CN108615886A - A kind of thin wall type porous carbon ball material and its preparation and the application as anode material of lithium-ion battery - Google Patents
A kind of thin wall type porous carbon ball material and its preparation and the application as anode material of lithium-ion battery Download PDFInfo
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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- 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
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- H01M10/00—Secondary cells; Manufacture thereof
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Abstract
The invention discloses a kind of thin wall type porous carbon ball material and its preparation and as the application of anode material of lithium-ion battery.Thin wall type porous carbon ball material is the porous nano carbon ball with thin-walled type hole；Preparation method is that biomass carbohydrate carbon source, water-soluble inorganic salt fluxing agent and surfactant are dissolved in water, obtains spray solution；The spray solution obtains porous carbon ball presoma by spray drying；The porous carbon ball presoma by be carbonized heat treatment to get.The thin wall type porous carbon ball material activity site of preparation is abundant, large specific surface area, is applied to sodium-ion battery, shows height ratio capacity, long circulating stability and high rate performance, and its preparation process is simple, reproducible, has wide industrial applications foreground.
Description
Technical field
The present invention relates to a kind of carbon materials, and in particular to a kind of thin wall type porous carbon ball material and preparation method thereof also relates to
And application of the thin wall type porous carbon ball material in sodium-ion battery, belong to sodium-ion battery field.
Background technology
With the traditional energies such as coal, oil, natural gas gradually decrease and increasingly serious environmental problem, small-sized point
Explosive growth trend is showed from mobile power demand, is got over by the various chargeable electrochmical power sources of representative of lithium ion battery
To be more taken seriously.However, since constituent content of the lithium in the earth's crust is relatively fewer, it is unevenly distributed, the extraction and recycling of lithium are tired
It is difficult, it is therefore necessary to develop novel battery system.
Sodium-ion battery is the high-performance energy storage system of fast development in recent years.Reserves of the sodium in nature are very rich
Richness accounts for about the 2.74% of the earth's crust, and widely distributed, significantly reduces cost.Sodium and lithium are all I major element simultaneously,
The two has similar physicochemical characteristics.Therefore, there is sodium-ion battery the deintercalation mechanism similar with lithium ion battery to be recognized
To be the ideal chose of extensive energy storage field.
Currently, in secondary cell field, based on the considerations of developing material cost and application prospect, study more sodium from
Sub- negative material is mainly various carbon-based materials, and carbon material includes mainly graphitic carbon and agraphitic carbon two major classes.Wherein, graphite has been
Through being widely used in lithium ion battery.For lithium ion, the radius of sodium ion is much bigger, the interlamellar spacing of graphitic carbon
The insertion of (0.335nm) too small unsuitable sodium ion.In addition, there is the intercalation compound that research points out that sodium is formed with graphite cannot be steady
Surely it is present in nature, can not effectively stores up sodium.And the unordered carbon material in agraphitic carbon can possess bigger interlamellar spacing, it is more suitable
The insertion of sodium ion is closed, while abundant pore structure is also conducive to the absorption storage sodium of sodium ion.According to relevant report, by being pyrolyzed grape
The amorphous carbon material that sugar obtains has similar embedded mechanism as the negative material of lithium ion battery and sodium-ion battery,
It is different to be only embedded in voltage value.With going deep into for research, academia is considered to build up porous carbon materials, by the size of control hole and
Structure regulating store up sodium performance, be improve carbon material capacity one of effective way, on this basis, porous hard carbon carbon ball material by
In its relatively large specific surface area and smaller Particle diffusion resistance, shown in sodium-ion battery field excellent hypovolemic
It can, it is considered to be promising anode material of lithium-ion battery.But traditional porous hard carbon carbon ball preparation process is often restricted
In hydro-thermal reaction or remove the cumbersome procedures such as hard template, it is difficult to large-scale industrial production, and the porous carbon ball prepared is uniform
Property is poor, and pore structure is undeveloped, hole wall thickness, and specific surface area is low, causes its ion low with electronic conductivity, and active site is not rich
Richness causes its high rate performance, volumetric properties to be difficult to play, and becomes limitation porous carbon ball material as anode material of lithium-ion battery
The critical issue of large-scale application.
Invention content
For defect existing for existing sodium ion battery electrode material, the first object of the present invention is to provide a kind of grain size
Uniformly, hole is flourishing, hole wall is thin, and specific surface is big, and hole holds larger thin wall type porous carbon ball material；The porous carbon ball has nearly ball
Shape structure helps to improve the tap density of material, improves the processing performance of its electrode, and the thin wall type porous structure of carbon ball has
Help increase the contact area of active material and electrolyte, promote ion transports and reduce diffusion length, while can accommodate storage
The volume change generated during sodium, improves the stability of electrode；Thin wall type porous carbon ball is made of graphite microcrystal, is possessed abundant
Crystal defect, edge and vacancy isoreactivity site and big interlamellar spacing, high surface area, abundant micro-nano pore passage structure it is rich
It rich active site and storage that big carbon-coating spacing is sodium ion and transports convenience is provided, contribute to the hair for storing up sodium performance
It waves.
