CN1846322A - Nonaqueous electrolyte secondary cell, carbon material for use therein, and precursor of said carbon material - Google Patents
Nonaqueous electrolyte secondary cell, carbon material for use therein, and precursor of said carbon material Download PDFInfo
- Publication number
- CN1846322A CN1846322A CNA2004800254534A CN200480025453A CN1846322A CN 1846322 A CN1846322 A CN 1846322A CN A2004800254534 A CNA2004800254534 A CN A2004800254534A CN 200480025453 A CN200480025453 A CN 200480025453A CN 1846322 A CN1846322 A CN 1846322A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- oil
- precursor
- temperature
- secondary cell
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
Landscapes
- Battery Electrode And Active Subsutance (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
A carbon material for a secondary cell which is prepared by holding a specific petroleum-based heavy oil under a pressure of 2.0 MPa at a temperature of 400 to 600 DEG C for 3 hours or more, to thereby form a precursor of the carbon material, and subjecting the precursor to a heat treatment at 800 to 1500 DEG C; a precursor of the carbon material; and a nonaqueous electrolyte secondary cell which uses, as a negative electrode active material, the above carbon material or another preferable carbon material prepared by further subjecting the above carbon material to an oxidizing treatment in nitrogen, argon, or a mixed gas thereof containing an oxidizing gas or the in the atmosphere at 200 to 1000 DEG C. The nonaqueous electrolyte secondary cell uses a carbon material prepared from a petroleum-based heavy oil being available at a low cost, has a high capacity, and is excellent in cycle characteristics at a high temperature.
Description
Technical field
The present invention relates to nonaqueous electrolytic solution secondary battery, be used for the carbon material and the precursor thereof of this battery.
Background technology
In recent years, as mobile device with or electric power deposit power supply, be that the nonaqueous electrolytic solution secondary battery of representative is attracted attention with energy density and the high lithium rechargeable battery of output characteristic.Usually, this lithium rechargeable battery is mainly by constituting as the lithium-contained composite oxide of the material that is used to positive pole, the carbon material that conduct is used to the material of negative pole, the various carbonic ester series solvents that contain lithium salts that conduct is used to the material of electrolyte.
As the carbon material that is used to negative pole, but illustration native graphite, with the MCMB is the graphite of carbon source, is that charcoal fiber or vapor-grown carbon fibers are the graphite materials such as graphite fibre of carbon source with pitch, and low-temperature sintering charcoals such as difficult graphitized charcoal and easy graphitized charcoal.Wherein, as the negative electrode active material of portable set, mainly use the smooth graphite material of high power capacity and discharge potential with lithium rechargeable battery.
As mobile device with or electric power deposit when using lithium rechargeable battery with power supply, the capacity of monocell must count+more than the Ah, requiring negative electrode active material is to obtain the more material of high power capacity.In addition, from the capacity check consideration of monocell, wish that negative electrode active material is the higher relatively material of inclined degree of different with the graphite material discharge potentials corresponding to capacity of negative plates.In addition, during especially for mobile device, because the needs of refresh charging etc. require this material must be able to adapt to high output.In addition, require cycle life more than thousands of circulations.And, because the maximization of monocell is risen because of the Joule heat battery temperature when discharging and recharging.Therefore, require as mobile device with or the electric power deposit possess high-energy-density, high output characteristic with the lithium secondary battery of power supply, particularly require it to possess the excellent high-temperature cycle characteristics.
In order to satisfy these requirements, what be expected as optimal negative electrode active material is to be the low-temperature sintering charcoal of raw material with oil, coal or ethylene reaction groove residue etc., particularly the bigger easy graphitized charcoal of the inclination of discharge potential in bigger range of capacity.
In these raw materials, oil is the mink cell focus low price and can obtains in a large number, heat treatment by delayed coking equipment etc., cost that can be cheap makes carbon hexagonal wire side (graphite flake in a large number, graphene) by the unlimited extensively mutual stacked structure of van der waals force, promptly the layer structure of graphite flake (being designated hereinafter simply as the graphite flake structure) forms all right needle coke.But, in the past will be not necessarily abundant by the capacity of the oil secondary cell that to be the carbon material that obtains of needle coke use as negative electrode active material.Also do not find the carbon material that possesses the excellent high-temperature cycle characteristics.Therefore, oil is that needle coke can not use as the negative electrode active material of lithium rechargeable battery.
The announcement of invention
Problem of the present invention be stable provide will be by low-cost oil under the jumbo aforementioned nonaqueous electrolytic solution secondary battery, particularly high temperature of carbon material that obtain of mink cell focus as the negative electrode active material of nonaqueous electrolytic solution secondary battery, the good lithium rechargeable battery of cycle characteristics 45～60 ℃ time for example.In addition, problem of the present invention provides the carbon material that uses as the negative electrode active material of aforementioned nonaqueous electrolytic solution secondary battery or lithium rechargeable battery and the precursor of this carbon material.
