CN102569753A - Carbon negative electrode material for lithium-ion secondary battery for power application and preparation method thereof - Google Patents
Carbon negative electrode material for lithium-ion secondary battery for power application and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a carbon negative electrode material for a lithium-ion secondary battery for power application. The carbon negative electrode material is prepared by dissolving artificial graphite powder and resin in an organic solvent, carrying out liquid-phase dehydration in a pressure container, coating for modification, carrying out low-temperature solidification, carbonizing, carrying out high-temperature thermal treatment, cooling, and screening, wherein the artificial graphite powder has a particle size of 6 to 30 mum, and a specific surface area of 6m<2>/g or less. The prepared modified carbon material has a spherical or ellipsoidal shape, and has an average particle size D50 of 0.5 to 30 mum, a tap density of 0.5 to 1.5g/cc, a BET (Brunauer-Emmett-Teller) specific surface area of 0.5 to 5.0m<2>/g and a true density of 0.8 to 2.25g/cc; and the modified carbon material has a large amount of nano-pores therein with a pore size of 0.1 to 0.6nm. The modified carbon material provided by the invention improves specific volumetric capacity and initial coulombic efficiency and lowers specific surface area, thereby eliminating the disadvantage of reversible capacity loss caused by hard carbon material pyrolysis sensitive to air, and improving the material processing performance. The modified carbon material is suitable for the lithium-ion secondary battery for power application.
Description
Technical field
The present invention relates to raw material of wood-charcoal material of a kind of lithium ion secondary battery negative pole that is used to provide power resources and preparation method thereof.
Background technology
At present; Along with developing rapidly of international new forms of energy new material; Being widely used and high speed development of various New-energy electric vehicles and portable electric appts, electric tool; The requirement of chemical power source is also improved in succession, and lithium ion battery is the more successful a kind of portable chemical power supply of exploitation at present, and it has, and voltage height, specific energy are big, discharging voltage balance, cryogenic property is good, security performance is excellent and advantages such as easy storage and long working life.Yet extensive use, electronics miniaturization and the microminiaturized degree of current electric automobile are increasingly high, and be also more deep with application to the research of lithium ion battery.
At present, negative material adopts graphite material mostly in the commercial lithium ion battery, its advantage be have higher specific capacity (＜372mAh/g), low electrode potential (＜1.0Vvs.Li
+/ Li), high efficient first, long cycle life.Graphite material again because of its kind, preparation method and heat treatment temperature not simultaneously, can cause the difference on the The Nomenclature Composition and Structure of Complexes, and then cause the difference of embedding behavior and performance.
Graphite is divided into Delanium and native graphite again, and that Delanium has is good with the electrolyte compatibility, its embedding, to take off speed bigger, and load character etc. is preferably arranged.It promptly is the steady phase spherical carbon of Jie that raw material is processed with pitch that PANASONIC has adopted graphited asphalt carbon microballoon, is called for short MCMB.But the volume and capacity ratio that it is low and first efficient be still waiting to improve.Native graphite is current comparatively ideal negative material, has that cost is low, capacity is higher and characteristics such as compaction capacity is good, has just adopted native graphite like SANYO GS company.Shortcoming is that they are relatively more responsive to some electrolyte, receives the restriction of theoretical lithium storage content again, is difficult to increase substantially very much through improving battery preparation technique merely.
Therefore, have the novel negative material of higher capacity and Development of New Generation, become the hot subject in the Study on Li-ion batteries using field.Once, alloy material once had been the first-selection that people study, but its low efficient first and high bulk effect cause relatively poor cyclical stability to fail to be well solved always; Tin-oxide reversible capacity like the preparation of employing CVD methods such as Hironorid reaches 600mAh/g; But its irreversible capacity reaches 800mAh/g [J.PowerSo μ rces, 2001,97-98:229] especially; Efficient is obviously on the low side first, its drawbacks limit its application in lithium ion battery.The compound system of the silicon grain outerwrap amorphous carbon layer of the subordinate's of Hitachi MAXwell company preparation, though improved the structure and the electric conductivity of silicon materials, because its technical process is restive, uncertain factor is many, causes being difficult to realize producing in batches.Reported negative material among the Chinese invention patent CN01807830.3 through the hard charcoal preparation of pyrolysis; Because of modifying on its surface; Irreversible capacity is quite high, causes the high reason of irreversible capacity except electrode solution is decomposed to form passivating film, the various active groups such as the hydroxyl of material surface; With and the moisture of absorption also be the main cause that forms irreversible capacity, though hydroxyl and moisture have been eliminated when pyrolysis; Because in the assembling and use of battery, if electrode contacts with various active gasess, like CO
2, O
2, also can strengthen irreversible reaction and lose reversible capacity, this also is the reason of commercialization pyrolyzed carbon materials to air-sensitive.
