CN104300150A - Asphalt-based nanoporous carbon material, negative material thereof, and lithium ion battery - Google Patents
Asphalt-based nanoporous carbon material, negative material thereof, and lithium ion battery Download PDFInfo
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- CN104300150A CN104300150A CN201410191815.2A CN201410191815A CN104300150A CN 104300150 A CN104300150 A CN 104300150A CN 201410191815 A CN201410191815 A CN 201410191815A CN 104300150 A CN104300150 A CN 104300150A
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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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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M10/00—Secondary cells; Manufacture thereof
- H01M10/05—Accumulators with non-aqueous electrolyte
- H01M10/052—Li-accumulators
- H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
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- 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 invention discloses an asphalt-based nanoporous carbon material, a negative material thereof, and a lithium ion battery. The asphalt-based nanoporous carbon material is prepared by mainly using 0.1-10g of asphalt, 3-50g of anhydrous aluminum trichloride, 100-400ml of anhydrous carbon tetrachloride and 200-500ml of a reaction terminating agent, and the amounts of the above raw materials can be freely adjusted in proportion. The asphalt-based nanoporous carbon material is prepared by mainly using asphalt, anhydrous aluminum chloride, anhydrous carbon tetrachloride and the reaction termination agent, and asphalt and anhydrous carbon tetrachloride undergo a Friedel-Crafts crosslinking reaction through a nanometer pore forming technology, so the obtained asphalt-based carbon material has a porous structure and a high specific surface area, and the negative material prepared by using the asphalt-based nanoporous carbon material has the characteristics of strong electrolyte imbibition and retention ability, good processing performance, low price and the like, and can greatly improve the cycle performances of the lithium ion battery.
Description
Technical field
The invention belongs to porous carbon materials technical field, be specifically related to a kind of asphalt-based nano porous carbon materials, also relate to a kind of negative material and the lithium ion battery that use this porous carbon materials simultaneously.
Background technology
Negative material is the chief component of lithium ion battery, and produces material impact to the cycle performance of lithium ion battery, security performance and high rate performance thereof.And market demands negative material has the imbibition ability of good cycle performance, processing characteristics and excellence thereof.Graphite negative electrodes material used is in the market owing to having less specific area, cause that the imbibition ability of material is poor, cycle performance be general, therefore develop a kind of have become one of selection improving negative material performance compared with the negative material of bigger serface.
Boring technique is one of method improving material specific surface area, namely prepares the material with carbon element with nano-pore at material surface, to improve the imbibition liquid-keeping property of material, thus improves the cycle performance of material.At present, the method preparing nano-pore material with carbon element mainly contains soft template method and hard template method, but these two kinds of methods all need to add template, has that complex procedures, synthesis condition are harsh, process is difficult to problems such as controlling, expensive, limits its extensive use.Therefore, employing becomes a kind of selection well without template synthesis porous carbon materials.
Pitch is the organic material as a form of gel of sepia, and main component is asphalitine and resin, and next has the compound of high boiling mineral oil and a small amount of oxygen, sulphur and chlorine, is viscous liquid or solid under normal temperature.Due to pitch there is aboundresources, cheap, phosphorus content is high, good fluidity, easy graphited advantage, therefore the common used material of preparation graphite type material is become, but because asphalt-based material has the defects such as specific area is little, absorbent is poor, limit giving full play to of its material property.
Summary of the invention
The object of this invention is to provide the asphalt-based nano porous carbon materials that a kind of specific area is large, absorbent is good.
Second object of the present invention is to provide a kind of negative material using above-mentioned asphalt-based nano porous carbon materials.
3rd object of the present invention is to provide a kind of lithium ion battery using above-mentioned negative material.
In order to realize above object, the technical solution adopted in the present invention is: a kind of asphalt-based nano porous carbon materials, described porous carbon materials is made primarily of following raw material: pitch 0.1 ~ 10g, aluminum trichloride (anhydrous) 3 ~ 50g, anhydrous carbon tetrachloride 100 ~ 400ml, reaction terminating agent 200 ~ 500ml, the amount of above-mentioned each raw material can adjust arbitrarily in proportion.
Described reaction terminating agent is the volume ratio of ethanol and water is the mixed liquor of 100:50 ~ 100.