Second object of the present invention is to be to provide a kind of preparation method of thin wall type porous carbon ball material, this method work
Skill is simple, reproducible, of low cost, environmental-friendly, and degree of controllability is high, it is easy to accomplish industrialization effectively prevents conventional porous
The removal step of hydro-thermal or hard template that carbon ball preparation process is often related to.
The third object of the present invention is to provide a kind of application of thin wall type porous carbon ball material in sodium-ion battery, uses
It can effectively improve sodium-ion battery specific capacity and long-term cycle stability energy as anode material of lithium-ion battery application.
In order to achieve the above technical purposes, the present invention provides a kind of thin wall type porous carbon ball materials, for thin wall type
The porous nano carbon ball in hole；The pore wall thickness of the thin-walled type hole is 1~16nm.
There is the porous carbon ball material of the present invention thin wall type porous structure, thin wall type porous structure to help to increase active material
The contact area of material and electrolyte, promote ion transports and reduces diffusion length, and thin wall type porous carbon ball has big interlayer
Away from high surface area, abundant micro-nano pore passage structure can accommodate the volume change generated during storage sodium, improve the steady of electrode
It is qualitative；And abundant active site and big carbon-coating spacing for the storage of sodium ion and will transport and provide convenience, contribute to
Store up the performance of sodium performance.
Preferred scheme, a diameter of 30~500nm of the porous nano carbon ball；More preferably it is 50~200nm.It is porous to receive
The grain size of rice carbon ball is more uniform, is conducive to the tap density for improving material, improves the processing performance of its electrode.
Preferred scheme, the porous nano carbon ball are made of disorderly arranged graphite microcrystal, the hole of porous nano carbon ball
It is 0.11~2.83cm to hold3/ g, specific surface area are 200~1500m2/g.Thin wall type porous carbon ball has high surface area, abundant
Micro-nano pore passage structure, and it is made of graphite microcrystal, possesses abundant defect, edge and vacancy isoreactivity site, therefore can be with
The more active sites of exposure are conducive to improve electro-chemical activity.
The thin wall type porous carbon ball pore wall thickness of the present invention is 5~50 graphite linings (1~16nm), preferred pore wall thickness
For 10~30 graphite linings (3~10nm)；Under the pore wall thickness, the electronics and ion conduction of porous carbon materials are good, store up sodium
Capacity is high.
It is 500~1500m that the thin wall type porous carbon ball material of the present invention, which has abundant gap, preferred specific surface area,2/g。
The present invention also provides a kind of preparation methods of thin wall type porous carbon ball material, specifically by biomass carbohydrate carbon
Source, water-soluble inorganic salt fluxing agent and surfactant are dissolved in water, obtain spray solution；The spray solution passes through spray drying
Obtain porous carbon ball presoma；The porous carbon ball presoma by be carbonized heat treatment to get.
More preferably scheme, the biomass carbohydrate carbon source include in starch, lactose, chitosan, glucose, sucrose at least
It is a kind of.Still more preferably, the biomass carbohydrate carbon source is fructose.Using the preferred object as carbon source, easily in surface-active
It polymerize balling-up under the action of agent, to help to improve the performance of carbon material used as anode obtained.
More preferably scheme, the water-soluble inorganic salt fluxing agent include at least one in the water-soluble salt containing lithium, sodium, zinc or potassium
Kind.Further preferably, the water-soluble inorganic salt fluxing agent is at least one of sodium chloride or potassium chloride, using the preferred object
Material is used as fluxing agent, can assign the suitable hole of negative material.Most preferred water-soluble inorganic salt fluxing agent is chlorination
Sodium.Water-soluble inorganic salt is used as template and fluxing agent simultaneously, using potassium chloride or sodium chloride as template and fluxing agent, in high temperature
Under the conditions of fusing moth erosion rapidly, form a large amount of hole, it is thin to ultimately generate hole wall, and hole is abundant and shaggy porous carbon
Ball.
More preferably scheme, the surfactant include cetyl trimethylammonium bromide, dodecyl sodium sulfate, gather
At least one of vinylpyrrolidone.These surfactants that the present invention uses play the role of similar balling-up template and are conducive to
Carbohydrate carbon source solution forms spherical.The surfactant is dodecyl sodium sulfate.
More preferably scheme, biomass carbohydrate carbon source, water-soluble inorganic salt fluxing agent and surfactant three mole
Than being 0.2~0.5：0.3~0.8：0.1~0.2.More preferably molar ratio is 0.3~0.4：0.4~0.7：0.1~0.2.