Summary of the invention
Thereby the technical problem that the present invention solved provide a kind of improved volume and capacity ratio and first efficient, reduced specific area and eliminated pyrolytic hard carbon material and air-sensitive lost the defective of reversible capacity, also improved carbon cathode material and its preparation method that the power of drawing abillity is suitable for lithium rechargeable battery simultaneously.
In order to achieve the above object; The technical scheme that the present invention adopts is: a kind of power is with lithium ion secondary battery negative pole raw material of wood-charcoal material; It is to be raw material with graphous graphite powder and resin; Be dissolved in and in pressure vessel, carry out liquid-phase dehydration behind the organic solvent again and handle, then through coating modification, low-temperature setting, charing, after high-temperature heat treatment, cooling process after screening; Its carbon modified material of processing is sphere or elliposoidal, and average grain diameter D50 is 0.5～30 μ m, and tap density is between 0.5～1.5g/cc, and the BET specific area is at 0.5～5.0m
2Between/the g, real density 0.8～2.25g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm; The particle diameter of wherein said graphous graphite powder is 6～30 μ m, and specific area is smaller or equal to 6m
2/ g; Said resin is furane resins, Lauxite, phenolic resins, epoxy resin, polymethyl methacrylate, Kynoar or polyacrylonitrile.Said organic solvent is the organic solvent that can dissolve petroleum coke or coal tar, can be benzene, toluene, ethylbenzene, xylenes, cycloalkanes, benzinum, quinoline, thiophene or carbon disulfide.The preferred carbon disulfide of the present invention.The resin that is adopted among the present invention is the coating modification material, and it in the end accounts for the 5wt%～20wt% of total carbon modified material in the product.Preferably be not more than 18wt%.
Charcoal preparation methods of the present invention, its step is following:
1. get the raw materials ready: with graphous graphite powder and resin by weight 5～20: 1 ratio, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent, alternately to join while stirring in the pressure vessel, continue to stir 2～4 hours, then in 10～30 minutes, add the reaction promoter of total weight 3%～15%;
3. heat up: the heating that heats up then, in 7～9 hours, temperature is raised to 400～600 ℃; The negative pressure that wherein heats up 2～3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 400～600 ℃, 4～9 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature carries out graphitization processing for 2600～3000 ℃;
Wherein, 6. 5. 4. 3. said step all carry out under anti-oxidation environment.
Above-mentioned preparation method, described anti-oxidation environment is to extract in negative pressure to feed inert gas or hydrogen under the state.Said inert gas is a nitrogen, and its flow is 0.5～2m
3/ h.
Above-mentioned preparation method, said reaction promoter is cycloalkane and/or aromatic solvent.Said aromatic solvent be selected from fear oil and washing oil in any.
Carbon modified material provided by the invention can be widely used in the ion secondary battery cathode material lithium.The present invention adopts the coating modification technology to overcome the shortcoming of existing pyrolytic hard carbon material; Compare with common raw material of wood-charcoal material; Volume and capacity ratio and efficient have first been improved; Reduce specific area, so not only eliminated pyrolytic hard carbon material air-sensitive is lost reversible capacity, also improved drawing abillity.The maximum characteristics of the present invention simultaneously are that its preparation technology's flow process is simple, and process is easy to control, and cost of manufacture is low; Environmentally friendly etc.; This material can not only satisfy the demand of high magnification capacity, can stop to overcharge and cross to put, reversible capacity and first efficient all be significantly improved; In lithium ion battery applications, open up new way, be fit to commercial exploitation.
Description of drawings
Fig. 1 is that carbon modified material in the embodiment of the invention 1 is as the first charge-discharge curve of lithium ion battery negative material;
Fig. 2 is that carbon modified material in the embodiment of the invention 2 is as the first charge-discharge curve of lithium ion battery negative material;
Fig. 3 is that carbon modified material in the embodiment of the invention 6 is as the first charge-discharge curve of lithium ion battery negative material.