The present inventor is that influence that the kind, heat-treat condition etc. of mink cell focus cause the characteristic of secondary cell that gained carbon material is used as negative electrode active material has been done at length the research back and found to oil, its characteristic depends on the heat-treat condition that kind that oil is a mink cell focus and aforementioned carbon material are experienced, air-distillation residue oil and/or fluid catalytic cracking residue oil as raw material, when heat-treating under given conditions, can be obtained big capacity.The present invention just is based on the invention that these discoveries are finished.
Promptly, the feedstock oil that the present invention relates to will to contain as principal component air-distillation residue oil and/or fluid catalytic cracking residue oil under the temperature of the pressure below the 2.0MPa and 400～600 ℃ keeps obtaining more than 3 hours the precursor of carbon material, under 800～1500 ℃ temperature this precursor is heat-treated then and the secondary cell carbon material that obtains.
In addition, the present inventor has also carried out systematically research to the various oxidation processes methods of the low-temperature sintering charcoal that uses as the negative electrode active material of lithium secondary battery, the result who passes through the sheet resistance that AC impedence method measures after the discharging and recharging of the negative pole that is made by the oxidation processes product is, the oxidation processes product are compared with the product of being untreated, and the sheet resistance of active material reduces.And, when oxidizing gas being used as oxidant, to compare with the product of being untreated with gas phase, the sheet resistance of active material further significantly reduces.
The present inventor has also used the cycle characteristics under 45 ℃ of two utmost point formula button cells (coin cell) of cobalt acid lithium to study to positive pole, found that oxidation processes has a significant impact cycle characteristics, particularly used the cycle characteristics of the oxidation processes product of oxidizing gas to be better than the product of being untreated.
The present invention is based on the invention that above-mentioned discovery is finished, that is, the above-mentioned precursor of the carbon material that uses as the negative electrode for lithium secondary battery active material of the present invention is preferably in 800～1500 ℃ and also carries out oxidation processes with oxidizing gas after heat-treating.This oxidation processes better be before the heat treatment step of making the carbon material and/or after, in containing the nitrogen of oxidizing gas, argon gas or their mist or in the atmosphere, the carbon materials of pulverizing are heat-treated in 200～1000 ℃.
Usually, carbon materials such as petroleum coke form oxygen containing functional groups such as carbonyl or hydroxyl by oxidation processes on carbon material surface, the functional group that forms be that the macromolecular compound (macromolecular solid surface) of reactant combines securely when discharging and recharging at the electrolyte solvent of negative electrode active material surface generation, on the other hand, the resistance height of the functional group that forms we can say that sheet resistance increases to some extent.Along with the increase of sheet resistance, the constricted flow of the electronics in the negative pole, consequently, the deterioration that causes circulating is serious.But, the oxidation processes product among the present invention, particularly the oxidation processes product that undertaken handling by oxidizing gas are compared with the product of being untreated, and its sheet resistance reduces.Therefore, can infer among the present invention and in fact not form functional group on the surface, the resistance components on surface disappears, and carbon occurs on the surface, and consequently, the mobile product of being untreated that are better than of the electronics in the negative pole are improved cycle characteristics.
In addition, the present invention relates to the nonaqueous electrolytic solution secondary battery of aforementioned carbon material as the negative electrode active material use.
The invention still further relates to that the feedstock oil that will contain air-distillation residue oil and/or fluid catalytic cracking residue oil under the temperature of the pressure below the 2.0MPa and 400～600 ℃ as principal component kept more than 3 hours and the precursor of the carbon material that is used to secondary cell that obtains.
The present invention be owing to will be that the carbon material that mink cell focus obtains uses as negative material by specific oil, so can provide the nonaqueous electrolytic solution secondary battery of high power capacity with cheap price and be used for the aforementioned carbon material and the precursor thereof of this nonaqueous electrolytic solution secondary battery.
In addition, the carbon material that passes through oxidation processes of the present invention is suitable as the good negative electrode for lithium secondary battery active material of high-temperature cycle and uses very much, helps realizing that mobile device is used or the high performance of electric power deposit usefulness lithium secondary battery.
The best mode that carries out an invention
Among the present invention, air-distillation residue oil and/or fluid catalytic cracking residue oil are used as raw material.Be more preferably the hydrodesulfurization oil that uses them.The air-distillation residue oil is that crude oil is carried out air-distillation and the residue oil that obtains.The hydrodesulfurization oil of air-distillation residue oil is directly the air-distillation residue oil to be carried out hydrodesulfurization (directly taking off) and the residue cut of acquisition.The fluid catalytic cracking residue oil typically refers to by making heavy light oil, decompression light oil, air-distillation residue oil contact slurry oil (slurry oil) or the clarified oil (decanted oil) that cracking generates the fluidized catalytic cracker by-product of gasoline fraction or light oil distillate at 430～550 ℃ with the powdery zeolite catalysts that flows.As the hydrodesulfurization oil of fluid catalytic cracking residue oil, can exemplify and utilize hydrodesulfurization unit aforementioned slurry oil or clarified oil to be handled and the sweet oil that obtains.In addition, utilize fluidized catalytic cracker to through the feedstock oil of hydrodesulfurization, for example the indirect desulfurization distillate oil, directly take off and distillate that wet goods is handled and the slurry oil or the clarification wet goods that obtain are also included within the hydrodesulfurization oil of fluid catalytic cracking residue oil.