The present invention can effectively control the pore wall thickness of thin-walled type hole within the scope of 1~16nm by strictly controlling the ratio of three, from
And make carbon material that there is best electro-chemical activity.
More preferably scheme, a concentration of 0.1~0.8mol/L of water-soluble inorganic salt fluxing agent in the spray solution.
The condition of preferred scheme, the spray drying is：120~280 DEG C, spray amount is 0.5~20mL/min, atomization
Pressure is 1~30MPa, and gas flow rate is≤10L/min.Further preferred spray drying temperature is 160~240 DEG C.Excellent
Under the spray drying temperature of choosing, carbon ball regular appearance, uniform carbon ball presoma.Under the conditions of spray drying temperature, lead to
The spray amount for crossing spraying system is 2~10mL/min, and atomizing pressure is 5~15MPa.Studies have shown that suitable spray amount and its
Atomisation pressure can control the diameter of carbon ball precursor, be conducive to that the suitable carbon ball precursor of size is made.
Preferred scheme, the process that the carbonization is heat-treated are：Under protective atmosphere, in 1000~1100 DEG C of temperature, heat
Handle 0.5~20h.For the present invention under higher heat treatment temperature, cooperation fluxing agent melt is conducive to carbon material etching property by force
Inside carbon ball and its surface forms abundant, pore passage structure of the pore wall thickness in 5~50 graphite linings (1~16nm)；To
It obtains one kind and possessing good electronics and ion conduction, height storage sodium capacity, the thin-walled of preferable cyclical stability and high-tap density
Type porous carbon ball material.Numerous studies find that carbon ball precursor controlling is heat-treated at preferred temperature, can be made and possess
Good electronics and ion conduction, abundant active site, moderate specific surface area, while hole wall are thin and pore passage structure is abundant hands over
The porous carbon materials of connection.Less than this lowest temperature, insufficient, the conduction of obtained thin wall type porous carbon ball material of presoma carbonization
Property is poor；Fluxing agent cannot be changed into melt simultaneously, cannot play moth erosion effect；When higher than the temperature upper limit, obtained thin-walled is more
Hole carbon ball material loses undefined structure and is converted to graphite material, and it is poor that capacity plays, and decaying is fast；Fluxing agent is at this time to carbon materials simultaneously
Material moth erosion is strong, leads to carbon ball structure collapses, carbon-coating stripping.
The heating rate in heat treatment process that is carbonized in technical solution of the present invention is 1~10 DEG C/min；More preferably heating speed
Rate is 1~3 DEG C/min.At a temperature of 1000~1100 DEG C, heat treatment time most preferably 2~10h.
The present invention also provides the application of the thin wall type porous carbon ball material, the cathode material as sodium-ion battery
Material application.
Existing method can be used in the method that the thin wall type porous carbon ball material of the present invention is used to prepare sodium-ion battery cathode,
For example, the thin wall type porous carbon ball material that the present invention obtains is mixed with conductive agent and binder, copper is coated in by rubbing method
On foil collector, sodium-ion battery cathode is made.
Thin wall type porous carbon ball material prepared by the present invention prepares the method and performance of sodium-ion battery as negative material
Detection method：Above-mentioned thin wall type porous carbon ball material is weighed, 10wt.%Super P are added as conductive agent, 10wt.% carboxylic first
Base sodium cellulosate (CMC) is used as binder, it is ground fully after a small amount of deionized water be added be mixed to form uniform black paste
Shape slurry, by these slurries be coated in copper foil current collector on as test electrode, with metallic sodium piece as a comparison electrode assembling at
For button cell, use electrolyte system for 1M NaClO4/EC:DEC(1:1).Charging and discharging currents used in test loop performance
Density is 100mA/g.
In order to achieve the above technical purposes, the present invention provides a kind of thin wall type porous carbon ball materials, including in detail below
Step：
Step (1)：Biomass carbohydrate carbon source, water-soluble inorganic salt fluxing agent are weighed, surfactant is dissolved in deionization
In water, the solution of a concentration of 0.1~0.8mol/L of water-soluble inorganic salt fluxing agent is made, wherein biomass carbohydrate carbon source, water
Soluble inorganic salt fluxing agent, surfactant molar ratio be 0.2~0.5：0.3~0.8：0.1~0.2, at 20~50 DEG C
Under the conditions of whipping temp condition and the mixing speed of 10~20r/s, spray solution is made until solution clarification in stirring；
Step (2)：Under an inert atmosphere, spray solution is sprayed by spray drying device at 120~280 DEG C
It is dry, collect the dry crude product of spray drying；
Step (3)：Obtained spray drying crude product is placed in tube furnace, in inert atmosphere, 1000~1100
DEG C further carbonization heat treatment, gained heat-treated products further wash, dry to get thin wall type porous carbon ball.