Described water is redistilled water.
Described porous carbon materials is that pitch is dissolved in anhydrous carbon tetrachloride, then adds aluminum trichloride (anhydrous) and carry out Friedel-Crafts reaction (friedel-crafts reaction) as catalyst, rear reaction terminating agent cessation reaction, gets after solid product carbonizes and obtains.
Described porous carbon materials is that pitch is dissolved in anhydrous carbon tetrachloride, then adds aluminum trichloride (anhydrous) and carry out Friedel-Crafts reaction as catalyst, rear reaction terminating agent cessation reaction, get solid product carry out successively carbonizing, activate after obtain.
The reaction temperature of described Friedel-Crafts reaction is 30 ~ 75 DEG C, and the reaction time is 2 ~ 72h.
The temperature of described charing is 300 ~ 1000 DEG C, and carbonization time is 2 ~ 12h.Described charing is carried out under an inert atmosphere.Described inert atmosphere is the nitrogen atmosphere of 200 ~ 800ml/min flow velocity.The heating rate reaching carbonization temperature is 2 ~ 5 DEG C/min.
Described activation is activated dose of activation successively, high-temperature activation.
In described activator activation, the mass ratio of the carbide that activator and described charing obtain is 1 ~ 10:1; The temperature of described high-temperature activation is 500 ~ 900 DEG C, and soak time is 6 ~ 12h.
Described activator is NaOH.During activator activation, the carbide described charing obtained adds in water/alcohol mixeding liquid with NaOH and fully mixes, rear drying.
Described high-temperature activation carries out under an inert atmosphere.Described inert atmosphere is the nitrogen atmosphere of 200 ~ 800ml/min flow velocity.The heating rate of the activation temperature that reaches a high temperature is 1 ~ 2 DEG C/min.
After high-temperature activation, activation products, after washing, filtration and drying, obtain described asphalt-based nano porous carbon materials.
Before described washing, the temperature of activation products is reduced to less than 50 DEG C.Described washing is washed 2 ~ 8 times under boiling condition with the solution that deionized water and concentrated hydrochloric acid mix by the volume ratio of 5 ~ 20:1, then spend deionized water 1 ~ 4 time.The temperature of described drying is 80 ~ 100 DEG C, and drying time is 12 ~ 24h.
Described asphalt-based nano porous carbon materials, specifically prepared by following methods:
1) pitch of 0.1 ~ 10g is added in the anhydrous carbon tetrachloride of 6 ~ 300ml, stirring and dissolving, obtain mixture A;
2) aluminum trichloride (anhydrous) of 3 ~ 50g is added (total consumption of anhydrous carbon tetrachloride is 100 ~ 400ml) in remaining anhydrous carbon tetrachloride, after aluminum trichloride (anhydrous) dissolves, add step 1 again) gained mixture A, add hot reflux under stirring condition and carry out Friedel-Crafts reaction, after add the reaction terminating agent cessation reaction of 200 ~ 500ml, negate answer gained mixed system successively after filtration, washing, filter, after drying, obtain solid product;
3) by step 2) gained solid product is placed in heating charing under inert gas atmosphere, obtains carbide;
4) by activator and step 3) gained carbide adds in water/alcohol mixeding liquid and fully mixes, rear filtration, drying, obtains mixture B;
5) by step 4) gained mixture B carries out high-temperature activation under being placed in inert gas atmosphere, gained activation products successively through washing, filter, after drying, obtain described asphalt-based nano porous carbon materials.
Wherein, step 4) described in water/alcohol mixeding liquid, the volume ratio of ethanol and water is 100:50 ~ 100.
Described water is redistilled water.
Step 4) described in the consumption of water/alcohol mixeding liquid be: every 5g carbide adds water/alcohol mixeding liquid 200 ~ 400ml.
Step 4) described in baking temperature be 80 ~ 100 DEG C.
Use a negative material for above-mentioned asphalt-based nano porous carbon materials, this negative material obtains graphitic carbon material after carrying out coating modification, carbonization, graphitization, pulverizing, spheroidization by described asphalt-based nano porous carbon materials and graphite.