In addition, when using the miscella of air-distillation residue oil and/or its hydrodesulfurization oil and fluid catalytic cracking residue oil and/or its hydrodesulfurization oil, the mixed proportion of air-distillation residue oil and/or its hydrodesulfurization oil is preferably in below the 60 capacity % (vol%), can obtain stable graphite flake layer structure.The mixed proportion that is more preferably air-distillation residue oil and/or its hydrodesulfurization oil is below 40 capacity %.
The raw material oil composition that utilizes above mixed to form better is that the aromatic hydrocarbons composition is that 40～95wt%, resinous principle are that 0.2～25wt%, carbon residue are 0.1～10wt%.Being more preferably the aromatic hydrocarbons composition is that 45～95wt%, resinous principle are that 0.5～20wt%, carbon residue are 0.2～8wt%.Further being more preferably the aromatic hydrocarbons composition is that 50～90wt%, resinous principle are that 1.0～15wt%, carbon residue are 0.5～5wt%.
As the raw material of coking process, the decompression residue oil also commonly used in the petroleum refinement field is if but adopt decompression residue oil or its hydrodesulfurization oil just can't obtain the precursor of desirable secondary cell with carbon material or this carbon material in the present invention.
The feedstock oil that will use for the precursor that obtains the carbon material under the temperature of the pressure below the 2.0MPa and 400～600 ℃ keeps more than 3 hours.Feedstock oil is generated when obtaining gas or light oils such as cracking naphtha and drippolene as the coke of secondary cell with the precursor of carbon material by thermal cracking during this.If exceed the scope of aforementioned pressure, temperature and retention time, then can't obtain the carbon material of stable graphite flake layer structure.Be preferably pressure 0.4～1.0MPa, 420～550 ℃ of temperature, retention time more than 20 hours.
For the precursor of making the carbon material can use various devices, as use the so-called bomb tube (tube bomb) of laboratory level, the delaying type coker can be used for stable and makes coke in large quantities, and the mini-reactor of delaying type coker (bench reactor) can be used for manufacturing scale between the two.
Bomb tube is the conventional equipment that uses in order to make needle coke with laboratory level, for example, Mochida etc., Chemistry and Physics of Carbon, 24, the thermal cracker of the mink cell focus of record in 111 (1994) is by the coke (being called as carbon material precursor here) of mink cell focus manufacturing cracked gas, cracked oil and comparison high-quality.This experimental provision be in iron jar, be packed into feedstock oil, be provided with exhaust channel at the top, by with this jar insertion and remain in the device of making coke in the sand bath through heating.In this bomb tube, can at random set reaction pressure, and reaction pressure can be kept certain by the Pressure gauge and the control valve of exhaust channel.In addition, reaction temperature is the design temperature of sand bath, and the reaction time, both also can at random set in order to insert the time till sand bath is extremely therefrom taken out.
If the reaction time (retention time) is different, then the characteristic of gained coke also can be slightly different.Here, will use as carbon material precursor of the present invention through the heat treated material more than 3 hours.
The delaying type coking plant is the thermal cracker of mink cell focus, is made the coke (being called as carbon material precursor here) of cracked gas, cracked oil and comparison high-quality by mink cell focus.Feedstock oil is sent into heating furnace continuously, is heated rapidly at short notice, is conducted to the bottom of coke drum again.In heat insulation coke drum, carry out carbonization, accumulated until filling up whole drum by the coke that liquid phase generates with suitable temperature and pressure.Cracking product (gas and cracked oil) is sent to rectifying column from the extraction of drum top and distills.The mink cell focus that extracts at the bottom of the tower is admitted to heating furnace once more with feedstock oil, repeats above-mentioned heat treatment.Coke drum has 2 usually, if 1 drum is filled up by coke, then feedstock oil is replaced and is conducted to another hollowing.After the drum cooling of being filled up, separating by coke, the coke of accumulating is removed by water under high pressure etc.
In the coke drum since coke (carbon material precursor) accumulate to the top from the drum bottom, so the coke on bottom and top the heat treatment time (retention time) of process different, the characteristic of the coke that is obtained by each position also slightly changes.Here, the carbon material precursor among the present invention adopts through the heat treated material more than 3 hours.Can be specific through the heat treated carbon material precursor more than 3 hours by being accumulated amount of coke (height of the coke of drum bottom beginning) and reaching the required time of this amount in coke drum.Specifically, remove, take out its following coke and use as carbon material precursor up to the drum bottom from accumulating the coke of the coke height before 3 hours when upper surface to the drum of the coke of coke drum is filled up the supply that stops feedstock oil by coke.