Technical scheme of the present invention key is to cooperate with by the component of carbohydrate carbon source, fluxing agent and surfactant,
By spray drying, pattern rule, uniform carbon ball persursor material is made；Pass through further high-temperature heat treatment, system again
Obtain thin wall type porous carbon ball material.This method passes through the components such as control surface activating agent and fluxing agent, coordinated regulation Carbon anode material
The surface roughness and hole of material, and then achieve the effect that collaboration promotes the electric property of carbon negative pole material.
Technical scheme of the present invention is thermally treated resulting in carbonized product, and carbonized product is washed, such as is gone by pickling
Except fluxing agent, the thin wall type porous carbon ball material is made；It washs obtained fluxing agent recycling, recycle.After pickling
Product again using being washed to neutrality, washing can be repeated, until fluxing agent is all removed.Product after washing, sets
Under 50~80 DEG C of temperature conditions, it is dried in vacuo 8~12h.The dilute acid soln that the acid solution of use is known in the art, use are dilute
Acid and water alternately and repeatedly wash, and can remove the impurity generated in remaining fluxing agent and carbonisation.The acid solution of use is such as
At least one of dilute hydrochloric acid, dilute sulfuric acid, dust technology；The acid solutions are generally in 0.5mol/L or so.
The preferred preparation method of the present invention, specifically includes following steps：
Step (1)：Biomass carbohydrate carbon source, water-soluble inorganic salt fluxing agent are weighed, surfactant is dissolved in deionization
In water, spray solution is made until solution clarification in stirring at a temperature of 20~50 DEG C；The biomass carbohydrate carbon source be starch,
One or more of lactose, chitosan, glucose or sucrose；The water-soluble inorganic salt fluxing agent is the water solubility of sodium
At least one of the water soluble salt of salt, the water soluble salt of zinc, potassium；The surfactant is cetyl trimethyl bromination
One or more of ammonium, dodecyl sodium sulfate, polyvinylpyrrolidone.Water-soluble inorganic salt fluxing agent：Surfactant
Molar ratio be 0.3~0.4：0.4~0.7：0.1~0.2.
Step (2)：Under an inert atmosphere, it by spray solution in spray drying device, is sprayed at 120~280 DEG C
Mist is dried, and spray drying crude product is collected；It is 2~10mL/min by the spray amount of spraying system, atomizing pressure is 5~
15MPa, gas flow rate are≤10L/min.
Step (3)：Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere, 1000~
1100 DEG C are further heat-treated, and gained heat-treated products further wash, and are dried to obtain thin wall type porous carbon ball material；
Step (4)：After the heat-treated products are washed using deionized water with diluted acid repeatedly, it is placed in 50~100 DEG C of temperature
Under the conditions of, it is dried in vacuo 8~12h.It is washed repeatedly with diluted acid using deionized water, it can will be in remaining fluxing agent and carbonisation
The impurity of generation removes.
The thin wall type porous carbon ball pore passage structure of the present invention is abundant, and storage sodium space is enough, and hole wall is thin, have good sodium from
The embedded abjection ability of son.The material also has good electric conductivity, abundant functional group, while having loose and porous structure, as
Sodium-ion battery cathode shows high specific capacity, good high rate performance and long circulating stability energy.
Compared with the prior art, the advantageous effects that technical scheme of the present invention is brought：
1) technical scheme of the present invention uses biomass carbohydrate for carbon source, and water-soluble inorganic salt is template and fluxing agent, warp
It crosses spray drying and carbon ball precursor is made, eat into borrosion hole road by being further heat-treated, be finally prepared for thin wall type porous carbon ball material,
This method avoid the removal step of hydro-thermal or hard template that conventional porous hard charcoal carbon ball preparation process is often related to, by adjusting
The ratio and carburizing temperature of fluxing agent and carbon source, realize the control of pore wall thickness, simple for process, reproducible, of low cost,
Environmental-friendly, degree of controllability is high, it is easy to accomplish industrialization.
2) thin wall type porous carbon ball material prepared by technical scheme of the present invention has abundant pore passage structure and thin hole
The overall structure of wall, porous carbon ball helps to improve the tap density of material, then improves the processing performance of its electrode.Carbon ball
Thin wall type porous structure contribute to increase active material and electrolyte contact area, promote ion transport and reduces spread away from
From, while the volume change generated during storage sodium can be accommodated, improve the stability of electrode.Thin wall type porous carbon ball is by unordered row
The graphite microcrystal of row forms, and possesses abundant defect, edge and vacancy isoreactivity site, big interlamellar spacing, high surface area, nothing
Also there are abundant micro-nano pore passage structure, abundant active site and big carbon-coating spacing will be for the storage of sodium ion inside sizing carbon
Offer convenience is deposited and transported, the performance for storing up sodium performance is contributed to.
3) thin wall type porous carbon ball material of the invention can be used for preparing with high coulombic efficiency, excellent high rate performance and
The sodium-ion battery of long circulating stability energy.