The preparation method of this negative material, comprises following concrete steps:
A) coating modification: by organic solvent, asphalt-based nano porous carbon materials, graphite powder mixing, under 500 DEG C of conditions after stirring reaction 8h, filter and drying, obtain coating modification material;
B) carbonization: under inert gas shielding, by step a) gained coating modification material warms to 1000 DEG C after being incubated 6h, be cooled to less than 100 DEG C, pulverizes to obtain char-forming material;
C) graphitization: under inert gas shielding, with the heating rate of 1 ~ 5 DEG C/min, by step b) gained char-forming material is warming up to 2800 DEG C and after being incubated 48h, substep is cooled to less than 100 DEG C, obtains graphitized material;
D) pulverize, spheroidization: by step c) gained graphitized material pulverize after, carry out material spherical and classification, obtain described negative material.
Described organic solvent is oxolane.
The mass ratio of described asphalt-based nano porous carbon materials and graphite is 10 ~ 40:100.
A kind of lithium ion battery, the negative material of this lithium ion battery is above-mentioned negative material.
Asphalt-based nano porous carbon materials of the present invention, make primarily of pitch, aluminum trichloride (anhydrous), anhydrous carbon tetrachloride and reaction terminating agent, adopt nanometer boring technique, make pitch and anhydrous carbon tetrachloride that Friedel-Crafts cross-linking reaction occur, gained pitch base carbon material has loose structure and high-specific surface area, the negative material using this asphalt-based nano porous carbon materials to prepare has the characteristics such as imbibition liquid-keeping property is strong, excellent processing performance, low price, can increase substantially the cycle performance of lithium ion battery.
Asphalt-based nano porous carbon materials of the present invention, adopt nanometer boring technique, pitch is dissolved in anhydrous carbon tetrachloride, add aluminum trichloride (anhydrous) again and carry out Friedel-Crafts reaction as catalyst, after use reaction terminating agent cessation reaction, get solid product carry out successively carbonizing, activate after obtain, its preparation method belongs to without template boring technique, compared with template, there is the advantage that synthesis condition is simple, process easily controls, cost is low, pore-creating is effective.Described activation process comprises activator activation and high-temperature activation, wherein activator is NaOH, have activation effect good, suitable hole can be produced, namely the porous carbon materials that specific area is moderate is obtained, compared with KOH activator, have little to consersion unit corrosivity, pore-creating ability is moderate (pore-creating hyperenergia can pore-creating too much, thus cause collapse of pore structure, the more difficult control of poration process), the advantage such as process easily controls, low price.
Cathode material of lithium ion battery of the present invention, adopt above-mentioned asphalt-based nano porous carbon materials graphite to be carried out to the graphitic carbon material that the series of process processes such as coating modification obtain, have loose structure and high-specific surface area, specific area (BET) is 100 ~ 1000m
2/ g, pore volume is 0.2 ~ 0.3cm
3/ g, wherein Micropore volume accounts for 20 ~ 50%, and outside mesopore and macropore pore volume account for 50 ~ 80%; The simple pitch class coated graphite that adopts prepares to obtain negative material comparatively at present, and its imbibition liquid-keeping property is greatly improved, and has excellent processing performance, the characteristics such as low price simultaneously, make lithium ion battery cycle performance be improved significantly.
Lithium ion battery of the present invention, negative material used is above-mentioned graphitic carbon material, because negative material has extremely strong imbibition liquid-keeping property, thus the cycle performance of lithium ion battery is significantly improved; For ferric phosphate lithium cell, through experimental test, use the rate of liquid aspiration of the battery of negative material of the present invention for 5.2g/min, 500 times circulation conservation rate is 96.2%, the rate of liquid aspiration 3.1g/min of the battery adopting conventional method to prepare under equal conditions, 500 times circulation conservation rate is 92.9%, and illustrate and use negative material of the present invention, the cycle performance of lithium ion battery is improved significantly.
Accompanying drawing explanation
Fig. 1 is the SEM figure of embodiment 1 gained negative material;
Fig. 2 is the cyclic curve figure of embodiment 1 gained lithium ion battery.
Embodiment
Below in conjunction with embodiment, the present invention is further illustrated.