As mentioned above, as the proterties of the coke (carbon material precursor) that adopts bomb tube or delaying type coking plant etc. to obtain, better be that volatile ingredient is that the hydrogeneous rate of 2～20wt%, dry substrate is 1～6wt%.
The gained precursor utilizes sintering furnaces such as atmosphere kiln, shuttle kiln (shuttle kiln), rotary kiln, carries out the heat treatment to a few hours in tens of minutes in 800～1500 ℃, can obtain secondary cell of the present invention carbon material.As the proterties of gained carbon material, better be volatile ingredient below 2wt%, the brilliant footpath of c direction of principal axis is 5～50 .In addition, if the aforementioned hot treatment temperature less than 800 ℃, then because the layer structure of graphite flake is fine, thus the efficient of lithium occlusion release reaction can descend, so undesirable.If surpass 1500 ℃, though then the layer structure of graphite flake forms all rightly, reduce the occlusion position of lithium ions such as lattice defect, when being used for secondary cell, confirms the tendency that has capacity to reduce, so undesirable.Be preferably 800～1300 ℃.
Pulverize before more than the carbon material of Huo Deing is preferably in heat treatment in its manufacturing process and/or back, carries out oxidation processes with known method again.Oxidation processes preferably heats in the atmosphere of oxidizing gas and carries out.The atmospheric condition of the oxidizing gas in the oxidation processes is to be adjusted into the state that comprises oxidizing gas in nitrogen, argon gas or their inert mixed gas.As oxidizing gas, can adopt oxygen, ozone, oxides of nitrogen gas, carbon dioxide, steam etc. to have the gas of oxidizability.The concentration of oxidizing gas better is more than 3 capacity %.If less than 3 capacity %, then the oxidation reaction of carbon material powder surface is carried out insufficiently.
Oxidizing gas atmosphere can make concentration reach desirable oxidizing gas concentration to form by add oxidizing gas such as oxygen, ozone, carbon dioxide in inert gases such as nitrogen, argon gas.Consider that from cost and environment aspect oxidizing gas such as inert gas such as the alternative nitrogen of atmosphere (air) or oxygen are used, and perhaps directly it are used as oxidizing gas atmosphere.
Temperature conditions in the oxidation processes is preferably 200～1000 ℃.If treatment temperature is less than 200 ℃, then the oxidation reaction of carbon material powder surface is not fully carried out, and on the other hand, if surpass 1000 ℃, then the specific area of carbon material powder is excessive, can cause harmful effect to battery behavior, so undesirable.
Above gained carbon material be can be used for nonaqueous electrolytic solution secondary battery as the known positive active material and the nonaqueous electrolytic solution appropriate combination of formation such as negative electrode active material and lithium-contained composite oxide.Nonaqueous electrolytic solution and positive active material can adopt the material that is generally used for lithium secondary battery, are not particularly limited.
In addition, negative pole can make by known method.For example, pulverize above-mentioned carbon material, the gained powder is mixed with adhesive, add solvent, the mixture that forms paste-like or pasty state is coated the surface and the drying of collector bodies such as Copper Foil, make negative pole for the raising electrode density carries out compression molding as required again.
The result that the electrochemical behavior of lithium rechargeable battery that the so-called low sintering carbon material of above acquisition is used as negative electrode active material is studied in great detail is, the capacity of inferring to oil be the kind of mink cell focus and heat-treat condition dependence by lithium ion to low-temperature sintering and the diffusion based on the layer structure inside of graphite flake structure of carbon material cause.Compare with difficult graphitized charcoal that to be the easy graphitized charcoal of raw material or carbon source with the coal obtain with oxidant thermal crackings such as nitric acid etc., with oil is that mink cell focus is that the occlusion position of the lithium ion in the easy graphitized charcoal of raw material is less, but the directionality height of the layer structure of graphite flake.Therefore, infer easy initiation lithium ion, compare, can at high speed the lithium ion occlusion be gone into the occlusion position of lithium ion with other material from the diffusion of carbon surface to negative electrode active material inside.Consequently, need not, the negative electricity potential drop is being proceeded charging to decide voltage again to the reduction potential of lithium for negative pole is completely charged as difficult graphitized charcoal.Along with the decline lithium of negative pole current potential by occlusion, realize full charging when reaching the reduction potential of lithium.The such lithium ion easily graphite flake layer structure of diffusion depends on material factor and heat-treat conditions such as C/H ratio that oil is the heavy carburetion, the degree of polymerization.
Below, the present invention will be described in more detail based on embodiment, but the present invention is not limited in described embodiment.
