CN102569752A - Carbon modified material for lithium ion secondary battery cathode and preparation method for carbon modified material - Google Patents
Carbon modified material for lithium ion secondary battery cathode and preparation method for carbon modified material Download PDFInfo
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Abstract
The invention relates to a carbon modified material for a lithium ion secondary battery cathode. The carbon modified material is prepared by dissolving needle-like petroleum coke and/or coal tar and resin serving as raw materials into an organic solvent, performing liquid phase dehydration treatment in a pressure container and performing coating modification, low-temperature solidification, carbonization, high-temperature heat treatment, cooling and screening; and the prepared carbon modified material is spherical or ellipsoidal, the average particle diameter D50 is 0.5 to 30 microns, the tap density is between 0.5 and 1.5g/cc, the BET specific surface area is between 0.5 and 5.0m<2>/g, the real density is 0.8 to 2.25g/cc, a large quantity of nano holes are formed in the carbon modified material, and the aperture is 0.1 to 0.6 nanometer. Through the carbon modified material, the volume specific capacity and the first efficiency are improved, the specific surface area is reduced so that the defect that the reversible capacity is lost because a pyrolytic hard carbon material is sensitive to air is overcome, and the processing performance of the material is improved; and the carbon modified material is suitable for a lithium ion secondary battery for power.
Description
Technical field
The present invention relates to a kind of carbon modified material that is used for lithium ion secondary battery negative pole 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.PowerSources, 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 carbon modified material that is used for lithium ion secondary battery negative pole; It is to be raw material by acicular petroleum coke and/or coal tar 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; The 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; Wherein 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.
Petroleum coke is a crude oil after distillation separates weight matter oil, and mink cell focus is again through the process of hot tearing, the product that is transformed; From seeing in appearance, coke is an out-of-shape, black not of uniform size block (or particle); Metallic luster is arranged, the particle tool multiple-void structure of coke, main element set becomes carbon; Occupy more than the 80wt%, remaining is hydrogen, oxygen, nitrogen, sulphur and metallic element.The form of petroleum coke is difference to some extent with the difference of processing procedure, operating condition and feed properties.The petroleum coke of being produced from the petroleum coke workshop all is called green coke, contains some not fugitive constituents of the carbon hydrocarbon compound of carbonization.The afocal that most petroleum coke workshop is produced is seen and is the irregular bulk of pitchy porosu solid, and this kind Jiao is called sponge coke.The preferable petroleum coke of another kind of quality is exactly a needle coke, and it has tangible acicular texture and fiber pattern, and is main as high power and ultra high power graphite electrode in the steel-making.The acicular petroleum coke that the present invention adopts promptly is this product.
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%.
The preparation method of carbon modified material of the present invention, step is following:
(1) preparation presoma: with acicular petroleum coke and/or coal tar and organic solvent formation mixture, add butadiene-styrene rubber and span80 activator therein, form homogeneous dispersion system; Then homogeneous dispersion system is placed the pressure vessel of belt stirrer, heating is stirred simultaneously, and programming rate is 10～50 ℃/min, and temperature is controlled at 200～380 ℃, and temperature retention time is 5～20 hours; Cooling is broken up then, crosses 200～500 mesh sieves and gets presoma; A large amount of nanometer micropores is arranged on the presoma that makes, and the size of micropore is about 0.1～0.6nm;
(2) modification is handled: with presoma for preparing and resin is that 10: 0.8～2.0 ratios are mixed by weight, heating then, and temperature is controlled at 150～280 ℃, mixes;
(3) heat treatment: take out the powder mix and pack into and heat in corundum crucible or the graphite crucible, heating-up temperature is 500～1300 ℃, and be 5～40 hours heating time; Powder after will heating again carries out high-temperature roasting, and sintering temperature is more than 2500 ℃, and roasting time is 5～48 hours;
(4) screening: the powder after the roasting is carried out selected screening, and sieve number is 200～500 orders.