Embodiment 1
The asphalt-based nano porous carbon materials of the present embodiment, makes primarily of following raw material: pitch 5g, aluminum trichloride (anhydrous) 20g, anhydrous carbon tetrachloride 250ml, reaction terminating agent 300ml.Described reaction terminating agent is the mixed liquor of ethanol and water.
The asphalt-based nano porous carbon materials of the present embodiment, prepared by following methods:
1) pitch of 5g is added in the anhydrous carbon tetrachloride of 200ml, stirring and dissolving, obtain mixture A;
2) aluminum trichloride (anhydrous) of 20g is placed in reactor, add (total consumption of anhydrous carbon tetrachloride is 250ml) in the anhydrous carbon tetrachloride of 50ml, after aluminum trichloride (anhydrous) dissolves, add step 1 again) gained mixture A, 50 DEG C are heated under stirring condition, Friedel-Crafts reaction is carried out in backflow, after reaction 24h, the mixed liquor (volume ratio of ethanol and redistilled water is 100:50) of the ethanol and redistilled water that add 300ml is as reaction terminating agent cessation reaction, negate answers gained mixed system successively after filtration, washing, filter, after drying, obtain solid product,
3) by step 2) gained solid product is placed in retort, and under inert gas (nitrogen) atmosphere, be heated to 900 DEG C carbonize with the heating rate of 3 DEG C/min, the flow velocity of nitrogen is 200ml/min, after charing 12h, obtains carbide;
4) by the step 3 of activator NaOH and the 5g of 50g) gained carbide (mass ratio is 10:1), add in the water/alcohol mixeding liquid (ethanol is 100:50 with the volume ratio of redistilled water) of 400ml and fully mix, dry under 100 DEG C of conditions after filtration, obtain mixture B;
5) by step 4) gained mixture B is placed in activation furnace, under inert gas (nitrogen) atmosphere, be heated to 500 DEG C with the heating rate of 1 DEG C/min and carry out high-temperature activation, the flow velocity of nitrogen is 600ml/min, after high-temperature activation 12h, after the temperature of gained activation products is reduced to 40 DEG C, wash 5 times under boiling condition with the solution that deionized water and concentrated hydrochloric acid mix by the volume ratio of 20:1, spend deionized water again 2 times, filter afterwards, under 100 DEG C of conditions after dry 24h, obtain described asphalt-based nano porous carbon materials.
The negative material of the asphalt-based nano porous carbon materials that the use of the present embodiment is above-mentioned is the graphitic carbon material with high-specific surface area obtained after carrying out coating modification, carbonization, graphitization, pulverizing, spheroidization by asphalt-based nano porous carbon materials described in 15g and 50g graphite.
The preparation method of this negative material, comprises following concrete steps:
A) coating modification: organic solvent (oxolane), asphalt-based nano porous carbon materials, graphite powder to be added successively in reactor and to mix, stirring reaction 8h under 500 DEG C of conditions, in reactor, mixing speed is 40r/min, filter after reaction and drying under 100 DEG C of conditions, obtain coating modification material;
B) carbonization: at inert gas (N
2) under protection, by step a) gained coating modification material warms to 1000 DEG C after being incubated 6h, be cooled to less than 100 DEG C, pulverize to obtain char-forming material;
C) graphitization: at inert gas (N
2) under protection, with the heating rate of 1 DEG C/min, by step b) gained char-forming material is warming up to 2800 DEG C and after being incubated 48h, substep is cooled to less than 100 DEG C, obtains graphitized material;
D) pulverize, spheroidization: by step c) gained graphitized material with pulverizer pulverize after, carry out material spherical and classification, obtain described negative material.
The SEM figure of the present embodiment gained negative material as shown in Figure 1.As can be seen from Figure 1, embodiment 1 gained negative material surface has more microcellular structure, and it is evenly distributed, rationally, Stability Analysis of Structures, without subsiding.
The lithium ion battery of the present embodiment, with above-mentioned graphitic carbon material for negative material, take LiFePO4 as positive electrode, adopts LiPF
6/ EC+DEC (volume ratio 1: 1) is electrolyte, and Celgard2400 film is barrier film, prepares 5AH soft-package battery.