Embodiment
For further specifying the present invention, specify in conjunction with following examples:
Embodiment 1:
1. get the raw materials ready: take by weighing graphous graphite powder (the clean stone carbon materials in Baofeng County, Henan Province Co., Ltd) 150g and epoxy resin 10g, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent carbon disulfide, alternately to join while stirring in the pressure vessel, continue to stir 3 hours, then in 20 minutes, add the oil of fearing of total weight 9%;
3. heat up: the heating that heats up then, in 8 hours, temperature is raised to 500 ℃ and carries out surface modification treatment; The negative pressure that wherein heats up 3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 500 ℃, 7 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature is 3000 ℃, carried out graphitization processing in 24 hours after, natural cooling.The powder that obtains is crossed 200 mesh sieves, and the powder behind the sieve is modification powdered carbon sample;
Feeding nitrogen or hydrogen are protected in the above-mentioned heat treatment process, also can feed other inert gas such as argon gas or its mist.
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 20 μ m, and tap density is about 1.0g/cc, and the BET specific area is at 2.0m
2About/g, about real density 1.25g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
Take by weighing active material modification powdered carbon and binding agent Kynoar in 94: 6 ratio (mass ratio) again; It is dissolved in dimethyl pyrrolidone; Stir repeatedly, again active material is coated on the copper mesh equably vacuumize 12h after binding agent and powdered carbon are mixed; Last compressing tablet, weighing require the electrode slice quality at 10～15mg.Electrochemical property test adopts the Experimental cell of two electrode structures, and negative material is a carbon powder material, lithium sheet just very, and the copper pool is collector; Electrolyte is 1mol/LLiClO
4The solution of/ethylene carbonate (EC)+diethyl carbonate (DEC); Barrier film is Celgard2400.Battery is lower than in 5% the dry glove box assembling in relative humidity to be accomplished.When requirement discharged and recharged, still in drying box, measuring current density was 0.1mA/cm to battery model
2, the charging cut-ff voltage is 2.00V, discharge cut-off voltage is 0.001V.
The discharge capacity first of this material is 361.8mAh/g, and first charge-discharge efficiency is 94.7%.
Embodiment 2:
1. get the raw materials ready: take by weighing graphous graphite powder 120g and Lauxite 12g, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent carbon disulfide, alternately to join while stirring in the pressure vessel, continue to stir 2 hours, then in 10 minutes, add the oil of fearing of total weight 3%;
3. heat up: the heating that heats up then, in 7 hours, temperature is raised to 400 ℃ and carries out surface modification treatment; The negative pressure that wherein heats up 2 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 400 ℃, 6 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature is 2800 ℃, carried out graphitization processing in 48 hours after, natural cooling.The powder that obtains is crossed 200 mesh sieves, and the powder behind the sieve is modification powdered carbon sample;
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 30 μ m, and tap density is about 1.5g/cc, and the BET specific area is at 5.0m
2About/g, about real density 2.25g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
Feeding nitrogen or hydrogen are protected in the above-mentioned heat treatment process, also can feed other inert gas such as argon gas or its mist.
Other part of present embodiment and embodiment 1 are identical.
The discharge capacity first of this material is 354.9mAh/g, and first charge-discharge efficiency is 93.5%.
Embodiment 3:
1. get the raw materials ready: take by weighing graphous graphite powder 100g and phenolic resins 15g, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent-benzene, alternately to join while stirring in the pressure vessel, continue to stir 4 hours, then in 30 minutes, add the washing oil of total weight 10%;
3. heat up: the heating that heats up then, in 9 hours, temperature is raised to 600 ℃ and carries out surface modification treatment; The negative pressure that wherein heats up 3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 600 ℃, 8 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature is 2900 ℃, carried out graphitization processing in 48 hours after, natural cooling.The powder that obtains is crossed 200 mesh sieves, and the powder behind the sieve is modification powdered carbon sample;
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 10 μ m, and tap density is about 1.2g/cc, and the BET specific area is at 3.0m
2About/g, about real density 1.85g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
Feeding nitrogen or hydrogen are protected in the above-mentioned heat treatment process, also can feed other inert gas such as argon gas or its mist.
Other part of present embodiment and embodiment 1 are identical.
Detection learns that the discharge capacity first of this material is 359.3mAh/g, and first charge-discharge efficiency is 94.5%.