Above-mentioned preparation method feeds protective gas during heat treatment in the said step (3), and said protective gas is nitrogen, inert gas or its mist; Gas flow rate is 10～20L/min; During heat treatment, below 600 ℃ the time, programming rate is controlled to be 50～100 ℃/hour; More than 600 ℃ the time, programming rate is controlled to be 200～300 ℃/hour.
Among the above-mentioned preparation method, the particle diameter that can under HTHP, control material with carbon element particulate bead through the cohesion and the residence time of adjusting homogeneous mixture system, pressure is greater than 15atm, and residence time was controlled at 5～48 hours, made microspherulite diameter be tending towards constant.
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:
Take by weighing 150 gram acicular petroleum cokes and pour in 500 milliliters the clean beaker, add solvent carbon disulfide 300 grams then, under mixer, fully stirred 2 hours, rotating speed is adjusted to 1000 rev/mins, it is fully dissolved form homogeneous dispersion system; In homogeneous dispersion system, add the butadiene-styrene rubber of 20 grams 50% and the span80 of 3 grams 3% and carry out activation; Continue to stir 1 hour, be placed on afterwards in the pressure vessel of 1 liter of belt stirrer, the limit heating starts simultaneously stirs; Mixing speed is 500 rev/mins; Speed with 10 ℃/min is warmed up to 350 ℃, is incubated to take out after 12 hours to be cooled to normal temperature, breaks up 325 mesh sieves and obtains presoma.
Get then 100 the gram presomas and 10 the gram polymethyl methacrylates mix; Even back to be mixed take out the graphite crucible of packing into carry out in warm processing; Heat treatment temperature is 1100 ℃; Processing time is 8 hours; Feed nitrogen in the heat treatment process and protect, also can feed other inert gas such as argon gas or its mist; Powder after afterwards middle temperature being handled carries out high-temperature process at 2800 ℃, feeds protective gas simultaneously, and the processing time is 20 hours.At last powder is cooled to cross 200 mesh sieves behind the normal temperature, the powder behind the sieve is modification powdered carbon sample.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 362.8mAh/g, and first charge-discharge efficiency is 94.7%.The first charge-discharge curve is as shown in Figure 1.
Embodiment 2:
Take by weighing 120 gram coal tar and be contained in 500 milliliters the clean beaker, add solvent carbon disulfide 250 grams then, be made into homogeneous dispersion system; The span80 that in homogeneous dispersion system, adds butadiene-styrene rubber and 5 grams 3% of 30 grams 50% carries out activation and obtains presoma.
Get 100 gram presomas and 12 gram epoxy resin mixing coating modifications again.
Other part of present embodiment and embodiment 1 are identical.
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.
The discharge capacity first of this material is 354.7mAh/g, and first charge-discharge efficiency is 93.6%.The first charge-discharge curve is as shown in Figure 2.
Embodiment 3:
Take by weighing 100 gram acicular petroleum cokes and 80 gram coal tar are contained in 500 milliliters the clean beaker, add solvent xylene 320 grams then, under mixer, fully stirred 2 hours, rotating speed is adjusted to 1200 rev/mins, it is fully dissolved form homogeneous dispersion and be; The span80 that in homogeneous dispersion system, adds butadiene-styrene rubber and 4 grams 3% of 35 grams 50% carries out activation and obtains presoma.
Get 100 gram presomas and 15 gram phenolic resins mixing coating modifications again.In the warm processing time be 12 hours, carried out high-temperature process 24 hours at 2800 ℃ again.
Other part of present embodiment and embodiment 1 are identical.
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.
Detection learns that the discharge capacity first of this material is 358.9mAh/g, and first charge-discharge efficiency is 94.3%.
Embodiment 4:
Take by weighing 130 gram acicular petroleum cokes and 50 gram coal tar are contained in 500 milliliters the clean beaker; Add solvent carbon disulfide 200 grams and xylenes 140 grams then; Under mixer, fully stirred 3 hours, rotating speed is adjusted to 1200 rev/mins, it is fully dissolved form homogeneous dispersion system; The span80 that in homogeneous dispersion system, adds butadiene-styrene rubber and 5 grams 3% of 15 grams 50% carries out activation and obtains presoma.