Embodiment 2
The asphalt-based nano porous carbon materials of the present embodiment, makes primarily of following raw material: pitch 10g, aluminum trichloride (anhydrous) 50g, anhydrous carbon tetrachloride 400ml, reaction terminating agent 500ml.Described reaction terminating agent is the mixed liquor of ethanol and water.
The asphalt-based nano porous carbon materials of the present embodiment, prepared by following methods:
1) pitch of 10g is added in the anhydrous carbon tetrachloride of 300ml, stirring and dissolving, obtain mixture A;
2) aluminum trichloride (anhydrous) of 50g is placed in reactor, add (total consumption of anhydrous carbon tetrachloride is 400ml) in the anhydrous carbon tetrachloride of 100ml, after aluminum trichloride (anhydrous) dissolves, add step 1 again) gained mixture A, 75 DEG C are heated under stirring condition, Friedel-Crafts reaction is carried out in backflow, after reaction 48h, the mixed liquor (volume ratio of ethanol and redistilled water is 100:70) of the ethanol and redistilled water that add 500ml is as reaction terminating agent cessation reaction, negate answers gained mixed system successively after filtration, washing, filter, after drying, obtain solid product,
3) by step 2) gained solid product is placed in retort, and under inert gas (nitrogen) atmosphere, be heated to 800 DEG C carbonize with the heating rate of 3 DEG C/min, the flow velocity of nitrogen is 800ml/min, after charing 4h, obtains carbide;
4) by the step 3 of activator NaOH and the 5g of 25g) gained carbide (mass ratio is 5:1), add in the water/alcohol mixeding liquid (ethanol is 100:70 with the volume ratio of redistilled water) of 200ml and fully mix, dry under 100 DEG C of conditions after filtration, obtain mixture B;
5) by step 4) gained mixture B is placed in activation furnace, under inert gas (nitrogen) atmosphere, be heated to 900 DEG C with the heating rate of 2 DEG C/min and carry out high-temperature activation, the flow velocity of nitrogen is 600ml/min, after high-temperature activation 6h, after the temperature of gained activation products is reduced to 40 DEG C, wash 5 times under boiling condition with the solution that deionized water and concentrated hydrochloric acid mix by the volume ratio of 5:1, spend deionized water again 2 times, filter afterwards, under 100 DEG C of conditions after dry 24h, obtain described asphalt-based nano porous carbon materials.
The negative material of the asphalt-based nano porous carbon materials that the use of the present embodiment is above-mentioned is the graphitic carbon material with high-specific surface area obtained after carrying out coating modification, carbonization, graphitization, pulverizing, spheroidization by asphalt-based nano porous carbon materials described in 5g and 50g graphite.
The preparation method of this negative material, comprises following concrete steps:
A) coating modification: organic solvent (oxolane), asphalt-based nano porous carbon materials, graphite powder to be added successively in reactor and to mix, stirring reaction 8h under 500 DEG C of conditions, in reactor, mixing speed is 40r/min, filter after reaction and drying under 100 DEG C of conditions, obtain coating modification material;
B) carbonization: at inert gas (N
2) under protection, by step a) gained coating modification material warms to 1000 DEG C after being incubated 6h, be cooled to less than 100 DEG C, pulverize to obtain char-forming material;
C) graphitization: at inert gas (N
2) under protection, with the heating rate of 5 DEG C/min, by step b) gained char-forming material is warming up to 2800 DEG C and after being incubated 48h, substep is cooled to less than 100 DEG C, obtains graphitized material;
D) pulverize, spheroidization: by step c) gained graphitized material with pulverizer pulverize after, carry out material spherical and classification, obtain described negative material.
The lithium ion battery of the present embodiment, with above-mentioned graphitic carbon material for negative material, take LiFePO4 as positive electrode, adopts LiPF
6/ EC+DEC (volume ratio 1: 1) is electrolyte, and Celgard2400 film is barrier film, prepares 5AH soft-package battery.
Embodiment 3
The asphalt-based nano porous carbon materials of the present embodiment, makes primarily of following raw material: pitch 0.1g, aluminum trichloride (anhydrous) 3g, anhydrous carbon tetrachloride 100ml, reaction terminating agent 200ml.Described reaction terminating agent is the mixed liquor of ethanol and water.