Embodiment 1
Adopt bomb tube, the miscella that uses air-distillation residue oil and fluid catalytic cracking residue oil to form as feedstock oil with 60: 40 mixed, the precursor of the pressure by this miscella being remained in about 0.5MPa and about 500 ℃ temperature acquisition in following 40 hours carbon material.This precursor heated up 16 hours with the programming rate of 0.6 ℃ of per minute in shuttle kiln, and heating up with the programming rate of 1.0 ℃ of per minutes makes that temperature reaches 900 ℃ in the stove again, keeps putting naturally after 1 hour being chilled to room temperature, makes the carbon material.With injector-type mill this carbon material is pulverized, carried out classification by gas flow sizing machine and obtain carbon material powder.
Then, make negative pole according to following step.To gather inclined to one side vinylidene fluoride powder 0.3g and be dissolved in N-N-methyl-2-2-pyrrolidone N-2.7cc, and add aforementioned carbon material powder 3.0g and mix, obtain slurry, and this slurry is coated be made its drying on the Copper Foil (dry back coating weight is 10mg/cm
2, coating thickness 100 μ m).With its stamping-out is the discoid of diameter 12.5mm, with 1T/cm
2The pressurized treatments of carrying out 10 seconds obtains negative pole.
Adopt the above negative pole that obtains, and use the lithium metal, use ethylene carbonate (EC): dimethyl carbonate (DMC)=1: 1 1M-LiClO as to electrode and reference electrode
4As electrolyte, charge-discharge characteristic is assessed.Charge condition is with 1mA/cm
2Constant-current charge to the current potential of 0V, discharging condition is with 1mA/cm
2Constant-current discharge to the current potential of 1.5V.It the results are shown in table 1.
Embodiment 2
Except use the miscella that air-distillation residue oil and fluid catalytic cracking residue oil form with 30: 70 mixed as feedstock oil, other obtains the powder of carbon material similarly to Example 1, makes negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Embodiment 3
Except using the fluid catalytic cracking residue oil as feedstock oil, other obtains the powder of carbon material similarly to Example 1, makes negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Embodiment 4
Except the miscella that uses air-distillation residue oil and fluid catalytic cracking residue oil to form as feedstock oil with 20: 80 mixed, the retention time that obtains carbon material precursor is 60 hours, thereafter the heat treatment temperature to this precursor is outside 1100 ℃, other similarly to Example 1, obtain the powder of carbon material, make negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Embodiment 5
Except the miscella that uses air-distillation residue oil and fluid catalytic cracking residue oil to form as feedstock oil with 40: 60 mixed, the retention time that obtains carbon material precursor is 20 hours, thereafter the heat treatment temperature to this precursor is outside 800 ℃, other similarly to Example 1, obtain the powder of carbon material, make negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Table 1
| The feedstock oil composite rate *1 (vol％) | Retention time *2 (hr) | Heat treatment temperature *3 (℃) | Charging capacity (mAh/g) | Discharge capacity (mAh/g) | |||
| A | B | C | |||||
| Embodiment 1 | 60 | 40 | 0 | 40 | 900 | 350 | 258 |
| Embodiment 2 | 30 | 70 | 0 | 40 | 900 | 343 | 259 |
| Embodiment 3 | 0 | 100 | 0 | 40 | 900 | 345 | 268 |
| Embodiment 4 | 20 | 80 | 0 | 60 | 1100 | 310 | 251 |
| Embodiment 5 | 40 | 60 | 0 | 20 | 800 | 410 | 280 |
| Comparative example 1 | 0 | 0 | 100 | 30 | 900 | 350 | 234 |
| Comparative example 2 | (tar: 100%) | 30 | 900 | 320 | 229 | ||
| Comparative example 3 | 30 | 70 | 0 | 30 | 1550 | 240 | 195 |
| Comparative example 4 | 30 | 70 | 0 | 2 | 900 | 319 | 237 |
* 1 A: air-distillation residue oil, B: fluid catalytic cracking residue oil, C: decompression distillation residue oil
* 2 retention times that obtain carbon material precursors
* the heat treatment temperature of 3 carbon material precursors
Comparative example 1
Adopt bomb tube, use decompression distillation residue oil (containing its hydrodesulfurization oil), by under the pressure of about 0.5MPa and about 500 ℃ temperature, keeping the precursor of acquisition carbon material 30 hours as feedstock oil.This precursor heated up 16 hours with the programming rate of 0.6 ℃ of per minute in shuttle kiln, and heating up with the programming rate of 1.0 ℃ of per minutes makes that temperature reaches 900 ℃ in the stove again, keeps heat-treating in 1 hour then putting naturally being chilled to room temperature, makes the carbon material.With injector-type mill this carbon material is pulverized, carried out classification by gas flow sizing machine and obtain carbon material powder.