Get 100 gram presomas and 15 gram furane resins mixing coating modifications again.In warm treatment temperature be 1200 ℃, heat treatment time is 20 hours, carries out high-temperature heat treatment 36 hours at 3000 ℃ again.
Other part of present embodiment and embodiment 1 are identical.
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.
The discharge capacity first of this material is 365.7mAh/g, and first charge-discharge efficiency is 93.8%
Embodiment 5:
Take by weighing 110 gram acicular petroleum cokes and be contained in 500 milliliters the clean beaker, add solvent carbon disulfide 230 grams and quinoline 120 grams then, under mixer, fully stirred 1 hour, rotating speed is adjusted to 1300 rev/mins, makes it fully dissolve the formation homogeneous dispersion and is; The span80 that in homogeneous dispersion system, adds butadiene-styrene rubber and 6 grams 3% of 18 grams 50% carries out activation and obtains presoma.
Get 100 gram presomas and 8 gram polyacrylonitrile mixing coating modifications again.
Other part of present embodiment and embodiment 1 are identical.
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.
The discharge capacity first of this material is 365.5mAh/g, and first charge-discharge efficiency is 93.7%
Embodiment 6:
Take by weighing 80 gram acicular petroleum cokes and 100 gram coal tar are contained in 500 milliliters the clean beaker, add then in solvent carbon disulfide 350 grams, under mixer, fully stirred 5 hours, rotating speed is adjusted to 800 rev/mins, it is fully dissolved form homogeneous dispersion and be; The span80 that in homogeneous dispersion system, adds butadiene-styrene rubber and 4 grams 3% of 19 grams 50% carries out activation and obtains presoma.
Get 100 gram presomas and 12 gram Lauxite mixing coating modifications again.In warm treatment temperature be 1000 ℃, heat treatment time is 8 hours, carries out high-temperature heat treatment 12 hours at 2900 ℃ again.
Other part of present embodiment and embodiment 1 are identical.
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.
The discharge capacity first of this material is 366.1mAh/g, and first charge-discharge efficiency is 93.8%.The first charge-discharge curve is as shown in Figure 3.
Embodiment 7:
Taking by weighing acicular petroleum coke, coal tar and resin respectively 50 restrains in the clean beaker that is contained in 500 milliliters; Add solvent carbon disulfide 150 grams and benzinum 200 grams then; Under mixer, fully stirred 6 hours, rotating speed is adjusted to 1500 rev/mins, it is fully dissolved form homogeneous dispersion system; The span80 that in homogeneous dispersion system, adds butadiene-styrene rubber and 6 grams 3% of 35 grams 50% carries out activation and obtains presoma.
Get 100 gram presomas and 12 gram polymethyl methacrylate mixing coating modifications again.In warm treatment temperature be 1200 ℃, heat treatment time is 16 hours, carries out high-temperature heat treatment 24 hours at 3000 ℃ again.
Other part of present embodiment and embodiment 1 are identical.
Resulting carbon modified material is sphere or elliposoidal, and average grain diameter D50 is 18 μ m, and tap density is about 1.3g/cc, and the BET specific area is at 2.8m
2About/g, about real density 1.55g/c, there are a large amount of nano-pores its inside, aperture 0.1～0.6nm.
The discharge capacity first of this material is 368.9mAh/g, and first charge-discharge efficiency is 94.5%.
Table 1 is the electrical performance data of the carbon modified material that makes among above-mentioned each embodiment of the present invention.
Table 1
Can find out that from table 1 carbon modified material that the present invention makes is 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 (3)
1. carbon modified material that is used for lithium ion secondary battery negative pole; It is characterized in that: it is to be raw material by acicular petroleum coke and/or coal tar 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; The 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; Wherein said resin is furane resins, Lauxite, phenolic resins, epoxy resin, polymethyl methacrylate, Kynoar or polyacrylonitrile.