The asphalt-based nano porous carbon materials of the present embodiment, prepared by following methods:
1) pitch of 0.1g is added in the anhydrous carbon tetrachloride of 6ml, stirring and dissolving, obtain mixture A;
2) aluminum trichloride (anhydrous) of 3g is placed in reactor, add (total consumption of anhydrous carbon tetrachloride is 100ml) in the anhydrous carbon tetrachloride of 94ml, after aluminum trichloride (anhydrous) dissolves, add step 1 again) gained mixture A, 30 DEG C are heated under stirring condition, Friedel-Crafts reaction is carried out in backflow, after reaction 72h, the mixed liquor (volume ratio of ethanol and redistilled water is 100:100) of the ethanol and redistilled water that add 200ml is as reaction terminating agent cessation reaction, negate answers gained mixed system successively after filtration, washing, filter, after drying, obtain solid product,
3) by step 2) gained solid product is placed in retort, and under inert gas (nitrogen) atmosphere, be heated to 300 DEG C carbonize with the heating rate of 2 DEG C/min, the flow velocity of nitrogen is 600ml/min, after charing 10h, obtains carbide;
4) by the step 3 of activator NaOH and the 5g of 10g) gained carbide (mass ratio is 2:1), add in the water/alcohol mixeding liquid (ethanol is 100:100 with the volume ratio of redistilled water) of 300ml and fully mix, dry under 80 DEG C of conditions after filtration, obtain mixture B;
5) by step 4) gained mixture B is placed in activation furnace, under inert gas (nitrogen) atmosphere, be heated to 750 DEG C with the heating rate of 1.5 DEG C/min and carry out high-temperature activation, the flow velocity of nitrogen is 800ml/min, after high-temperature activation 8h, after the temperature of gained activation products is reduced to 45 DEG C, wash 8 times under boiling condition with the solution that deionized water and concentrated hydrochloric acid mix by the volume ratio of 10:1, spend deionized water again 1 time, filter afterwards, under 90 DEG C of conditions after dry 12h, obtain described asphalt-based nano porous carbon materials.
The negative material of the asphalt-based nano porous carbon materials that the use of the present embodiment is above-mentioned is the graphitic carbon material with high-specific surface area obtained after carrying out coating modification, carbonization, graphitization, pulverizing, spheroidization by asphalt-based nano porous carbon materials described in 20g and 50g graphite.
The preparation method of this negative material, comprises following concrete steps:
A) coating modification: organic solvent (oxolane), asphalt-based nano porous carbon materials, graphite powder to be added successively in reactor and to mix, stirring reaction 8h under 500 DEG C of conditions, in reactor, mixing speed is 40r/min, filter after reaction and drying under 100 DEG C of conditions, obtain coating modification material;
B) carbonization: at inert gas (N
2) under protection, by step a) gained coating modification material warms to 1000 DEG C after being incubated 6h, be cooled to less than 100 DEG C, pulverize to obtain char-forming material;
C) graphitization: at inert gas (N
2) under protection, with the heating rate of 3 DEG C/min, by step b) gained char-forming material is warming up to 2800 DEG C and after being incubated 48h, substep is cooled to less than 100 DEG C, obtains graphitized material;
D) pulverize, spheroidization: by step c) gained graphitized material with pulverizer pulverize after, carry out material spherical and classification, obtain described negative material.
The lithium ion battery of the present embodiment, with above-mentioned graphitic carbon material for negative material, take LiFePO4 as positive electrode, adopts LiPF
6/ EC+DEC (volume ratio 1: 1) is electrolyte, and Celgard2400 film is barrier film, prepares 5AH soft-package battery.
Embodiment 4
The asphalt-based nano porous carbon materials of the present embodiment, makes primarily of following raw material: pitch 1g, aluminum trichloride (anhydrous) 10g, anhydrous carbon tetrachloride 200ml, reaction terminating agent 400ml.Described reaction terminating agent is the mixed liquor of ethanol and water.
