CN106099109A - A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet - Google Patents
A kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet Download PDFInfo
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- CN106099109A CN106099109A CN201610459292.4A CN201610459292A CN106099109A CN 106099109 A CN106099109 A CN 106099109A CN 201610459292 A CN201610459292 A CN 201610459292A CN 106099109 A CN106099109 A CN 106099109A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/02—Electrodes composed of, or comprising, active material
- H01M4/36—Selection of substances as active materials, active masses, active liquids
- H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
- H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
- H01M4/587—Carbonaceous material, e.g. graphite-intercalation compounds or CFx for inserting or intercalating light metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/054—Accumulators with insertion or intercalation of metals other than lithium, e.g. with magnesium or aluminium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The present invention relates to material with carbon element preparing technical field, a kind of preparation method and applications of asphaltic base hard charcoal nanometer sheet, the method includes procedure below: with medium temperature coal pitch as raw material, with terephthalyl alcohol as cross-linking agent, p-methyl benzenesulfonic acid is that catalyst carries out cross-linking reaction at 100~170 DEG C, prepare hard carbon precursor modified pitch: again by sodium chloride and ethanol mixing and ball milling, obtain micron order sodium chloride template after drying;After mixing according to a certain percentage with sodium chloride template after finally modified pitch being dissolved in N-methyl ketopyrrolidine, after 650~850 DEG C of carbonizations, washing obtains asphaltic base hard charcoal nanometer sheet, is applied to sodium-ion battery negative pole.Preparation method provided by the present invention is simple, and the preparation process of charcoal nanometer sheet need not pickling and goes removing template, environmental protection;Sodium chloride template and N-methyl pyrrolidinone solvent can recycle, and production cost is relatively low;Asphaltic base hard charcoal nanometer sheet prepared by the present invention shows higher reversible storage sodium capacity, preferable high rate performance and excellent cycle performance as anode material of lithium-ion battery.
Description
Technical field
The present invention relates to the preparation method and applications of a kind of asphaltic base hard charcoal nanometer sheet, belong to material with carbon element technology of preparing neck
Territory.
Background technology
Lithium ion battery due to advantages such as its running voltage are high, capacity is big, have extended cycle life, become mancarried electronic aid,
The first-selection of the energy storage system on a small scale such as electric automobile.But in the earth's crust, lithium resource reserves are few and skewness, it is impossible to meet not
Carry out the great demand of energy storage system.Sodium and lithium belong to same main group, and chemical property is close, and reserves are the abundantest, sodium ion electricity
The production cost in pond will be far below lithium ion battery, and exploitation sodium-ion battery is applied to advise greatly as the succedaneum of lithium ion battery
Mould energy storage system reasonable.
Owing to the radius of sodium ion is relatively big, the charcoal base negative material used in sodium-ion battery research is mainly carbon-coating spacing
Compared with hard carbon material big, that degree of graphitization is relatively low.Hard carbon precursor is mainly biomass, high molecular polymer, resin etc., wherein
Asphaltic base hard carbon cathode material has high Carbon yield, suitable carbon-coating spacing and the electric conductivity of excellence, be expected to commercialization sodium from
Sub-battery is used widely.
Microscopic appearance and the structure of hard carbon cathode material can affect material and electrolyte contacts area, sodium ion the evolving path
Deng, finally affect material electrochemical performance.Patent CN105098186A hard carbon presoma is mixed with soft carbon matrix precursor after through hand over
After connection, solidification, carbonization etc. process, obtain unformed Carbon Materials and be applied to sodium-ion battery, but hard charcoal prepared by the method is born
Pole material is that micron particles, electrolyte and negative material contact not fully, have impact on the chemical property of negative material.Will
Hard carbon material nanorize is an up the effective means of material electrochemical performance, and wherein charcoal nanometer sheet has and electrolyte contacts area
Greatly, the advantages such as sodium ion transmission path is short, obtain researcher extensive concern.Tradition charcoal nanometer sheet with metal-oxide as template,
Pickling is needed to remove removing template after carbonization, complicated process of preparation and easily pollute environment, constrain its widespread adoption.
Summary of the invention
In order to solve above-mentioned problems of the prior art, it is an object of the present invention to provide a kind of asphaltic base hard charcoal nanometer sheet
Preparation method and applications.The method preparation process is simple, abundant raw material source, prepared hard charcoal nanometer sheet be used as sodium from
Sub-battery cathode has the advantages such as specific capacity height, good rate capability and cycle performance excellence.