Embodiment 4:
1. get the raw materials ready: take by weighing graphous graphite powder 130g and furane resins 15g, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent-benzene xylenes, alternately to join while stirring in the pressure vessel, continue to stir 4 hours, then in 30 minutes, add the washing oil of total weight 9%;
3. heat up: the heating that heats up then, in 9 hours, temperature is raised to 600 ℃ and carries out surface modification treatment; The negative pressure that wherein heats up 3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 600 ℃, 8 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature is 2900 ℃, carried out graphitization processing in 48 hours after, natural cooling.The powder that obtains is crossed 200 mesh sieves, and the powder behind the sieve is modification powdered carbon sample;
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 1 μ m, and tap density is about 0.5g/cc, and the BET specific area is at 0.5m
2About/g, about real density 0.8g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
Feeding nitrogen or hydrogen are protected in the above-mentioned heat treatment process, also can feed other inert gas such as argon gas or its mist.
Other part of present embodiment and embodiment 1 are identical.
The discharge capacity first of this material is 366.7mAh/g, and first charge-discharge efficiency is 94.1%
Embodiment 5:
1. get the raw materials ready: take by weighing graphous graphite powder 110g and polymethyl methacrylate 8g, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent quinoline, alternately to join while stirring in the pressure vessel, continue to stir 2 hours, then in 10 minutes, add the washing oil of total weight 5%;
3. heat up: the heating that heats up then, in 7 hours, temperature is raised to 450 ℃ and carries out surface modification treatment; The negative pressure that wherein heats up 3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 450 ℃, 5 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature is 2600 ℃, carried out graphitization processing in 60 hours after, natural cooling.The powder that obtains is crossed 200 mesh sieves, and the powder behind the sieve is modification powdered carbon sample;
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 5 μ m, and tap density is about 0.8g/cc, and the BET specific area is at 1.5m
2About/g, about real density 1.0g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
Feeding nitrogen or hydrogen are protected in the above-mentioned heat treatment process, also can feed other inert gas such as argon gas or its mist.
Other part of present embodiment and embodiment 1 are identical.
The discharge capacity first of this material is 364.7mAh/g, and first charge-discharge efficiency is 93.2%
Embodiment 6:
1. get the raw materials ready: take by weighing graphous graphite powder 80g and polyacrylonitrile 12g, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent carbon disulfide, alternately to join while stirring in the pressure vessel, continue to stir 3 hours, then in 20 minutes, add the washing oil of total weight 4%;
3. heat up: the heating that heats up then, in 7 hours, temperature is raised to 550 ℃ and carries out surface modification treatment; The negative pressure that wherein heats up 3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 550 ℃, 8 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature is 2700 ℃, carried out graphitization processing in 48 hours after, natural cooling.The powder that obtains is crossed 200 mesh sieves, and the powder behind the sieve is modification powdered carbon sample;
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 15 μ m, and tap density is about 1.0g/cc, and the BET specific area is at 2.5m
2About/g, about real density 1.5g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
Feeding nitrogen or hydrogen are protected in the above-mentioned heat treatment process, also can feed other inert gas such as argon gas or its mist.
Other part of present embodiment and embodiment 1 are identical.
The discharge capacity first of this material is 368.1mAh/g, and first charge-discharge efficiency is 93.4%
Table 1 is the electrical performance data of carbon modified material in the various embodiments of the present invention.
Table 1
Can find out that from table 1 carbon modified material that the present invention makes belongs to composite artificial graphite, gram volume is high, and compacted density is high, and specific area is little, and processing characteristics is good, good cycle.Be used to prepare lithium ion battery, have very high electrical property, its reversible capacity and first efficient all be significantly improved, can satisfy the demand of high magnification capacity, can stop to overcharge and cross and put, be well suited for being used for lithium ion battery.
Above-described embodiment describes preferred implementation of the present invention; Be not that scope of the present invention is limited; Design under the prerequisite of spirit not breaking away from the present invention; Various distortion and improvement that the common engineers and technicians in this area make technical scheme of the present invention all should fall in the definite protection range of claims of the present invention.
Claims (6)
1. a power is with lithium ion secondary battery negative pole raw material of wood-charcoal material; It is characterized in that: it is to be raw material with graphous graphite powder and resin; In pressure vessel, carry out the liquid-phase dehydration processing again after being dissolved in organic solvent; Then through coating modification, low-temperature setting, charing, after process after the high-temperature heat treatment, cooling screening; Its carbon modified material of processing is sphere or elliposoidal, and average grain diameter D50 is 0.5～30 μ m, and tap density is between 0.5～1.5g/cc, and the BET specific area is at 0.5～5.0m
2Between/the g, real density 0.8～2.25g/cc, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm; The particle diameter of wherein said graphous graphite powder is 6～30 μ m, and specific area is smaller or equal to 6m
2/ g; Said resin is furane resins, Lauxite, phenolic resins, epoxy resin, polymethyl methacrylate, Kynoar or polyacrylonitrile.