Description of the drawings
【Fig. 1】For the SEM electron microscopes of thin wall type porous carbon ball material made from embodiment 1.
【Fig. 2】For the N of thin wall type porous carbon ball material made from embodiment 12Absorption/desorption curve figure.
【Fig. 3】The cycle number of turns-cycle electric discharge for thin wall type porous carbon ball made from embodiment 1 for sodium-ion battery is held
Amount, coulombic efficiency figure.
Specific implementation mode
Following embodiment is intended to be described in further details the content of present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
5.4g fructose, 4.13g sodium chloride and 2.72g dodecyl sodium sulfates are added into 100ml deionized waters, 50
Spray solution is made until solution clarification in stirring at a temperature of DEG C.Under an argon atmosphere, it is arranged through the spray amount of spraying system and is
Spray solution is spray-dried for 160 DEG C by 3mL/min, atomizing pressure 5MPa in spray drying device, and it is dry to collect spraying
Dry crude product；Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere, at a temperature of 1100 DEG C into
One step is heat-treated, and gained heat-treated products further wash, and are dried to obtain thin wall type porous carbon ball material；Heat-treated products use
It after deionized water is washed repeatedly with diluted acid, is placed under 70 DEG C of temperature conditions, is dried in vacuo 12h.It is anti-with diluted acid using deionized water
After backwashing is washed, and can remove the impurity generated in remaining fluxing agent and carbonisation.Obtain that pore passage structure is abundant and hole wall is thin
Thin wall type porous carbon ball material.It is 2.83cm that thin wall type porous carbon materials hole, which holds,3/ g, specific surface area 1401m2/ g, carbon pores
Wall thickness 3.31nm, the scanning electron microscope (SEM) photograph (SEM) that thin wall type porous carbon materials are made are shown in Fig. 1.
Using porous carbon ball material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binder, and ground fully a small amount of deionized water, which is added, is mixed to form uniform black later
These slurries are coated in copper foil current collector as test electrode, with metallic sodium piece electrode assembling as a comparison by pasty slurry
As button cell, use electrolyte system for 1M NaClO4/EC:DEC(1:1) it, under the current density of 50mA/g, surveys
Try cycle performance；The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.Test result table
Bright, sodium-ion battery cathode prepared by this example has good chemical property：Under the current density of 50mA/g, first circle library
Human relations efficiency is 71%, and first circle discharge capacity is 366mA/g, after cycle 100 is enclosed, remains to the specific capacity for keeping 291mA/g；
Under the power-discharging density of 1000mA/g and 2000mA/g, the specific capacity for keeping 241mAh/g and 201mAh/g respectively is remained to.It is made half
50 circle cyclic discharge capacities are shown in Fig. 2 with coulombic efficiency figure before battery.
Embodiment 2
3.6g lactose, 2.22g potassium chloride and 3.01g dodecyl sodium sulfates are added into 100ml deionized waters, 50
Spray solution is made until solution clarification in stirring at a temperature of DEG C.Under an argon atmosphere, it is arranged through the spray amount of spraying system and is
Spray solution is spray-dried for 120 DEG C by 5mL/min, atomizing pressure 10MPa in spray drying device, collects spraying
Dry crude product；Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere, at a temperature of 1000 DEG C
Further heat treatment, gained heat-treated products further wash, and are dried to obtain thin wall type porous carbon ball material；Heat-treated products are adopted
It after being washed repeatedly with deionized water and diluted acid, is placed under 50~100 DEG C of temperature conditions, is dried in vacuo 8~12h.Using deionization
Water washs repeatedly with diluted acid, can remove the impurity generated in remaining fluxing agent and carbonisation.It is abundant to obtain pore passage structure
And the thin wall type porous carbon materials that hole wall is thin.It is 2.01cm that thin wall type porous carbon materials hole, which holds,3/ g, specific surface area are
720m2/ g, carbon pores wall thickness 1.6nm.Using porous carbon ball material manufactured in the present embodiment, 10wt.%Super P conducts are added
Conductive agent, 10wt.% sodium carboxymethylcelluloses (CMC) are used as binder, it is ground fully after that a small amount of deionized water is added is mixed
Conjunction forms uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode, with metallic sodium piece
Electrode assembling becomes button cell as a comparison, uses electrolyte system for 1M NaClO4/EC:DEC(1:1), in 50mA/g
Current density under, test loop performance；The multiplying power of battery is tested under the different current density such as 1000mA/g, 2000mA/g
Performance.Test result shows that sodium-ion battery cathode prepared by this example has good chemical property：In the electric current of 50mA/g
Under density, first circle coulombic efficiency is 69%, and first circle discharge capacity is 297mA/g, after cycle 100 is enclosed, remains to keep 258mA/g
Specific capacity；Under the power-discharging density of 1000mA/g and 2000mA/g, the ratio for keeping 230mAh/g and 201mAh/g respectively is remained to
Capacity.