In order to realize foregoing invention purpose, adopt the technical scheme that to topic, the present invention present in solution prior art:
The preparation method of a kind of asphaltic base hard charcoal nanometer sheet, comprises the following steps:
Step 1, with medium temperature coal pitch as raw material, terephthalyl alcohol as cross-linking agent, p-methyl benzenesulfonic acid joins for catalyst
In reactor, preparing modified pitch by catalytic polymerization, catalytic polymerization temperature controls at 100~170 DEG C, and the response time is controlled
System is 1~10h, and the mass ratio of described medium temperature coal pitch, terephthalyl alcohol and p-methyl benzenesulfonic acid is 1:0.2-0.5:0.03-0.1;
Step 2, sodium chloride and ethanol are joined in ball grinder, mixing and ball milling, be evaporated ethanol and prepare sodium chloride template, ball
Time consuming controls 1~5h, and drum's speed of rotation controls 100~500rpm;Described sodium chloride and ethanol mass ratio are 1:0.25-
1;
Step 3, by step 1 prepare modified pitch be dissolved in N-methyl ketopyrrolidine (NMP) solvent, be added thereto to by step
The rapid 2 sodium chloride templates prepared, the lower solvent evaporated of stirring, and said mixture is carried out at carbonization under inert gas shielding
Reason, carbonization temperature controls at 650~850 DEG C, and carbonization time controls 1~3h, and described noble gas is in nitrogen or argon
One, the mass ratio of modified pitch and N-methyl ketopyrrolidine is 1:2-20, the mass ratio of modified pitch and sodium chloride template
For 1:3-20;
After step 4, carbonization step 3 prepared process, sample is cooled to room temperature, employing deionized water wash sodium chloride mould
Plate, is dried to obtain target material asphaltic base hard charcoal nanometer sheet.
The preparation method of described a kind of asphaltic base hard charcoal nanometer sheet, prepared asphaltic base hard charcoal nanometer sheet is at sodium-ion battery
In application.
The medicine have the advantages that compared with the prior art, the invention have the advantages that, (1) is provided by the present invention
Preparation method is simple, and the preparation process of charcoal nanometer sheet need not pickling and goes removing template, environmental protection;(2) sodium chloride template
Can recycle with N-methyl ketopyrrolidine (NMP) solvent, production cost is relatively low;(3) prepare raw material and template price is low
Honest and clean, abundance, it is easy to accomplish large-scale production;(4) the asphaltic base hard charcoal nanometer sheet that prepared by the present invention is as sodium-ion battery
Negative material shows higher reversible storage sodium capacity, preferable high rate performance and excellent cycle performance.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph figure of the asphaltic base hard charcoal nanometer sheet of the embodiment of the present invention 2 preparation.
Fig. 2 is the asphaltic base hard charcoal nanometer sheet transmission electron microscope photo figure of the embodiment of the present invention 2 preparation.
Fig. 3 is the X-ray diffractogram spectrogram of the asphaltic base hard charcoal nanometer sheet of the embodiment of the present invention 2 preparation.
Fig. 4 is the asphaltic base hard charcoal nanometer sheet of the embodiment of the present invention 2 preparation different electric current densities in sodium ion half-cell
Under charge-discharge performance curve chart.
Detailed description of the invention
Below in conjunction with embodiment and comparative example, the invention will be further described.
Embodiment 1
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 30g to benzene two
Methanol, adds 5g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 160 DEG C of reaction 3h, system is viscous liquid, cooling
Take out to room temperature.
Step 2,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 12g ethanol,
Ball milling 4h under 400rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 3, modified pitch powder 2g step 1 prepared, be dissolved in 30g NMP, be added thereto to 20g step 2
The sodium chloride template prepared, in 200 DEG C of oil baths, heating is evaporated NMP.The mixture carbonization that will obtain, in tube furnace under nitrogen protection
It is warming up to 650 DEG C with 5 DEG C/min and maintains 2h, taking out after cooling, and use deionized water dissolving sodium chloride, by hard for gained charcoal nanometer
Sheet is dried.XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.388nm.
Step 4, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity reach 271.3mAh g-1。
Embodiment 2
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 30g to benzene two
Methanol, adds 7g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 160 DEG C of reaction 3h, system is viscous liquid, cooling
Take out to room temperature.