2. the described charcoal preparation methods of claim 1, it is characterized in that: step is following:
1. get the raw materials ready: with graphous graphite powder and resin by weight 5～20: 1 ratio, ready for use;
2. reinforced: as the raw material of getting ready to be dissolved in the organic solvent, alternately to join while stirring in the pressure vessel, continue to stir 2～4 hours, then in 10～30 minutes, add the reaction promoter of total weight 3%～15%;
3. heat up: the heating that heats up then, in 7～9 hours, temperature is raised to 400～600 ℃; The negative pressure that wherein heats up 2～3 hours the time is extracted the volatile matter in the above-mentioned substance out;
4. keep constant temperature: keep constant temperature at 400～600 ℃, 4～9 hours time, extract volatile matter simultaneously out;
5. naturally cool to room temperature;
6. high temperature carries out graphitization processing for 2600～3000 ℃;
Wherein, 6. 5. 4. 3. said step all carry out under anti-oxidation environment.
3. preparation method according to claim 2 is characterized in that: described anti-oxidation environment is to extract in negative pressure to feed inert gas or hydrogen under the state.
4. preparation method according to claim 3 is characterized in that: said inert gas is a nitrogen, and its flow is 0.5～2m
3/ h.
5. according to each described preparation method of claim 2-4, it is characterized in that: said reaction promoter is cycloalkane and/or aromatic solvent.
6. preparation method according to claim 5 is characterized in that: said aromatic solvent be selected from fear oil and washing oil in any.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103078088A (en) * | 2013-02-05 | 2013-05-01 | 新乡远东电子科技有限公司 | Lithium ion battery cathode material |
| CN103094536A (en) * | 2013-02-05 | 2013-05-08 | 新乡远东电子科技有限公司 | High-capacity lithium ion secondary battery cathode carbon material |
| CN113346076A (en) * | 2021-05-14 | 2021-09-03 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN115010109A (en) * | 2022-04-29 | 2022-09-06 | 湖南大学 | Preparation method of novolac epoxy resin-based hard carbon material, hard carbon material and sodium ion battery |
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| CN101209831A (en) * | 2007-12-25 | 2008-07-02 | 程先桃 | Carbon modified material for lithium ion secondary battery negative pole and preparation thereof |
| CN101318820A (en) * | 2008-01-25 | 2008-12-10 | 宁波杉杉新材料科技有限公司 | Composite plumbago-carbon negative pole material and method of manufacturing the same |
| CN100447077C (en) * | 2005-09-07 | 2008-12-31 | 宁波杉杉新材料科技有限公司 | Preparation method of artificial graphite charcoal negative electrode material and prepared artificial graphite charcoal negative electrode material |
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| CN100447077C (en) * | 2005-09-07 | 2008-12-31 | 宁波杉杉新材料科技有限公司 | Preparation method of artificial graphite charcoal negative electrode material and prepared artificial graphite charcoal negative electrode material |
| CN101209831A (en) * | 2007-12-25 | 2008-07-02 | 程先桃 | Carbon modified material for lithium ion secondary battery negative pole and preparation thereof |
| CN101318820A (en) * | 2008-01-25 | 2008-12-10 | 宁波杉杉新材料科技有限公司 | Composite plumbago-carbon negative pole material and method of manufacturing the same |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103078088A (en) * | 2013-02-05 | 2013-05-01 | 新乡远东电子科技有限公司 | Lithium ion battery cathode material |
| CN103094536A (en) * | 2013-02-05 | 2013-05-08 | 新乡远东电子科技有限公司 | High-capacity lithium ion secondary battery cathode carbon material |
| CN113346076A (en) * | 2021-05-14 | 2021-09-03 | 沁新集团(天津)新能源技术研究院有限公司 | Surface modified graphite negative electrode material of lithium ion battery and preparation method thereof |
| CN115010109A (en) * | 2022-04-29 | 2022-09-06 | 湖南大学 | Preparation method of novolac epoxy resin-based hard carbon material, hard carbon material and sodium ion battery |
| CN115010109B (en) * | 2022-04-29 | 2023-08-25 | 湖南大学 | Preparation method of phenolic epoxy resin-based hard carbon material, hard carbon material and sodium ion battery |
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Application publication date: 20120711 |