Embodiment 3
It will be added to 100ml deionizations in 3.6g lactose, 1.77g sodium chloride and 3.64g cetyl trimethylammonium bromides
In water, spray solution is made until solution clarification in stirring at a temperature of 50 DEG C.Under an argon atmosphere, setting passes through spraying system
Spray amount be 10mL/min, atomizing pressure 15MPa, by spray solution in spray drying device 120 DEG C to carry out spraying dry
It is dry, collect spray drying crude product；Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere,
It is further heat-treated at a temperature of 1050 DEG C, gained heat-treated products further wash, and are dried to obtain thin wall type porous carbon ball material；
After heat-treated products are washed using deionized water with diluted acid repeatedly, it is placed under 50~100 DEG C of temperature conditions, vacuum drying 8~
12h.It is washed, the impurity generated in remaining fluxing agent and carbonisation can be removed repeatedly with diluted acid using deionized water.
To the thin wall type porous carbon materials that pore passage structure is abundant and hole wall is thin.It is 2.22cm that thin wall type porous carbon materials hole, which holds,3/ g,
Specific surface area is 649m2/ g, carbon pores wall thickness 3.3nm.Using porous carbon ball material manufactured in the present embodiment, 10wt.% is added
For Super P as conductive agent, 10wt.% sodium carboxymethylcelluloses (CMC) are used as binder, ground to be fully added later on a small quantity
Deionized water is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector as test electrode,
With metallic sodium piece, electrode assembling becomes button cell as a comparison, uses electrolyte system for 1M NaClO4/EC:DEC(1:
1), under the current density of 50mA/g, test loop performance；It is surveyed under the different current density such as 1000mA/g, 2000mA/g
Try the high rate performance of battery.Test result shows that sodium-ion battery cathode prepared by this example has good chemical property：
Under the current density of 50mA/g, first circle coulombic efficiency is 69%, and first circle discharge capacity is 263mA/g, after cycle 100 is enclosed, still
It can keep the specific capacity of 249mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to keep respectively 293mAh/g and
The specific capacity of 179mAh/g.
Embodiment 4
It will be added into 100ml deionized waters in 17.1g lactose, 2.55g potassium chloride and 2.48g polyvinylpyrrolidones,
Spray solution is made until solution clarification in stirring at a temperature of 50 DEG C.Under an argon atmosphere, the spraying that setting passes through spraying system
Amount is 15mL/min, atomizing pressure 20MPa, and spray solution is spray-dried for 120 DEG C in spray drying device, is collected
It is spray-dried crude product；Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere, in 1100 DEG C of temperature
Degree lower further heat treatment, gained heat-treated products further wash, and are dried to obtain thin wall type porous carbon ball material；Heat treatment production
After object is washed using deionized water with diluted acid repeatedly, under 70 DEG C of temperature conditions, it is dried in vacuo 12h.Using deionized water with it is dilute
Acid washs repeatedly, obtains the thin wall type porous carbon materials that pore passage structure is abundant and hole wall is thin.Thin wall type porous carbon materials hole
It is 1.72cm to hold3/ g, specific surface area 561m2/ g, carbon pores wall thickness 5.5nm.Using porous carbon ball material manufactured in the present embodiment
10wt.%Super P are added as conductive agent in material, and 10wt.% sodium carboxymethylcelluloses (CMC) are used as binder, ground to fill
/ a small amount of deionized water is added afterwards is mixed to form uniform black paste slurry, these slurries are coated in copper foil current collector
As test electrode, with metallic sodium piece, electrode assembling becomes button cell as a comparison, uses electrolyte system for 1M
NaClO4/EC:DEC(1:1), under the current density of 50mA/g, test loop performance；1000mA/g, 2000mA/g etc. no
The high rate performance of battery is tested under same current density.It is good that test result shows that sodium-ion battery cathode prepared by this example has
Good chemical property：Under the current density of 50mA/g, first circle coulombic efficiency is 63%, and first circle discharge capacity is 252mA/
G after cycle 100 is enclosed, remains to the specific capacity for keeping 222mA/g；Under the power-discharging density of 1000mA/g and 2000mA/g, remain to point
Not Bao Chi 198mAh/g and 152mAh/g specific capacity.