The asphalt-based nano porous carbon materials of the present embodiment, prepared by following methods:
1) pitch of 1g is added in the anhydrous carbon tetrachloride of 100ml, stirring and dissolving, obtain mixture A;
2) aluminum trichloride (anhydrous) of 10g is placed in reactor, add (total consumption of anhydrous carbon tetrachloride is 200ml) in the anhydrous carbon tetrachloride of 100ml, after aluminum trichloride (anhydrous) dissolves, add step 1 again) gained mixture A, 75 DEG C are heated under stirring condition, Friedel-Crafts reaction is carried out in backflow, after reaction 2h, the mixed liquor (volume ratio of ethanol and redistilled water is 100:80) of the ethanol and redistilled water that add 400ml is as reaction terminating agent cessation reaction, negate answers gained mixed system successively after filtration, washing, filter, after drying, obtain solid product,
3) by step 2) gained solid product is placed in retort, and under inert gas (nitrogen) atmosphere, be heated to 1000 DEG C carbonize with the heating rate of 5 DEG C/min, the flow velocity of nitrogen is 400ml/min, after charing 2h, obtains carbide;
4) by the step 3 of activator NaOH and the 5g of 5g) gained carbide (mass ratio is 1:1), add in the water/alcohol mixeding liquid (ethanol is 100:80 with the volume ratio of redistilled water) of 200ml and fully mix, dry under 100 DEG C of conditions after filtration, obtain mixture B;
5) by step 4) gained mixture B is placed in activation furnace, under inert gas (nitrogen) atmosphere, be heated to 600 DEG C with the heating rate of 1 DEG C/min and carry out high-temperature activation, the flow velocity of nitrogen is 200ml/min, after high-temperature activation 10h, after the temperature of gained activation products is reduced to 35 DEG C, wash 2 times under boiling condition with the solution that deionized water and concentrated hydrochloric acid mix by the volume ratio of 15:1, spend deionized water again 4 times, filter afterwards, under 80 DEG C of conditions after dry 16h, obtain described asphalt-based nano porous carbon materials.
The negative material of the asphalt-based nano porous carbon materials that the use of the present embodiment is above-mentioned is the graphitic carbon material with high-specific surface area obtained after carrying out coating modification, carbonization, graphitization, pulverizing, spheroidization by asphalt-based nano porous carbon materials described in 10g and 50g graphite.
The preparation method of this negative material, comprises following concrete steps:
A) coating modification: organic solvent (oxolane), asphalt-based nano porous carbon materials, graphite powder to be added successively in reactor and to mix, stirring reaction 8h under 500 DEG C of conditions, in reactor, mixing speed is 40r/min, filter after reaction and drying under 100 DEG C of conditions, obtain coating modification material;
B) carbonization: at inert gas (N
2) under protection, by step a) gained coating modification material warms to 1000 DEG C after being incubated 6h, be cooled to less than 100 DEG C, pulverize to obtain char-forming material;
C) graphitization: at inert gas (N
2) under protection, with the heating rate of 2 DEG C/min, by step b) gained char-forming material is warming up to 2800 DEG C and after being incubated 48h, substep is cooled to less than 100 DEG C, obtains graphitized material;
D) pulverize, spheroidization: by step c) gained graphitized material with pulverizer pulverize after, carry out material spherical and classification, obtain described negative material.
The lithium ion battery of the present embodiment, with above-mentioned graphitic carbon material for negative material, take LiFePO4 as positive electrode, adopts LiPF
6/ EC+DEC (volume ratio 1: 1) is electrolyte, and Celgard2400 film is barrier film, prepares 5AH soft-package battery.
Experimental example 1
This experimental example is tested the configuration of surface of embodiment 1-4 gained negative material, specific area, pore volume and imbibition liquid-keeping property, and result is as shown in table 1,2.
In table 1, the method for testing of specific surface method of testing and pore volume is with reference to GB/T24533-2009 silicon/carbon/graphite in lithium ion batteries class negative material.
The imbibition ability method of testing of material is: the pipette 10ml electrolyte adopting 10ml in glove box, with the speed of 1/3 seconds, electrolyte is dripped on cathode pole piece afterwards, along with the dripping quantity of electrolyte increases, material surface presents saturation condition and is considered as terminating, and calculates the electrolyte content at unit interval internal consumption afterwards.
