CN107895797A - A kind of preparation method of carbon nanosheet material and its application in sodium-ion battery - Google Patents
A kind of preparation method of carbon nanosheet material and its application in sodium-ion battery Download PDFInfo
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- CN107895797A CN107895797A CN201711261632.3A CN201711261632A CN107895797A CN 107895797 A CN107895797 A CN 107895797A CN 201711261632 A CN201711261632 A CN 201711261632A CN 107895797 A CN107895797 A CN 107895797A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
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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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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/13—Electrodes for accumulators with non-aqueous electrolyte, e.g. for lithium-accumulators; Processes of manufacture thereof
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Abstract
The invention discloses a kind of preparation method of carbon nanosheet material and its application in sodium-ion battery；Phenolic resin and KCl are mixed in absolute ethyl alcohol or dimethylformamide and form suspension；After taking suspension to carry out hydro-thermal reaction, take product to be placed in stirring in the aqueous solution of transition metal salt and obtain presoma to adsorb transition metal ions；It is carbonized and produces at 800~1200 DEG C of presoma.This method raw material is easy to get, and preparation technology is simple, reproducible；The material longrange disorder of preparation, shortrange order, there is larger interlamellar spacing, abundant pore passage structure, big specific surface area and good electric conductivity, use it for sodium-ion battery, high circulation efficiency, height ratio capacity and high rate performance are shown, there is wide industrial applications prospect.
Description
Technical field
Answering the present invention relates to a kind of preparation method of carbon nanosheet material and its as Carbon negative electrode material of sodium ion battery
With belonging to sodium-ion battery field.
Background technology
With the traditional energy such as coal, oil, natural gas gradually decrease and increasingly serious environmental problem, small-sized point
Explosive growth trend is showed from portable power source demand, the various chargeable electrochmical power sources using lithium ion battery as representative are got over
To be more taken seriously.With the increase of hybrid vehicle and the demand of electrical energy storage device, the consumption of lithium also drastically increases
It is long.However, the constituent content due to lithium in the earth's crust is relatively fewer, the extraction and recovery of lithium are difficult, therefore, have and lithium ion
The sodium-ion battery of the similar deintercalation mechanism of battery is considered as the ideal chose in extensive energy storage field.
At present, the consideration based on developing material cost and application prospect, it is main to study more sodium ion negative material
It is various carbon-based materials, such as graphite, graphene, agraphitic carbon, the chemical property of carbon-based material is relevant with each self-structure.Example
Such as, although graphite is with higher lithium storage content, the ability of its storage sodium is very weak, is widely considered to be sodium ion radius and graphite
Caused by interlamellar spacing mismatches.And the degree of graphitization of amorphous carbon is low, its structure is mainly to be interlocked by a large amount of unordered carbon crystallites
Accumulation forms, and interlamellar spacing is big, contains a large amount of nanometer micropores again, provides preferable avtive spot for the storage of sodium ion, therefore
Amorphous carbon material has higher reversible storage sodium capacity, but such material conductivity is poor, performance cycle stability is poor, capacity
Decay is fast, strongly limit it and is applied in sodium-ion battery.Therefore, carbon material how is improved as sodium-ion battery negative pole
Specific capacity and long-term cycle stability energy, turn into key of the limitation carbon material as anode material of lithium-ion battery large-scale application
Problem.
The content of the invention
The defects of existing for existing sodium ion battery electrode material, it is an object of the invention to provide a kind of short distance to have
Sequence, longrange disorder, specific surface area are big, reactivity site is abundant, interlamellar spacing is moderate, the carbon nanometer with certain degree of graphitization
The preparation method of piece, this method technique is simple, reproducible, cost is cheap, environment-friendly, it is easy to accomplish industrialization.
It is applied to sodium-ion battery as negative material it is a further object to provide above-mentioned carbon nanosheet material
In, gained sodium-ion battery shows high specific capacity, good high rate performance and long circulating stability energy.