Then, make negative pole according to following step.To gather inclined to one side vinylidene fluoride powder 0.3g and be dissolved in N-N-methyl-2-2-pyrrolidone N-2.7cc, and add aforementioned carbon material powder 3.0g and mix, obtain slurry, and this slurry is coated be made its drying on the Copper Foil (dry back coating weight is 10mg/cm
2, coating thickness 100 μ m).With its stamping-out is the discoid of diameter 12.5mm, with 1T/cm
2The pressurized treatments of carrying out 10 seconds obtains negative pole.
Adopt the above negative pole that obtains, and use the lithium metal, use EC: DMC=1: 1 1M-LiClO as to electrode and reference electrode
4As electrolyte, charge-discharge characteristic is assessed.Charge condition is with 1mA/cm
2Constant-current charge to the current potential of 0V, discharging condition is with 1mA/cm
2Constant-current discharge to the current potential of 1.5V.It the results are shown in table 1.
Comparative example 2
Except using the tar as feedstock oil, other obtains the powder of carbon material similarly to Example 1, makes negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Comparative example 3
Except the miscella that uses air-distillation residue oil and fluid catalytic cracking residue oil to form as feedstock oil with 30: 70 mixed, the retention time that obtains carbon material precursor is 30 hours, thereafter the heat treatment temperature to this precursor is outside 1550 ℃, other similarly to Example 1, obtain the powder of carbon material, make negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Comparative example 4
Except the miscella that uses air-distillation residue oil and fluid catalytic cracking residue oil to form as feedstock oil with 30: 70 mixed, the retention time that obtains carbon material precursor is outside 2 hours, and other obtains the powder of carbon material similarly to Example 1, make negative pole, the assessment charge-discharge characteristic.It the results are shown in table 1.
Embodiment 6
Adopt bomb tube, the miscella that uses air-distillation residue oil and fluid catalytic cracking residue oil to form with 60: 40 mixed as feedstock oil is by maintenance under the pressure of about 0.5MPa and about 500 ℃ temperature 40 hours, the precursor of acquisition carbon material.Pulverize this precursor with injector-type mill, carry out classification, obtain the powder of carbon material precursor by gas flow sizing machine.
The powder of this precursor heated up 16 hours with the programming rate of 0.6 ℃ of per minute in shuttle kiln, and heating up with the programming rate of 1.0 ℃ of per minutes makes that temperature reaches 1100 ℃ in the stove again, keeps heat-treating in 1 hour then putting naturally being chilled to room temperature, makes the carbon material.
(oxygen 20 capacity %, flow 3L/min) is warming up to 800 ℃ with the programming rate of 200 ℃/hr with gained carbon material powder under the airflow of mixed gas of oxygen and nitrogen, and in 800 ℃ of oxidation processes of carrying out 1 hour, the yield after the oxidation processes is about 90%.
Then, make negative pole according to following step.To gather inclined to one side vinylidene fluoride powder 0.3g and be dissolved in N-N-methyl-2-2-pyrrolidone N-2.7cc, and add aforementioned carbon material powder 3.0g and mix, obtain slurry, and this slurry is coated be made its drying on the Copper Foil (dry back coating weight is 10mg/cm
2, coating thickness 100 μ m).With its stamping-out is the discoid of diameter 12.5mm, with 1T/cm
2The pressurized treatments of carrying out 10 seconds obtains negative pole.The thick 30 μ m that are about of the electrode of gained negative pole, electrode density is 1.2g/cm
3, active material weight is about 3mg/cm
2
On the other hand, be positive active material with cobalt acid lithium, with acetylene black electric conducting material, by the method making positive pole same with negative pole.The anodal thick 35 μ m that are about of electrode, electrode density is 2.7g/cm
3, active material weight is about 8mg/cm
2
Make electrolyte (EC: DMC=1: 1 1M-LiPF
6) contain and be dipped in positive pole and negative pole, polyethylene system multiple aperture plasma membrane is clipped in two interpolars, be assembled into button cell (CR2032).
At 25 ℃, charging: about 0.3mA 4.2V 10 hours, discharge: under the condition of about 0.3mA 2.5V to discharging and recharging that this button cell carries out circulating for 1 time.Then, at 45 ℃, charging: about 2mA 4.2V 2 hours, discharge: that carries out under the condition of about 2mA 2.5V circulating for 50 times discharges and recharges.Try to achieve the ratio (45 ℃ of cycle characteristicss) of the discharge capacity and the discharge capacity that the 50th time circulates of the 1st circulation under 45 ℃.It the results are shown in table 2.
Embodiment 7
Except the sintering temperature of carbon material precursor powder in shuttle kiln is 800 ℃, other assesses 45 ℃ of cycle characteristicss similarly to Example 6.The results are shown in table 2.