Comparative example 1
3.6g lactose, 1.77g sodium chloride and 3.01g dodecyl sodium sulfates are added into 100ml deionized waters, 50
Spray solution is made until solution clarification in stirring at a temperature of DEG C.Under an argon atmosphere, it is arranged through the spray amount of spraying system and is
Spray solution is spray-dried for 120 DEG C by 2mL/min, atomizing pressure 5MPa in spray drying device, collects spray drying
Crude product；Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere, at a temperature of 900 DEG C further
Heat treatment, gained heat-treated products further wash, and are dried to obtain thin wall type porous carbon ball material；Heat-treated products using go from
It after sub- water washs repeatedly with diluted acid, is placed under 50 DEG C of temperature conditions, is dried in vacuo 8h.It is washed repeatedly with diluted acid using deionized water
It washs, the impurity generated in remaining fluxing agent and carbonisation can be removed.Obtain the thin-walled that pore passage structure is abundant and hole wall is thin
Type porous carbon materials.It is 0.11cm that thin wall type porous carbon materials hole, which holds,3/ g, specific surface area 210m2/ g, carbon pores wall thickness
16nm.Using porous carbon ball material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylic first
Base sodium cellulosate (CMC) is used as binder, it is ground fully after a small amount of deionized water be added be mixed to form uniform black paste
Shape slurry, by these slurries be coated in copper foil current collector on as test electrode, with metallic sodium piece as a comparison electrode assembling at
For button cell, use electrolyte system for 1M NaClO4/EC:DEC(1:1), under the current density of 50mA/g, test
Cycle performance；The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.Test result table
Bright, sodium-ion battery cathode prepared by this example has following chemical property：Under the current density of 50mA/g, first circle library
Human relations efficiency is 60%, and first circle discharge capacity is 193mA/g, after cycle 100 is enclosed, remains to the specific capacity for keeping 158mA/g；
Under the power-discharging density of 1000mA/g and 2000mA/g, the specific capacity for keeping 139mAh/g and 112mAh/g respectively is remained to.The implementation
Example heat treatment temperature is less than preferred scope, and fluxing agent cannot play etching effect, its material capacity is caused to be lower, and high rate performance becomes
Difference.
Comparative example 2
It compares, differs only in embodiment 1, the temperature of heat treatment (carbonization) is 1200 DEG C, and obtained thin wall type is porous
The Kong Rongwei 1.55cm of carbon ball3/ g, specific surface area 461m2/ g, carbon layers having thicknesses 1.01nm；It is assembled into button electricity using the material
Its chemical property is tested in pond under the same conditions, and under the current density of 50mA/g, first circle coulombic efficiency is 66%, first
Circle discharge capacity is 285mA/g, after cycle 100 is enclosed, remains to the specific capacity for keeping 236mA/g；In 1000mA/g and 2000mA/g
Power-discharging density under, remain to the specific capacity for keeping 210mAh/g and 199mAh/g respectively.Being heat-treated excessively high makes thin-walled porous carbon ball
Material loses undefined structure and is converted to graphite material, and it is poor that capacity plays, and decaying is fast；Fluxing agent eats into carbon material lose at this time simultaneously
Strongly, lead to carbon ball structure collapses, carbon-coating stripping.
Comparative example 3
5.4g fructose and 4.13g sodium chloride are added into 100ml deionized waters, stirring is until solution at a temperature of 50 DEG C
Spray solution is made in clarification.Under an argon atmosphere, the spray amount that setting passes through spraying system is 5mL/min, and atomizing pressure is
Spray solution is spray-dried for 160 DEG C by 10MPa in spray drying device, collects spray drying crude product；Dry gained
The spray drying crude product arrived, is placed in tube furnace, in inert atmosphere, is further heat-treated at a temperature of 1100 DEG C, gained heat
Processing product further washs, and is dried to obtain heat-treated products；After heat-treated products are washed using deionized water with diluted acid repeatedly,
It is placed under 70 DEG C of temperature conditions, is dried in vacuo 12h.It is washed repeatedly with diluted acid using deionized water.The heat treatment material hole holds
For 2.01cm3/ g, specific surface area 355m2/ g, carbon pores wall thickness 2.01nm.
Material is prepared using this comparative example, 10wt.%Super P are added as conductive agent, 10wt.% carboxymethyl celluloses
Sodium (CMC) is used as binder, and ground fully a small amount of deionized water, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic sodium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M NaClO4/EC:DEC(1:1), under the current density of 50mA/g, test loop performance；
The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.Test result shows prepared by this example
Sodium-ion battery cathode have following chemical property：Under the current density of 50mA/g, first circle coulombic efficiency is
71%, first circle discharge capacity is 289mA/g, after cycle 100 is enclosed, remains to the specific capacity for keeping 251mA/g；In 1000mA/g and
Under the power-discharging density of 2000mA/g, the specific capacity for keeping 197mAh/g and 173mAh/g respectively is remained to.It is compared with embodiment 1, it is right
Ratio does not add surfactant, and spray drying process is caused to be difficult to form chondritic, eventually lead to material particle and
Electron-transporting is poor, and dynamics is unfavorable, and high rate performance is deteriorated.
