mA/g using the blue electric battery test system in Wuhan
Charge and discharge cycles test specific capacity and cycle performance.Electrochemical property test the results are shown in Table 1 and table 2.
Table 1 is prepared into the test result of sodium-ion battery
Table 2 is prepared into the test result of kalium ion battery
Based on the above embodiments with comparative example it is found that method of the present invention by secondary hydro-thermal, obtained two cobalts of phosphatization/carbon
The unique structure of composite material, Co2P nanometer sheet is embedded in carbon material substrate, alleviates phosphide particle in ion insertion and extraction process
The volume change problem of middle generation, to improve the cyclical stability of composite material；On the other hand, the association between carbon and phosphide
Same-action improves the specific capacity and high rate performance of composite material.Result unique in this way makes phosphatization two provided by the invention
Cobalt/carbon composite good conductivity, specific capacity is high, high rate performance and good cycle, is particularly suitable for application as negative electrode material use
In sodium-ion battery or kalium ion battery.Comparative example does not use the solution of the present invention, therefore can not obtain of the invention excellent
Effect.
The Applicant declares that the present invention is explained by the above embodiments detailed process equipment and process flow of the invention,
But the present invention is not limited to the above detailed process equipment and process flow, that is, it is above-mentioned detailed not mean that the present invention must rely on
Process equipment and process flow could be implemented.It should be clear to those skilled in the art, any improvement in the present invention,
Addition, selection of concrete mode of equivalence replacement and auxiliary element to each raw material of product of the present invention etc., all fall within of the invention
Within protection scope and the open scope.
Claims (10)
1. a kind of two cobalts of phosphatization/carbon composite, which is characterized in that two cobalts of the phosphatization/carbon composite includes carbon material base
Bottom and the Co being embedded in the carbon material substrate2P nanometer sheet.
2. two cobalts of phosphatization/carbon composite according to claim 1, which is characterized in that the Co2P nanometer sheet is monodispersed
Co2P nanometer sheet；
Preferably, the Co2The size of P nanometer sheet is 1-6 μm；
Preferably, the Co2P nanometer sheet with a thickness of 3-14nm；
Preferably, two cobalts of the phosphatization/carbon composite is layer structure；
Preferably, in two cobalts of the phosphatization/carbon composite, carbon material substrate and Co2The mass ratio of P nanometer sheet is 0.1:1-
0.5:1；
Preferably, the specific surface area of two cobalts of the phosphatization/carbon composite is 220-260m2g-1；
Preferably, two cobalts of the phosphatization/carbon composite is porous material；
Preferably, the porosity of two cobalts of the phosphatization/carbon composite is 30%-60%；
Preferably, the aperture of two cobalts of the phosphatization/carbon composite is 1-10nm.
3. a kind of preparation method of two cobalts of phosphatization/carbon composite as claimed in claim 1 or 2, which is characterized in that the method
The following steps are included:
(1) after mixing cobalt source, phosphorus source and surfactant with water, hydro-thermal reaction is carried out, Co is obtained2P presoma；
(2) by step (1) Co2After P presoma is mixed with organic carbon source solution, hydro-thermal reaction is carried out, Co is obtained2P/C is compound
Material precursor；
(3) by step (2) Co2P/C composite material precursor is calcined under protective atmosphere, obtains the phosphatization two
Cobalt/carbon composite.
4. preparation method according to claim 3, which is characterized in that step (1) cobalt source is soluble cobalt；
Preferably, the soluble cobalt include in cobalt nitrate, cobalt acetate or cobalt chloride any one or at least two group
It closes；
Preferably, step (1) phosphorus source is red phosphorus；
Preferably, the molar ratio of step (1) cobalt source and phosphorus source is 1:4.5-1:6.0；
Preferably, step (1) described surfactant includes cetyl trimethylammonium bromide, polyvinylpyrrolidine or dodecane
In base benzene sulfonic acid sodium salt any one or at least two combination；
Preferably, in the hydro-thermal reaction system of step (1), the concentration of the surfactant is 1.43-4.29g/L；
Preferably, step (1) the mixed method is to be stirred.
5. preparation method according to claim 3 or 4, which is characterized in that the temperature of step (1) described hydro-thermal reaction is
140-220℃；
Preferably, the time of step (1) described hydro-thermal reaction is 15-60h；
Preferably, step (1) described hydro-thermal reaction carries out in the stainless steel autoclave for having teflon lining；
Preferably, step (1) further include: to the Co2P presoma is washed and is dried；
Preferably, the washing methods is first to use salt acid elution, then with water and ethanol washing；
Preferably, the concentration of the hydrochloric acid is 1-3mol/L.