A kind of preparation method of carbon nanosheet material of the present invention, comprises the following steps：
Step 1
It is dissolved in using phenolic resin as carbon source in absolute ethyl alcohol or dimethylformamide, adds KCl and stir to form suspension,
Suspension is subjected to hydro-thermal reaction, after having reacted, first time separation of solid and liquid obtains solid particle A, washing, dries i.e. acquisition carbon nanometer
Sheet material material precursor；
In the suspension, phenolic resin and KCl mass ratio are 1~10:1；
The reaction temperature of the hydro-thermal reaction is 160 DEG C~220 DEG C, and the reaction time is 16h~24h；
Step 2
By carbon nanosheet material precursor obtained by step 1；It is placed in transition metal salt solution and obtains mixing turbid, stirring,
Second of separation of solid and liquid obtains solid particle B, drying, produces the carbon nanosheet material precursor of absorption transition metal ions；
Mass fraction of the carbon nanosheet material precursor in transition metal saline solution is 1 wt%~15wt%；
Step 3
By the carbon nanosheet material precursor of absorption transition metal ions obtained by step 2；It is carbonized under inert atmosphere protection
Crude product is obtained, the carburizing temperature is 800 DEG C~1200 DEG C, and crude product is washed, is drying to obtain product carbon nanosheet material.
A kind of preparation method of carbon nanosheet material of the present invention, in step 1, the quality of phenolic resin in the suspension
Fraction is 15wt%~30wt%.Preferably, the mass fraction of phenolic resin is 17 wt%~25wt% in the suspension.
A kind of preparation method of carbon nanosheet material of the present invention, in step 1, the carbon source is dissolved in absolute ethyl alcohol.
A kind of preparation method of carbon nanosheet material of the present invention, in step 1, the mass ratio of the phenolic resin and KCl is
2~6：1.
A kind of preparation method of carbon nanosheet material of the present invention, in step 1, the reaction temperature of the hydro-thermal reaction is 160
DEG C~180 DEG C, the reaction time is 16h~18h.
A kind of preparation method of carbon nanosheet material of the present invention, in step 2, the transition metal salt solution is selected from chlorination
At least one of ferrous solution, cobalt nitrate solution, copper-bath, the concentration of the transition metal salt solution for 1mol/L~
3mol/L。
A kind of preparation method of carbon nanosheet material of the present invention, in step 2, the carbon nanosheet material precursor is in mistake
The mass fraction crossed in aqueous metal salt is 4wt%~8wt%.
A kind of preparation method of carbon nanosheet material of the present invention, in step 2, the time of the stirring is 16h~24h.
A kind of preparation method of carbon nanosheet material of the present invention, in step 3, the inert atmosphere is argon gas atmosphere or nitrogen
Gas atmosphere.Preferably, the inert atmosphere is nitrogen atmosphere.
A kind of preparation method of carbon nanosheet material of the present invention, in step 3, the temperature of the carbonization is 800 DEG C~900
DEG C, the time of carbonization is 1h~4h, and the heating rate of the carbonization is 1 DEG C/min~10 DEG C/min.Preferably, the carbonization
Time is 2h~3h.
A kind of preparation method of carbon nanosheet material of the present invention, in step 3, the crude product uses concentration as 1mol/L
~3mol/L inorganic acid solution replaces washing >=3 time with water, is placed under 50 DEG C~80 DEG C of temperature conditionss, and vacuum drying 8h~
12h；Obtain the carbon nanosheet material.
A kind of preparation method of carbon nanosheet material of the present invention, in step 3, the carbon nanosheet material is by graphitized carbon
With agraphitic carbon nanometer sheet form, graphitized carbon even dispersion on unformed carbon nanosheet, the carbon nanosheet material
Thickness is 50nm~500nm.
In the present invention, graphitized carbon refers to the carbon of degree of graphitization R≤1.2, and the calculation formula of the R is R=ID/IG, the IDRefer to 1360cm in Raman collection of illustrative plates-1Integrated intensity, the IGRefer to 1580cm in Raman collection of illustrative plates-1(G peaks)
Integrated intensity.
A kind of preparation method of carbon nanosheet material of the present invention, in step 3, the specific surface area of the carbon nanosheet material
For 100m2/ g~1200m2/g.In preferable scheme, the specific surface area of the carbon nanosheet material is 200 m2/ g~1000m2/
g.In further preferred scheme, the specific surface area of the carbon nanosheet material is 400m2/ g~800m2/g
Present invention also offers a kind of application of carbon nanosheet material, using the carbon nanosheet material as sodium-ion battery
Negative material is applied in sodium-ion battery.
Carbon nanosheet material prepared by the present invention prepares method and the performance detection side of sodium-ion battery as negative material
Method：Above-mentioned carbon nanosheet material is weighed, adds 10wt.%Super P as conductive agent, 10wt.% sodium carboxymethylcelluloses
(CMC) binding agent is used as, ground fully adding a small amount of deionized water is mixed to form uniform black paste slurry afterwards, by this
A little slurries are coated in test electrode is used as in copper foil current collector, with metallic sodium piece, electrode assembling turns into button cell as a comparison,
It uses electrolyte system as 1M NaClO4/ EC:DEC(1:1).Charging and discharging currents density is used in test loop performance
100mA/g。
Compared with the prior art, the beneficial effect that technical scheme is brought：
The present invention using the phenolic resin that is readily available as carbon source, using KCl as crystal structure template, then anti-by hydro-thermal
Should, the carbon nanosheet presoma of regular appearance is prepared, while upper common transition metal ions is adsorbed as catalyst,
High temperature cabonization produces on the basis of this.This method raw material is cheap and easy to get, and technique is simple, reproducible, environment-friendly, it is easy to accomplish work
Industry metaplasia is produced.
Technical scheme, its basis mechanism are；Using inorganic salt crystal as template in its Surface coating organic layer, have
In the presence of transition metal ions inversion of phases occurs during high temperature cabonization for machine layer, and part carbon conversion is into orderly graphite
Change carbon material, so as to obtain the carbon nanosheet material, it has by graphitized carbon even dispersion in unformed carbon nanosheet
On composite construction, effectively facilitate insertion of the sodium ion between carbon-coating and abjection process, and then drastically increase porous carbon
The specific capacity of material, the coulombic efficiency of battery is effectively increased, improve sodium-ion battery performance.The present invention realizes high storage sodium ratio
The perfect adaptation of capacity and high circulation coulombic efficiency.
Carbon nanosheet material prepared by the present invention is good with electrolyte wellability as anode material of lithium-ion battery, leads
Electrically it is good, interlamellar spacing is moderate, and specific surface area is big, and avtive spot enriches, and can shorten sodium ion transmission range, have good sodium from
The embedded abjection ability of son, ordered graphitic cyclic structure are enriched, and electrical conductivity is high, are advantageous to electronics conduction, reduce impedance, improve battery
High rate performance and cycle efficieny.
The present invention's overcomes poorly conductive in traditional amorphous carbon material, the inappropriate problem of interlamellar spacing, the carbon nanometer
Sheet material has special compound carbon structure, and loose and porous structure provides abundant avtive spot for the storage of sodium ion, more
Carbon material relatively large carbon-coating spacing in hole can effectively facilitate insertion and abjection process of the sodium ion between carbon-coating, improve carbon material
Specific capacity, while even dispersion obtain highly-graphitized carbon provide excellent conductive capability and storage sodium ability.Have available for preparing
There is the sodium-ion battery of high coulombic efficiency, excellent high rate performance and long circulating stability energy.
Brief description of the drawings
【Fig. 1】For the SEM scanning electron microscope (SEM) photographs of carbon nanosheet material made from embodiment 1.
【Fig. 2】The circulation number of turns-circulation the electric discharge for being used for sodium-ion battery for carbon nanosheet material made from embodiment 1 is held
Amount, coulombic efficiency figure.
【Fig. 3】For the Raman spectrogram of carbon nanosheet material made from embodiment 1.
【Fig. 4】For the XRD diffraction pattern spectrograms of carbon nanosheet material made from embodiment 1.
Embodiment
Following examples are intended to be described in further details present invention；And the protection domain of the claims in the present invention
It is not limited by the example.
Embodiment 1
12.8g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 2.23g KCl is added and continues stirring extremely
Suspension is formed, suspension is transferred into ptfe autoclave carries out hydro-thermal reaction, 180 DEG C of holding temperature, soaking time
18h.Adopt and be washed with deionized 3 times after product filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain Two-dimensional Carbon and receive
Rice piece presoma.3.1g two dimension carbon nanosheet presomas are placed in the cobalt nitrate solution that 50mL concentration is 2mol/L, stirring
24h, by filtering drying, obtain adsorbing the two-dimentional carbon nanosheet presoma of transition metal ions.By presoma under nitrogen atmosphere
It is carbonized, 900 DEG C, carbonization time 2h of carburizing temperature, heating rate is 2 DEG C/min.Subsequent high temperature cabonization product is using dense
Spend and washed repeatedly three times with water for 2mol/L dilute hydrochloric acid solution, is placed under 50 DEG C of temperature conditionss, be dried in vacuo 8h.Obtain carbon
Nanometer sheet material.The carbon nanosheet material specific surface area is 792m2/ g, the scanning electron microscope (SEM) photograph of carbon nanosheet material is made
(SEM) Fig. 1 is seen.
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, survey
Try cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result
Show, sodium-ion battery negative pole prepared by this example has good chemical property：Under 50mA/g current density, its first circle
Coulombic efficiency is 75%, and first circle discharge capacity is 366mA/g, after the circle of circulation 100, remains to keep 296mA/g specific capacity；
Under 1000mA/g and 2000mA/g power-discharging density, remain to keep 252mAh/g and 209mAh/g specific capacity respectively.
Embodiment 2
13.1g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 3.34g KCl is added and continues stirring extremely
Suspension is formed, suspension is transferred into ptfe autoclave carries out hydro-thermal reaction, 180 DEG C of holding temperature, soaking time
16h.Adopt and be washed with deionized 3 times after filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain two-dimentional carbon nanosheet
Presoma.3.1g two dimension carbon nanosheet presomas are placed in the ferric chloride solution that 50mL concentration is 1mol/L, stir 24h, warp
Suction filtration drying is crossed, obtains adsorbing the two-dimentional carbon nanosheet presoma of transition metal ions.Presoma is subjected to carbon under nitrogen atmosphere
Change, 1200 DEG C, carbonization time 2h of carburizing temperature, heating rate is 2 DEG C/min.Subsequent high temperature cabonization product use concentration for
After 2mol/L dilute acid soln washs three times repeatedly with water, it is placed under 50 DEG C of temperature conditionss, is dried in vacuo 8h.Obtain carbon nanosheet
Material.The material specific surface area is 690m2/g
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, survey
Try cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result
Show, sodium-ion battery negative pole prepared by this example has good chemical property：Under 50mA/g current density, its first circle
Coulombic efficiency is 74%, and first circle discharge capacity is 341mA/g, after the circle of circulation 100, remains to keep 283mA/g specific capacity；
Under 1000mA/g and 2000mA/g power-discharging density, remain to keep 244mAh/g and 201mAh/g specific capacity respectively.
Embodiment 3
9.8g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 3.3g KCl is added and continues stirring to shape
Into suspension, suspension is transferred to ptfe autoclave and carries out hydro-thermal reaction, 180 DEG C of holding temperature, soaking time
16h.Adopt and be washed with deionized 3 times after filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain two-dimentional carbon nanosheet
Presoma.3.1g two dimension carbon nanosheet presomas are placed in the cobalt nitrate solution that 50mL concentration is 3mol/L, stir 24h, warp
Suction filtration drying is crossed, obtains adsorbing the two-dimentional carbon nanosheet presoma of transition metal ions.Presoma is subjected to carbon under nitrogen atmosphere
Change, 900 DEG C, carbonization time 2h of carburizing temperature, heating rate is 2 DEG C/min.Subsequent high temperature cabonization product use concentration for
After 2mol/L dilute nitric acid solution washs repeatedly with water, it is placed under 50 DEG C of temperature conditionss, is dried in vacuo 8h.Obtain carbon nanosheet material
Material.The material specific surface area is 581m2/g。
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, survey
Try cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result
Show, sodium-ion battery negative pole prepared by this example has good chemical property：Under 50mA/g current density, its first circle
Coulombic efficiency is 70%, and first circle discharge capacity is 310mA/g, after the circle of circulation 100, remains to keep 230mA/g specific capacity；
Under 1000mA/g and 2000mA/g power-discharging density, remain to keep 201mAh/g and 188mAh/g specific capacity respectively.
Embodiment 4
12.8g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 1.28g KCl is added and continues stirring extremely
Suspension is formed, suspension is transferred into ptfe autoclave carries out hydro-thermal reaction, 160 DEG C of holding temperature, soaking time
16h.Adopt and be washed with deionized 3 times after filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain two-dimentional carbon nanosheet
Presoma.3.1g two dimension carbon nanosheet presomas are placed in the nickel chloride solution that 50mL concentration is 2mol/L, stir 24h, warp
Suction filtration drying is crossed, obtains adsorbing the two-dimentional carbon nanosheet presoma of transition metal ions.Presoma is subjected to carbon under nitrogen atmosphere
Change, 800 DEG C, carbonization time 3h of carburizing temperature, heating rate is 2 DEG C/min.Subsequent high temperature cabonization product use concentration for
After 2mol/L dilution heat of sulfuric acid washs three times repeatedly with water, it is placed under 50 DEG C of temperature conditionss, is dried in vacuo 8h.Obtain carbon nanometer
Sheet material.The material specific surface area is 433m2/ g, using carbon nanosheet material manufactured in the present embodiment, add 10wt.%
For Super P as conductive agent, 10wt.% sodium carboxymethylcelluloses (CMC) are used as binding agent, ground fully to add afterwards on a small quantity
Deionized water is mixed to form uniform black paste slurry, and these slurries are coated in copper foil current collector as test electrode,
With metallic sodium piece, electrode assembling turns into button cell as a comparison, and it uses electrolyte system as 1M NaClO4/EC:DEC(1:
1), under 50mA/g current density, test loop performance；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 negative pole prepared by this example has good chemical property：
Under 50mA/g current density, its first circle coulombic efficiency is 65%, and first circle discharge capacity is 289mA/g, after the circle of circulation 100, still
233mA/g specific capacity can be kept；Under 1000mA/g and 2000mA/g power-discharging density, remain to keep respectively 195mAh/g and
177mAh/g specific capacity.
Comparative example 1
12.8g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 2.23g KCl is added and continues stirring extremely
Suspension is formed, suspension is transferred into ptfe autoclave carries out hydro-thermal reaction, 160 DEG C of holding temperature, soaking time
24h.Adopt and be washed with deionized 3 times after filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain two-dimentional carbon nanosheet
Presoma, presoma is carbonized in a nitrogen atmosphere, 900 DEG C, carbonization time 2h of carburizing temperature, heating rate be 2 DEG C/
min.After subsequent high temperature cabonization product uses concentration to be washed three times repeatedly with water for 2mol/L dilute hydrochloric acid solution, 50 DEG C are placed in
Under temperature conditionss, 8 h are dried in vacuo.Obtain carbon nanosheet material.The material specific surface area is 683m2/g。
Carbon nanosheet material is prepared using this comparative example, adds 10wt.%Super P as conductive agent, 10wt.% carboxylic first
Base sodium cellulosate (CMC) is used as binding agent, it is ground fully after add a small amount of deionized water and be mixed to form uniform black paste
Shape slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece as a comparison electrode assembling into
For button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, test
Cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result table
Bright, sodium-ion battery negative pole prepared by this example has good chemical property：Under 50mA/g current density, its first circle storehouse
Human relations efficiency is 77%, and first circle discharge capacity is 202mA/g, after the circle of circulation 100, keeps 142mA/g specific capacity；In 1000mA/g
Under 2000mA/g power-discharging density, 126mAh/g and 102mAh/g specific capacity is kept respectively.
Comparative example 2
13.1g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, is transferred to ptfe autoclave
Carry out hydro-thermal reaction, 180 DEG C of holding temperature, soaking time 16h.Adopt and be washed with deionized 3 times after filtering, be then placed on vacuum
The dry 10h of 60 DEG C of drying box, obtains two-dimentional carbon nanosheet presoma.It is dense that 3.1g two dimension carbon nanosheet presomas are placed in 50mL
Spend in the ferric chloride solution for 1mol/L, stir 24h, by filtering drying, the Two-dimensional Carbon for obtaining adsorbing transition metal ions is received
Rice piece presoma.Presoma is carbonized under nitrogen atmosphere, 1200 DEG C, carbonization time 2h of carburizing temperature, heating rate 2
℃/min.After subsequent high temperature cabonization product uses concentration to be washed three times repeatedly with water for 2mol/L dilute acid soln, 50 DEG C are placed in
Under temperature conditionss, 8h is dried in vacuo.Obtain carbon nanosheet material.The material specific surface area is 302m2/g。
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, survey
Try cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result
Show, material is under 50mA/g current density, and its first circle coulombic efficiency is 64%, and first circle discharge capacity is 201mA/g, is followed
After ring 100 encloses, 130mA/g specific capacity is kept；Under 1000mA/g and 2000mA/g power-discharging density, remain to keep respectively
101mAh/g and 91mAh/g specific capacity.
Comparative example 3
12.8g phenolic resin is dissolved in 20ml absolute ethyl alcohol and stirrings to being completely dissolved, it is evenly laid out to be covered with 2.23g
On KCl culture dish, culture dish is placed in 60 DEG C of baking oven and dried to ethanol evaporating completely.Deionization is used after product filtering
Water washing 3 times, the dry 10h of 60 DEG C of vacuum drying chamber is then placed on, obtains two-dimentional carbon nanosheet presoma.3.1g Two-dimensional Carbons are received
Rice piece presoma is placed in the cobalt nitrate solution that 50mL concentration is 2mol/L, stirs 24h, by filtering drying, is adsorbed
Cross the two-dimentional carbon nanosheet presoma of metal ion.Presoma is carbonized under nitrogen atmosphere, 900 DEG C of carburizing temperature, carbonization
Time is 2h, and heating rate is 2 DEG C/min.Subsequent high temperature cabonization product uses concentration anti-for 2mol/L dilute hydrochloric acid solution and water
After backwashing is washed three times, is placed under 50 DEG C of temperature conditionss, is dried in vacuo 8h.Obtain carbon nanosheet material.The carbon nanosheet material ratio
Surface area is 633m2/g。
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, survey
Try cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result
Show, sodium-ion battery negative pole prepared by this example has good chemical property：Under 50mA/g current density, its first circle
Coulombic efficiency is 66%, and first circle discharge capacity is 249mA/g, after the circle of circulation 100, keeps 180mA/g specific capacity；
Under 1000mA/g and 2000mA/g power-discharging density, 152mAh/g and 109mAh/g specific capacity is kept respectively.
Comparative example 4：
12.8g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 2.23g KCl is added and continues stirring extremely
Suspension is formed, suspension is transferred into ptfe autoclave carries out hydro-thermal reaction, 150 DEG C of holding temperature, soaking time
18h.Adopt and be washed with deionized 3 times after product filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain Two-dimensional Carbon and receive
Rice piece presoma.3.1g two dimension carbon nanosheet presomas are placed in the cobalt nitrate solution that 50mL concentration is 2mol/L, stirring
24h, by filtering drying, obtain adsorbing the two-dimentional carbon nanosheet presoma of transition metal ions.By presoma under nitrogen atmosphere
It is carbonized, 900 DEG C, carbonization time 2h of carburizing temperature, heating rate is 2 DEG C/min.Subsequent high temperature cabonization product is using dense
Spend and washed repeatedly three times with water for 2mol/L dilute hydrochloric acid solution, is placed under 50 DEG C of temperature conditionss, be dried in vacuo 8h.Obtain carbon
Nanometer sheet material.The carbon nanosheet material specific surface area is 401m2/g。
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/
EC:DEC(1:1), under 50mA/g current density, test loop performance；In 1000mA/g, 2000 mA/g etc.
The high rate performance of battery is tested under different current densities.Test result shows that sodium-ion battery negative pole prepared by this example has
Good chemical property：Under 50mA/g current density, its first circle coulombic efficiency is 66%, and first circle discharge capacity is
233mA/g, after circulation 100 is enclosed, keep 168mA/g specific capacity；Under 1000mA/g and 2000mA/g power-discharging density, respectively
Keep 144mAh/g and 101mAh/g specific capacity.
Comparative example 5
17.1g phenolic resin is dissolved in 50ml absolute ethyl alcohol and stirrings to being completely dissolved, 1.13g KCl is added and continues stirring extremely
Suspension is formed, suspension is transferred into ptfe autoclave carries out hydro-thermal reaction, 180 DEG C of holding temperature, soaking time
18h.Adopt and be washed with deionized 3 times after product filtering, be then placed on the dry 10h of 60 DEG C of vacuum drying chamber, obtain Two-dimensional Carbon and receive
Rice piece presoma.3.1g two dimension carbon nanosheet presomas are placed in the cobalt nitrate solution that 50mL concentration is 2mol/L, stirring
24h, by filtering drying, obtain adsorbing the two-dimentional carbon nanosheet presoma of transition metal ions.By presoma under nitrogen atmosphere
It is carbonized, 900 DEG C, carbonization time 2h of carburizing temperature, heating rate is 2 DEG C/min.Subsequent high temperature cabonization product is using dense
Spend and washed repeatedly three times with water for 2mol/L dilute hydrochloric acid solution, is placed under 50 DEG C of temperature conditionss, be dried in vacuo 8h.Obtain carbon
Nanometer sheet material.The carbon nanosheet material specific surface area is 299m2/g。
Using carbon nanosheet material manufactured in the present embodiment, 10wt.%Super P are added as conductive agent, 10wt.% carboxylics
Sodium carboxymethylcellulose pyce (CMC) is used as binding agent, and ground fully adding a small amount of deionized water is mixed to form uniform black afterwards
Pasty slurry, using these slurries coated in copper foil current collector as testing electrode, with metallic sodium piece electrode assembling as a comparison
As button cell, it uses electrolyte system as 1M NaClO4/ EC:DEC(1:1), under 50mA/g current density, survey
Try cycle performance；The high rate performance of battery is tested under the different current densities such as 1000mA/g, 2000 mA/g.Test result
Show, sodium-ion battery negative pole prepared by this example has good chemical property：Under 50mA/g current density, its first circle
Coulombic efficiency is 66%, and first circle discharge capacity is 245mA/g, after the circle of circulation 100, keeps 177mA/g specific capacity；
Under 1000mA/g and 2000mA/g power-discharging density, 156mAh/g and 110mAh/g specific capacity is kept respectively.
Claims (10)
1. a kind of preparation method of carbon nanosheet material, it is characterised in that comprise the following steps：
Step 1
It is dissolved in using phenolic resin as carbon source in absolute ethyl alcohol or dimethylformamide, adds KCl and stir to form suspension, will be outstanding
Turbid carries out hydro-thermal reaction, and after having reacted, first time separation of solid and liquid obtains solid particle A, washing, dries i.e. acquisition carbon nanosheet material
Material precursor；
In the suspension, phenolic resin and KCl mass ratio are 1~10:1；
The reaction temperature of the hydro-thermal reaction is 160 DEG C~220 DEG C, and the reaction time is 16h~24h；
Step 2
By carbon nanosheet material precursor obtained by step 1；It is placed in transition metal salt solution and obtains mixing turbid, stirring, second
Secondary separation of solid and liquid obtains solid particle B, drying, produces the carbon nanosheet material precursor of absorption transition metal ions；
Mass fraction of the carbon nanosheet material precursor in transition metal saline solution is 1wt%~15wt%；
Step 3
By the carbon nanosheet material precursor of absorption transition metal ions obtained by step 2；It is carbonized under inert atmosphere protection slightly
Product, the carburizing temperature are 800 DEG C~1200 DEG C, and crude product is washed, is drying to obtain product carbon nanosheet material.
2. the preparation method of a kind of carbon nanosheet material according to claim 1, it is characterised in that described in step 1
The mass fraction of phenolic resin is 15wt%~30wt% in suspension.
3. the preparation method of a kind of carbon nanosheet material according to claim 1, it is characterised in that described in step 1
Phenolic resin and KCl mass ratio are 2~6：1.
4. the preparation method of a kind of carbon nanosheet material according to claim 1, it is characterised in that described in step 1
The reaction temperature of hydro-thermal reaction is 160 DEG C~180 DEG C, and the reaction time is 16h~18h.
5. the preparation method of a kind of carbon nanosheet material according to claim 1, it is characterised in that described in step 2
Transition metal salt solution is selected from least one of ferric chloride solution, cobalt nitrate solution, copper-bath, the transition metal salt
The concentration of solution is 1mol/L~3mol/L.
6. the preparation method of a kind of carbon nanosheet material according to claim 1, it is characterised in that described in step 2
The time of stirring is 16h~24h；
In step 2, mass fraction of the carbon nanosheet material precursor in transition metal saline solution be 4 wt%~
8wt%.
7. the preparation method of a kind of carbon nanosheet material according to claim 1, it is characterised in that described in step 3
The temperature of carbonization is 800 DEG C~900 DEG C, and the time of carbonization is 1h~4h, and the heating rate of the carbonization is 1 DEG C/min~10
℃/min。
A kind of 8. preparation method of carbon nanosheet material according to claim 1-7 any one, it is characterised in that step
In three, the carbon nanosheet material is made up of graphitized carbon and agraphitic carbon nanometer sheet, and graphitized carbon even dispersion is unformed
Carbon nanosheet on, the thickness of the carbon nanosheet material is 50nm~500nm, and the specific surface area of the carbon nanosheet material is
100m2/ g~1200m2/g。
A kind of 9. preparation method of carbon nanosheet material according to claim 8, it is characterised in that the carbon nanosheet material
The specific surface area of material is 400m2/ g~800m2/g。
10. application of a kind of carbon nanosheet material in sodium-ion battery, it is characterised in that the claims 1-7 is any
One carbon nanosheet material is applied in sodium-ion battery as anode material of lithium-ion battery.
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