Step 2,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 10g ethanol,
Ball milling 4h under 400rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 3, modified pitch powder 2g step 1 prepared, be dissolved in 40g NMP, be added thereto to 20g step 2
The sodium chloride template prepared, is evaporated NMP in 200 DEG C of oil baths.The mixture carbonization that will obtain, with 5 under nitrogen protection in tube furnace
DEG C/min is warming up to 750 DEG C and maintains 2h, take out after cooling, and use deionized water dissolving sodium chloride, by hard for gained charcoal nanometer sheet
It is dried.XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.381nm.
Step 4, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity reach 270.4mAh g-1。
Embodiment 3
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 30g to benzene two
Methanol, adds 7g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 170 DEG C of reaction 2h, system is viscous liquid, cooling
Take out to room temperature.
Step 2,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 8g ethanol,
Ball milling 5h under 300rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 3, modified pitch powder 2g step 1 prepared, be dissolved in 35g NMP, be added thereto to 40g step 2
The sodium chloride template prepared, is evaporated NMP in 200 DEG C of oil baths.The mixture carbonization that will obtain, with 5 under nitrogen protection in tube furnace
DEG C/min is warming up to 850 DEG C and maintains 2h, take out after cooling, and use deionized water dissolving sodium chloride, by hard for gained charcoal nanometer sheet
It is dried.XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.356nm.
Step 4, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity reach 218.7mAh g-1。
Embodiment 4
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 35g to benzene two
Methanol, adds 5g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 160 DEG C of reaction 3h, system is viscous liquid, cooling
Take out to room temperature.
Step 2,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 10g ethanol,
Ball milling 2h under 500rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 3, modified pitch powder 2g step 1 prepared, be dissolved in 40g NMP, be added thereto to 20g step 2
The sodium chloride template prepared, is evaporated NMP in 200 DEG C of oil baths.The mixture carbonization that will obtain, with 5 under nitrogen protection in tube furnace
DEG C/min is warming up to 850 DEG C and maintains 2h, take out after cooling, and use deionized water dissolving sodium chloride, by hard for gained charcoal nanometer sheet
It is dried.XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.357nm.
Step 4, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity reach 220.1mAh g-1。
Embodiment 5
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 30g to benzene two
Methanol, adds 10g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 150 DEG C of reaction 3h, system is viscous liquid, cold
But take out to room temperature.
Step 2,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 15g ethanol,
Ball milling 3h under 500rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 3, modified pitch powder 2g step 1 prepared, be dissolved in 30g NMP, be added thereto to 25g step 2
The sodium chloride template prepared, in 200 DEG C of oil baths, heating is evaporated NMP.The mixture carbonization that will obtain, in tube furnace under argon shield
It is warming up to 700 DEG C with 5 DEG C/min and maintains 1h, taking out after cooling, and use deionized water dissolving sodium chloride, by hard for gained charcoal nanometer
Sheet is dried.XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.383nm.
Step 4, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity reach 268.9mAh g-1。
Embodiment 6
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 40g to benzene two
Methanol, adds 7g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 140 DEG C of reaction 3h, system is viscous liquid, cooling
Take out to room temperature.
Step 2,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 10g ethanol,
Ball milling 4h under 400rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 3, modified pitch powder 2g step 1 prepared, be dissolved in 40g NMP, be added thereto to 30g step 2
The sodium chloride template prepared, in 200 DEG C of oil baths, heating is evaporated NMP.The mixture carbonization that will obtain, in tube furnace under argon shield
It is warming up to 800 DEG C with 5 DEG C/min and maintains 2h, taking out after cooling, and use deionized water dissolving sodium chloride, by hard for gained charcoal nanometer
Sheet is dried.XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.372nm.
Step 4, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity reach 262.8mAh g-1。
Comparative example 1
Step 1,20g sodium chloride is put in ball grinder, is added thereto to appropriate zirconia ball, add 10g ethanol,
Ball milling 4h under 400rpm rotating speed, is evaporated ethanol after being taken out by mixture, is separated with zirconia ball by sample, obtain micron order chlorination
Sodium template.