6. according to the described in any item preparation methods of claim 3-5, which is characterized in that in step (2), the organic carbon source packet
Include in glucose, sucrose or citric acid any one or at least two combination；
Preferably, in step (2) the organic carbon source solution, the concentration of organic carbon source is 0.05-0.5mol/L；
Preferably, in step (2), the Co2The mass ratio of P presoma and organic carbon source is 1:0.15-1:0.55.
7. according to the described in any item preparation methods of claim 3-6, which is characterized in that the temperature of step (2) described hydro-thermal reaction
Degree is 160-200 DEG C；
Preferably, the time of step (2) described hydro-thermal reaction is 2-5h；
Preferably, step (2) described hydro-thermal reaction carries out in the stainless steel autoclave for having teflon lining.
8. according to the described in any item preparation methods of claim 3-7, which is characterized in that step (3) the protective atmosphere packet
Include argon gas；
Preferably, the temperature of step (3) described calcining is 500-700 DEG C；
Preferably, the time of step (3) described calcining is 2-6h；
Preferably, the heating rate of step (3) described calcining is 1-10 DEG C/min.
9. according to the described in any item preparation methods of claim 3-8, which is characterized in that the described method comprises the following steps:
(1) after mixing soluble cobalt, red phosphorus and surfactant with water, in the stainless steel autoclave for having teflon lining
Hydro-thermal reaction is carried out, the temperature of hydro-thermal reaction is 140-220 DEG C, the hydro-thermal reaction time 15-60h, to the product of hydro-thermal reaction
1-3mol/L salt acid elution is first used, then with water and ethanol washing, finally dries, obtains Co2P presoma；
Wherein, soluble cobalt and the molar ratio of red phosphorus are 1:4.5-1:6.0；In hydro-thermal reaction system, the surfactant
Concentration be 1.43-4.29g/L；
(2) by step (1) Co2After P presoma is mixed with the organic carbon source solution of 0.05-0.5mol/L, there is teflon lining
In stainless steel autoclave in carry out hydro-thermal reaction, the temperature of hydro-thermal reaction is 160-200 DEG C, the hydro-thermal reaction time 2-5h,
Obtain Co2P/C composite material precursor；
Wherein, the Co2The mass ratio of P presoma and organic carbon source is 1:0.15-1:0.55g/mol；
(3) by step (2) Co2P/C composite material precursor is heated up under an argon atmosphere with the heating rate of 1-10 DEG C/min
It is calcined to 500-700 DEG C, calcination time 2-6h, obtains two cobalts of the phosphatization/carbon composite.
10. a kind of purposes of two cobalts of phosphatization/carbon composite as claimed in claim 1 or 2, which is characterized in that the phosphatization two
Cobalt/carbon composite is used for sodium-ion battery or kalium ion battery as negative electrode material.
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| CN113903890A (en) * | 2021-06-09 | 2022-01-07 | 天津大学 | Integrated nano porous cobalt oxide/cobaltous phosphide hybrid material, preparation and energy storage application |
| CN114300676A (en) * | 2021-11-01 | 2022-04-08 | 北京航空航天大学 | Flexible sodium-ion battery negative electrode material, preparation method thereof and battery negative electrode |
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| CN105789584A (en) * | 2016-03-27 | 2016-07-20 | 华南理工大学 | Cobalt selenide/carbon sodium ion battery composite negative electrode material as well as preparation method and application of cobalt selenide/carbon-sodium ion battery composite negative electrode material |
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| CN110975899A (en) * | 2019-11-15 | 2020-04-10 | 北京科技大学 | Preparation method of cobalt phosphide nanosheet composite material with carbon particle intercalation |
| CN110975899B (en) * | 2019-11-15 | 2020-12-22 | 北京科技大学 | Preparation method and application of cobalt phosphide nanosheet composite material with carbon particle intercalation |
| CN111525127A (en) * | 2020-04-09 | 2020-08-11 | 上海应用技术大学 | Graphene-based cobalt phosphide cathode material and preparation and application thereof |
| CN113258083A (en) * | 2021-03-24 | 2021-08-13 | 宁波工程学院 | CoXBifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof |
| CN113258083B (en) * | 2021-03-24 | 2022-09-06 | 宁波工程学院 | Co X Bifunctional catalyst with P nanoparticles embedded with nitrogen and phosphorus doped carbon and preparation method and application thereof |
| CN113903890A (en) * | 2021-06-09 | 2022-01-07 | 天津大学 | Integrated nano porous cobalt oxide/cobaltous phosphide hybrid material, preparation and energy storage application |
| CN113903890B (en) * | 2021-06-09 | 2023-07-14 | 天津大学 | Integrated nano porous cobalt oxide/cobalt phosphide hybrid material, preparation and energy storage application |
| CN114300676A (en) * | 2021-11-01 | 2022-04-08 | 北京航空航天大学 | Flexible sodium-ion battery negative electrode material, preparation method thereof and battery negative electrode |
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