Embodiment 8
Under air draught (flow 5L/min), with 200 ℃/hr of programming rate the carbon material powder that embodiment 4 obtains is warming up to 800 ℃, in 800 ℃ of heat treatments of carrying out 1 hour.
Similarly to Example 6, the oxidation processes product are carried out the assessment of 45 ℃ of cycle characteristicss.The results are shown in table 2.
Embodiment 9
Except the oxidation processes condition for being warming up to 600 ℃ at (flow 5L/min) under the air draught, with 200 ℃/hr of programming rate, carrying out 1 hour the heat treatment in 600 ℃, other assesses 45 ℃ of cycle characteristicss similarly to Example 6.The results are shown in table 2.
Embodiment 10
The carbon material precursor of embodiment 4 acquisitions is ground into the particle of average grain diameter 35 μ m with pulverizer.(3L/min) is warming up to 1100 ℃ with the programming rate of 200 ℃/hr under nitrogen current, in 1100 ℃ of roastings of carrying out 1 hour.Yield after the roasting is 94%, almost finds no agglutinator.With injector-type mill sinter is carried out pulverizing for the 2nd time (pulverizing) again and make its average grain diameter reach 19 μ m, carry out classification with gas flow sizing machine again.Then, carry out oxidation processes similarly to Example 6, assess 45 ℃ of cycle characteristicss.The results are shown in table 2.
Comparative example 5
Except using the carbon material powder of embodiment 6, but do not carry out outside its oxidation processes, other operation with embodiment 6 is identical, modulates carbon material powder, makes lithium secondary battery then, measures its cycle characteristics.The results are shown in table 2.
Table 2
| 45 ℃ of cycle characteristicss (%) | |
| Embodiment 6 | 72 |
| Embodiment 7 | 73 |
| Embodiment 8 | 68 |
| Embodiment 9 | 70 |
| Embodiment 10 | 72 |
| Comparative example 5 | 54 |
The possibility of utilizing on the industry
The present invention will be used as negative material by the carbon material that specific petroleum-derived heavy oil obtains, so the nonaqueous electrolytic solution secondary battery of high power capacity can be provided with low cost. Particularly used the lithium secondary battery of aforementioned carbon material owing to possess good high-temperature cycle, mobile device is used or electric power storage stand-by power supply uses so be suitable as.
Claims (5)
1. secondary cell carbon material, it is characterized in that, the feedstock oil that will contain air-distillation residue oil and/or fluid catalytic cracking residue oil under the temperature of the pressure below the 2.0MPa and 400～600 ℃ as principal component keeps obtaining more than 3 hours the precursor of carbon material, under 800～1500 ℃ temperature this precursor is heat-treated and is obtained then.
2. secondary cell carbon material as claimed in claim 1, its feature also is, also the carbon material is carried out oxidation processes.
3. secondary cell carbon material as claimed in claim 2, its feature are that also oxidation processes is meant in containing the nitrogen of oxidizing gas, argon gas or their mist or in the atmosphere, heat-treats in 200～1000 ℃.
4. nonaqueous electrolytic solution secondary battery is characterized in that, has used in the claim 1～3 each described carbon material as negative electrode active material.
5. the precursor of carbon material is characterized in that, the feedstock oil that will contain air-distillation residue oil and/or fluid catalytic cracking residue oil under the temperature of the pressure below the 2.0MPa and 400～600 ℃ as principal component keeps more than 3 hours and obtains.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP316751/2003 | 2003-09-09 | ||
| JP2003316751 | 2003-09-09 | ||
| JP065411/2004 | 2004-03-09 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1846322A true CN1846322A (en) | 2006-10-11 |
Family
ID=37064668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2004800254534A Pending CN1846322A (en) | 2003-09-09 | 2004-08-05 | Nonaqueous electrolyte secondary cell, carbon material for use therein, and precursor of said carbon material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1846322A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707246B (en) * | 2009-04-03 | 2011-12-21 | 湖州创亚动力电池材料有限公司 | Method for preparing carbon cathode material of lithium ion battery, carbon cathode material and lithium ion battery |
| CN102959771A (en) * | 2010-06-30 | 2013-03-06 | 吉坤日矿日石能源株式会社 | Stock oil composition for carbonaceous material for negative electrodes of lithium-ion secondary batteries |
| CN103361097A (en) * | 2012-03-30 | 2013-10-23 | 韩国化学研究院 | Pitch manufactured from petrochemical coproduct and high-yield manufacturing method thereof, and high-performance carbon negative electrode material utilizing the same |
| CN104766952A (en) * | 2015-04-21 | 2015-07-08 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing lithium ion battery cathode material by utilizing biomass gasification furnace filter residue |
| CN104956528A (en) * | 2013-02-19 | 2015-09-30 | 株式会社吴羽 | Carbon material for non-aqueous electrolyte secondary battery negative electrode |