Step 2, by mid temperature pitch powder 2g, be dissolved in 40g NMP, be added thereto to 20g step 1 prepare sodium chloride
Template, is evaporated NMP in 200 DEG C of oil baths.The mixture carbonization that will obtain, with 5 DEG C/min liter under inert gas shielding in tube furnace
Temperature is to 750 DEG C and maintains 2h, takes out, and uses deionized water dissolving sodium chloride, hard for gained charcoal nanometer sheet be dried after cooling.XRD
Characterizing and find, 002 interlamellar spacing of hard charcoal nanometer sheet is 0.342nm.
Step 3, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity be 168.3mAh g-1。
Comparative example 2
Step 1,100g medium temperature coal pitch is added in round-bottomed flask, oil bath is heated to melted after, add 30g to benzene two
Methanol, adds 7g p-methyl benzenesulfonic acid after mix homogeneously, after continuing to be heated to 160 DEG C of reaction 3h, system is viscous liquid, cooling
Take out to room temperature.
Step 2, modified pitch powder 2g step 1 prepared put in tube furnace under inert gas shielding with 5 DEG C/min
It is warming up to 750 DEG C and maintains 2h, taking out after cooling, and use deionized water dissolving sodium chloride, hard for gained charcoal nanometer sheet is dried.
XRD characterizes discovery, and 002 interlamellar spacing of hard charcoal nanometer sheet is up to 0.374nm.
Step 3, hard charcoal nanometer sheet and acetylene black, PVDF (polyvinylidene fluoride) are prepared negative pole according to 7:2:1 mass ratio
Material, collector is Copper Foil, assembles sodium-ion battery in glove box.Land CT2001A type battery test system is tested
Battery performance, charging/discharging voltage scope is 0.01-3V, records this asphaltic base hard charcoal nanometer sheet at charge-discharge velocity 0.1A
g-1Under conditions of first reversible capacity be 209.6mAh g-1。
Claims (2)
1. the preparation method of an asphaltic base hard charcoal nanometer sheet, it is characterised in that comprise the following steps:
Step 1, with medium temperature coal pitch as raw material, terephthalyl alcohol as cross-linking agent, p-methyl benzenesulfonic acid join reaction for catalyst
In device, preparing modified pitch by catalytic polymerization, catalytic polymerization temperature controls at 100~170 DEG C, and the response time controls
1~10h, the mass ratio of described medium temperature coal pitch, terephthalyl alcohol and p-methyl benzenesulfonic acid is 1:0.2-0.5:0.03-0.1;
Step 2, sodium chloride and ethanol are joined in ball grinder, mixing and ball milling, be evaporated ethanol and prepare sodium chloride template, during ball milling
Between control 1~5h, drum's speed of rotation controls 100~500rpm;Described sodium chloride and ethanol mass ratio are 1:0.25-1;
Step 3, the modified pitch that step 1 prepares is dissolved in N-methyl pyrrolidinone solvent, is added thereto to be prepared by step 2
Sodium chloride template, the lower solvent evaporated of stirring, and said mixture is carried out under inert gas shielding carbonization process, carbonization temperature
Controlling at 650~850 DEG C, carbonization time controls 1~3h, described noble gas one in nitrogen or argon, modified
Colophonium is 1:2-20 with the mass ratio of N-methyl ketopyrrolidine, and modified pitch is 1:3-20 with the mass ratio of sodium chloride template;
After step 4, carbonization step 3 prepared process, sample is cooled to room temperature, employing deionized water wash sodium chloride template, does
Dry obtain target material asphaltic base hard charcoal nanometer sheet.
A kind of preparation method of asphaltic base hard charcoal nanometer sheet, prepared asphaltic base hard charcoal nanometer sheet
Application in sodium-ion battery.
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CN111320161A (en) * | 2020-03-08 | 2020-06-23 | 大连理工大学 | Preparation method and application of asphalt-based carbon nanosheet |
CN112758911A (en) * | 2020-12-31 | 2021-05-07 | 宁波杉杉新材料科技有限公司 | Hard carbon material, preparation method and application thereof, and lithium ion battery |
CN116613300A (en) * | 2023-07-18 | 2023-08-18 | 成都锂能科技有限公司 | Coal-based carbonized sodium battery anode material, preparation method thereof and sodium ion battery comprising coal-based carbonized sodium battery anode material |
CN116613300B (en) * | 2023-07-18 | 2023-09-22 | 成都锂能科技有限公司 | Coal-based carbonized sodium battery anode material, preparation method thereof and sodium ion battery comprising coal-based carbonized sodium battery anode material |
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