Comparative example 4
5.4g fructose and 2.72g dodecyl sodium sulfates are added into 100ml deionized waters, stirred at a temperature of 50 DEG C
Until solution is clarified, spray solution is made.Under an argon atmosphere, the spray amount that setting passes through spraying system is 5mL/min, atomization
Pressure is 10MPa, and spray solution is spray-dried for 160 DEG C in spray drying device, collects spray drying crude product；It is dry
Dry obtained spray drying crude product, is placed in tube furnace, in inert atmosphere, is further heat-treated at a temperature of 1100 DEG C,
Gained heat-treated products further wash, and are dried to obtain heat-treated products；Heat-treated products use deionized water and diluted acid repeatedly
It after washing, is placed under 70 DEG C of temperature conditions, is dried in vacuo 12h.It is washed repeatedly with diluted acid using deionized water.The heat-treated wood
Expect Kong Rongwei 0.11cm3/ g, specific surface area 215m2/ g, carbon pores wall thickness 17nm.
Material is prepared using this comparative example, 10wt.%Super P are added as conductive agent, 10wt.% carboxymethyl celluloses
Sodium (CMC) is used as binder, and ground fully a small amount of deionized water, which is added, is mixed to form uniform black paste slurry later, will
These slurries are coated in copper foil current collector as test electrode, and with metallic sodium piece, electrode assembling becomes button electricity as a comparison
Pond uses electrolyte system for 1M NaClO4/EC:DEC(1:1), under the current density of 50mA/g, test loop performance；
The high rate performance of battery is tested under the different current density such as 1000mA/g, 2000mA/g.Test result shows prepared by this example
Sodium-ion battery cathode have following chemical property：Under the current density of 50mA/g, first circle coulombic efficiency is
81%, first circle discharge capacity is 179mA/g can keep the specific capacity of 133mA/g after cycle 100 is enclosed；In 1000mA/g and
Under the power-discharging density of 2000mA/g, the specific capacity for keeping 125mAh/g and 102mAh/g respectively is remained to.It is compared with embodiment 1, it is right
Ratio does not have fluxing agent and forms porous structure to etch carbon material, causes prepared carbon ball pore passage structure deficient, storage sodium capacity is low.
Claims (10)
1. a kind of thin wall type porous carbon ball material, it is characterised in that：For the porous nano carbon ball with thin-walled type hole；The thin-walled
The pore wall thickness of type hole is 1~16nm.
2. a kind of thin wall type porous carbon ball material according to claim 1, it is characterised in that：The porous nano carbon ball it is straight
Diameter is 30~500nm.
3. a kind of thin wall type porous carbon ball material according to claim 1 or claim 2, it is characterised in that：The porous nano carbon ball
It is made of disorderly arranged graphite microcrystal, 0.11~2.83cm of Kong Rongwei of porous nano carbon ball3/ g, specific surface area be 200~
1500m2/g。
4. a kind of any one of claims 1 to 3 preparation method of thin wall type porous carbon ball material, it is characterised in that：It will give birth to
Substance carbohydrate carbon source, water-soluble inorganic salt fluxing agent and surfactant are dissolved in water, obtain spray solution；The spray solution is logical
It crosses spray drying and obtains porous carbon ball presoma；The porous carbon ball presoma by be carbonized heat treatment to get.
5. a kind of preparation method of thin wall type porous carbon ball material according to claim 4, it is characterised in that：
The biomass carbohydrate carbon source includes at least one of starch, lactose, chitosan, glucose, sucrose；
The water-soluble inorganic salt fluxing agent includes at least one of the water-soluble salt containing lithium, sodium, zinc or potassium；
The surfactant include in cetyl trimethylammonium bromide, dodecyl sodium sulfate, polyvinylpyrrolidone extremely
Few one kind.
6. a kind of preparation method of thin wall type porous carbon ball material according to claim 5, it is characterised in that：Biomass sugar
The molar ratio of class carbon source, water-soluble inorganic salt fluxing agent and surfactant three is 0.2~0.5：0.3~0.8：0.1~
0.2。
7. a kind of preparation method of thin wall type porous carbon ball material according to any one of claim 4 to 6, feature exist
In：A concentration of 0.1~0.8mol/L of water-soluble inorganic salt fluxing agent in the spray solution.
8. a kind of preparation method of thin wall type porous carbon ball material according to claim 4, it is characterised in that：The spraying
Dry condition is：Temperature is 120~280 DEG C, and spray amount is 0.5~20mL/min, and atomizing pressure is 1~30MPa, gas stream
Speed is≤10L/min.
9. a kind of preparation method of thin wall type porous carbon ball material according to claim 4, it is characterised in that：The carbonization
The process of heat treatment is：Under protective atmosphere, in 1000~1100 DEG C of temperature, it is heat-treated 0.5~20h.
10. the application of claims 1 to 3 any one of them thin wall type porous carbon ball material, it is characterised in that：As sodium ion
The negative material application of battery.
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