Liquid-keeping property method of testing is: take a certain size, the cathode pole piece of certain mass, to be placed in electrolyte 5 minutes afterwards, take weight A afterwards, after afterwards pole piece being placed 24 hours in glove box, taking weight is B, calculate afterwards and protect liquid rate=(A-B)/A, be the liquid-keeping property of material.
Wherein, comparative example is Delanium.
The specific area of the different negative material of table 1 and pore volume
The imbibition liquid-keeping property contrast table of the different negative material of table 2
| Object | Rate of liquid aspiration (ml/min) | Protect liquid rate (24h electrolyte content/0h electrolyte content) |
| Embodiment 1 | 5.2 | 95.3％ |
| Embodiment 2 | 5.4 | 94.2％ |
| Embodiment 3 | 5.1 | 94.4％ |
| Embodiment 4 | 5.0 | 93.9％ |
| Comparative example | 3.1 | 83.7％ |
As can be seen from Table 1, 2, specific area, the pore volume of embodiment gained negative material have had great growth relative to comparative example, and imbibition liquid-keeping property is improved significantly.
Experimental example 2
The cycle performance of this experimental example to embodiment 1-4 gained lithium ion battery is tested, and result is as shown in Fig. 2 and table 3.
Method of testing: take charge-discharge magnification as 2.0C/2.0C; Charging/discharging voltage scope: 3.65V ~ 2.5V; Temperature: 25 ± 2.0 DEG C; 5AH soft-package battery cycle performance prepared by testing example and comparative example.
Wherein comparative example is: be negative material with Delanium, take LiFePO4 as positive electrode, adopts LiPF
6/ EC+DEC (volume ratio 1: 1) is electrolyte, and Celgard2400 film is barrier film, prepares 5AH soft-package battery.
The cycle performance test result of the lithium ion battery of the different negative material of table 3
As can be seen from Fig. 2 and table 3, the cycle performance of the lithium ion battery using negative material of the present invention to prepare, relative to comparative example, obtains and significantly improves.
Claims (10)
1. an asphalt-based nano porous carbon materials, it is characterized in that: described porous carbon materials is made primarily of following raw material: pitch 0.1 ~ 10g, aluminum trichloride (anhydrous) 3 ~ 50g, anhydrous carbon tetrachloride 100 ~ 400ml, reaction terminating agent 200 ~ 500ml, the amount of above-mentioned each raw material can adjust arbitrarily in proportion.
2. asphalt-based nano porous carbon materials according to claim 1, is characterized in that: described reaction terminating agent is the volume ratio of ethanol and water is the mixed liquor of 100:50 ~ 100.
3. asphalt-based nano porous carbon materials according to claim 1 and 2, it is characterized in that: described porous carbon materials is that pitch is dissolved in anhydrous carbon tetrachloride, add aluminum trichloride (anhydrous) again and carry out Friedel-Crafts reaction as catalyst, after use reaction terminating agent cessation reaction, get solid product carry out successively carbonizing, activate after obtain.
4. asphalt-based nano porous carbon materials according to claim 3, is characterized in that: the reaction temperature of described Friedel-Crafts reaction is 30 ~ 75 DEG C, and the reaction time is 2 ~ 72h.
5. asphalt-based nano porous carbon materials according to claim 3, is characterized in that: the temperature of described charing is 300 ~ 1000 DEG C, and carbonization time is 2 ~ 12h.
6. asphalt-based nano porous carbon materials according to claim 3, is characterized in that: described activation is activated dose of activation successively, high-temperature activation.
7. asphalt-based nano porous carbon materials according to claim 6, is characterized in that: in described activator activation, the mass ratio of the carbide that activator and described charing obtain is 1 ~ 10:1; The temperature of described high-temperature activation is 500 ~ 900 DEG C, and soak time is 6 ~ 12h.
8. use a negative material for asphalt-based nano porous carbon materials as claimed in claim 1, it is characterized in that: this negative material obtains graphitic carbon material after carrying out coating modification, carbonization, graphitization, pulverizing, spheroidization by described asphalt-based nano porous carbon materials and graphite.
9. negative material according to claim 8, is characterized in that: the mass ratio of described asphalt-based nano porous carbon materials and graphite is 10 ~ 40:100.
10. a lithium ion battery, is characterized in that: the negative material of this lithium ion battery is the negative material described in claim 8 or 9.
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