2. the preparation method of the described carbon modified material of claim 1, it is characterized in that: step is following:
(1) preparation presoma: with acicular petroleum coke and/or coal tar and organic solvent formation mixture, add butadiene-styrene rubber and span80 activator therein, form homogeneous dispersion system; Then homogeneous dispersion system is placed the pressure vessel of belt stirrer, heating is stirred simultaneously, and programming rate is 10～50 ℃/min, and temperature is controlled at 200～380 ℃, and temperature retention time is 5～20 hours; Cooling is broken up then, crosses 200～500 mesh sieves and gets presoma;
(2) modification is handled: with presoma for preparing and resin is that 10: 0.8～2.0 ratios are mixed by weight, heating then, and temperature is controlled at 150～280 ℃, mixes;
(3) heat treatment: take out the powder mix and pack into and heat in corundum crucible or the graphite crucible, heating-up temperature is 500～1300 ℃, and be 5～40 hours heating time; Powder after will heating again carries out high-temperature roasting, and sintering temperature is more than 2500 ℃, and roasting time is 5～48 hours;
(4) screening: the powder after the roasting is carried out selected screening, and sieve number is 200～500 orders.
3. preparation method according to claim 2; It is characterized in that: feed protective gas in the said step (3) during heat treatment; Said protective gas is nitrogen, inert gas or its mist, and gas flow rate is 10～20L/min, during heat treatment; Below 600 ℃ the time, programming rate is controlled to be 50～100 ℃/hour; More than 600 ℃ the time, programming rate is controlled to be 200～300 ℃/hour.
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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 |
| CN103214245A (en) * | 2013-03-29 | 2013-07-24 | 中国科学院过程工程研究所 | Carbon/carbon composite microsphere material, production method and lithium ion battery |
| US20160372737A1 (en) * | 2015-06-18 | 2016-12-22 | Panasonic Intellectual Property Management Co., Ltd. | Electrode material and battery |
| CN107601490A (en) * | 2017-08-11 | 2018-01-19 | 天津爱敏特电池材料有限公司 | A kind of fast charge graphite cathode material and preparation method thereof |
| CN108598378A (en) * | 2018-01-29 | 2018-09-28 | 齐鲁工业大学 | A kind of lithium/anode material of lithium-ion battery Fe1-xThe preparation method of S/C |
| CN108598476A (en) * | 2018-03-11 | 2018-09-28 | 贵州格瑞特新材料有限公司 | A kind of negative electrode of lithium ion battery high first spherical hard carbon material of effect and preparation method thereof |
| CN113097489A (en) * | 2021-04-01 | 2021-07-09 | 辽宁奥亿达新材料有限公司 | Lithium ion battery carbon negative electrode liquid phase coating material, preparation and coating method |
| WO2022266798A1 (en) * | 2021-06-21 | 2022-12-29 | 宁德新能源科技有限公司 | Negative electrode material, electrochemical apparatus, and electronic apparatus |
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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 |
| CN103214245A (en) * | 2013-03-29 | 2013-07-24 | 中国科学院过程工程研究所 | Carbon/carbon composite microsphere material, production method and lithium ion battery |
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| CN107601490A (en) * | 2017-08-11 | 2018-01-19 | 天津爱敏特电池材料有限公司 | A kind of fast charge graphite cathode material and preparation method thereof |
| CN108598378A (en) * | 2018-01-29 | 2018-09-28 | 齐鲁工业大学 | A kind of lithium/anode material of lithium-ion battery Fe1-xThe preparation method of S/C |
| CN108598476A (en) * | 2018-03-11 | 2018-09-28 | 贵州格瑞特新材料有限公司 | A kind of negative electrode of lithium ion battery high first spherical hard carbon material of effect and preparation method thereof |
| CN113097489A (en) * | 2021-04-01 | 2021-07-09 | 辽宁奥亿达新材料有限公司 | Lithium ion battery carbon negative electrode liquid phase coating material, preparation and coating method |
| CN113097489B (en) * | 2021-04-01 | 2022-02-22 | 辽宁奥亿达新材料有限公司 | Preparation method of carbon cathode of lithium ion battery |
| WO2022266798A1 (en) * | 2021-06-21 | 2022-12-29 | 宁德新能源科技有限公司 | Negative electrode material, electrochemical apparatus, and electronic apparatus |
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Application publication date: 20120711 |