| US10573891B2 (en) | 2012-08-30 | 2020-02-25 | Kuraray Co., Ltd. | Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery |
-
2004
- 2004-08-05 CN CNA2004800254534A patent/CN1846322A/en active Pending
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101707246B (en) * | 2009-04-03 | 2011-12-21 | 湖州创亚动力电池材料有限公司 | Method for preparing carbon cathode material of lithium ion battery, carbon cathode material and lithium ion battery |
| CN102959771A (en) * | 2010-06-30 | 2013-03-06 | 吉坤日矿日石能源株式会社 | Stock oil composition for carbonaceous material for negative electrodes of lithium-ion secondary batteries |
| CN102959771B (en) * | 2010-06-30 | 2015-11-25 | 吉坤日矿日石能源株式会社 | The raw oil composition of lithium ion secondary battery negative pole material with carbon element |
| EP2590247A4 (en) * | 2010-06-30 | 2016-11-02 | Jx Nippon Oil & Energy Corp | Stock oil composition for carbonaceous material for negative electrodes of lithium-ion secondary batteries |
| CN103361097A (en) * | 2012-03-30 | 2013-10-23 | 韩国化学研究院 | Pitch manufactured from petrochemical coproduct and high-yield manufacturing method thereof, and high-performance carbon negative electrode material utilizing the same |
| US10573891B2 (en) | 2012-08-30 | 2020-02-25 | Kuraray Co., Ltd. | Carbon material for nonaqueous electrolyte secondary battery and method for manufacturing same, and negative electrode using carbon material and nonaqueous electrolyte secondary battery |
| CN104956528A (en) * | 2013-02-19 | 2015-09-30 | 株式会社吴羽 | Carbon material for non-aqueous electrolyte secondary battery negative electrode |
| US10504635B2 (en) | 2013-02-19 | 2019-12-10 | Kuraray Co., Ltd. | Carbonaceous material for nonaqueous electrolyte secondary battery negative electrode |
| CN104766952A (en) * | 2015-04-21 | 2015-07-08 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing lithium ion battery cathode material by utilizing biomass gasification furnace filter residue |
| CN104766952B (en) * | 2015-04-21 | 2017-01-25 | 武汉凯迪工程技术研究总院有限公司 | Method for preparing lithium ion battery cathode material by utilizing biomass gasification furnace filter residue |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101855757B (en) | Nonaqueous lithium-type storage element | |
| CN107993853B (en) | A kind of negative electrode material that soft or hard carbon is compound, preparation method and the capacitor comprising the negative electrode material | |
| EP3670475A1 (en) | Method for producing negative electrode active material for lithium secondary battery, and lithium secondary battery including same | |
| CN107579249B (en) | Hard carbon negative electrode material prepared from traditional Chinese medicine residues and preparation method thereof | |
| JP2020516570A (en) | Activated carbon manufacturing method | |
| JP2016509739A (en) | Negative electrode active material for secondary battery, conductive composition for secondary battery, negative electrode material including the same, negative electrode structure and secondary battery including the same, and manufacturing method thereof | |
| CN108807876B (en) | Preparation method of modified carbon negative electrode material for lithium ion battery | |
| CN1906780A (en) | Negative electrode for lithium secondary battery and lithium secondary battery | |
| EP3358656A1 (en) | Carbonaceous material for negative electrode of nonaqueous-electrolyte secondary battery, and process for producing same | |
| JP2007179879A (en) | Manufacturing method of negative electrode material for lithium-ion secondary battery | |
| KR101433720B1 (en) | The method for manufacturing the hard carbon and the hard carbon manufactured thereby | |
| CN109319758B (en) | Co-production process method of mesocarbon microbeads and negative electrode material coke | |
| CN107093711A (en) | Monodispersed SiOxThe magnanimity preparation method of C complex microspheres | |
| JP4488523B2 (en) | Non-aqueous electrolyte secondary battery, carbon material used therefor, and precursor of the carbon material | |
| CN103325997A (en) | Carbon material applied to negative electrode of lithium ion power battery and preparation method of carbon material | |
| CN102640330B (en) | Negative electrode for secondary battery, and secondary battery using same | |
| KR101790699B1 (en) | Method for synthesis of anode material using active carbon and pitch prepared by chemical activation | |
| CN1846322A (en) | Nonaqueous electrolyte secondary cell, carbon material for use therein, and precursor of said carbon material | |
| JP2008204758A (en) | Negative electrode material for lithium ion secondary battery, and its manufacturing method | |
| CN1136624C (en) | Chargeable lithium battery | |
| CN107879343A (en) | A kind of preparation method of super capacitor carbon | |
| JP4234356B2 (en) | Method for producing negative electrode material | |
| CN108199026B (en) | Preparation method of power battery cathode material and cathode material prepared by same | |
| CN1175098A (en) | Accumulator with no water electrolytic solution | |
| JP2006252817A (en) | Nonaqueous electrolyte secondary battery and carbon material used in it |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |