CN101728535A - Lithium ion battery conducting material and preparation method and application thereof - Google Patents

Lithium ion battery conducting material and preparation method and application thereof Download PDF

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CN101728535A
CN101728535A CN200910236785A CN200910236785A CN101728535A CN 101728535 A CN101728535 A CN 101728535A CN 200910236785 A CN200910236785 A CN 200910236785A CN 200910236785 A CN200910236785 A CN 200910236785A CN 101728535 A CN101728535 A CN 101728535A
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lithium ion
ion battery
conducting material
preparation
graphene
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宋怀河
郭鹏
陈晓红
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Beijing University of Chemical Technology
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Abstract

The invention relates to a lithium ion battery conducting material and a preparation method and application thereof. A graphene lithium ion battery conducting material is prepared by adopting a graphite oxide rapid heat expansion method and has high aspect ratio, which is beneficial to shortening the migration distance of lithium ions and improving the wetting quality of an electrolyte, thereby, the rate performance of an electrode is improved; the graphene lithium ion battery conducting material also has high conductivity and can ensure that an electrode active substance has higher utilization ratio and excellent cyclical stability. Compared with a common acetylene black conductive agent under the same using amount, the specific capacity of a lithium ion battery cathode constructed by the conducting material is improved by 25-40 percent, and the coulomb efficiency is improved by 10-15 percent. In addition, the method has low cost, simple process, high security and low energy consumption and is suitable for large-scale production.

Description

A kind of lithium ion battery conducting material and its production and use
Technical field:
The present invention relates to a kind of lithium ion battery conducting material and its production and use, be about to this lithium ion battery conducting material and be used for electrode preparation.
Background technology:
Lithium ion battery is a kind of novel energy storage device, has the energy density height, the average output voltage height, and self discharge is little, and power output is big, but fast charging and discharging, operating temperature range is wide, environmental friendliness, long characteristics such as useful life.Because above many advantages, since Sony commercial applications in 1992, obtain the concern of countries in the world scientific research institution and government, and be widely used in the portable type electronic products such as notebook computer, mobile phone, digital camera, in addition, the applied lithium ion batteries in field such as military affairs, Aero-Space, electric vehicle also are in the development process.
Lithium ion battery discharges and recharges in the course of reaction, be accompanied by the transmission of lithium ion and the transfer of electronics, this just requires on the one hand, and electrode has good electrical conductivity and bigger aspect ratio, guarantee the formation of favorable conductive network, thereby have lower resistivity, on the other hand, with active material, collector has the good interface contact, guarantees the integrality and the continuity of conductive structure in cyclic process.The conductive additive that possesses above two aspect features could guarantee that electrode active material has higher utilance and good cyclical stability.
The agent of conventional conductive such as graphite, acetylene black has characteristics such as conductivity is good, density is low, chemical stability is good, be often used as the conductive agent of lithium ion battery electrode material, when charge-discharge magnification or current density lower, when cycle-index was less, they can bring into play the favorable conductive effect, but when high-power discharging and recharging, conductive agent easily polarizes, produce phenomenons such as ablation, make to occur the space between active material particle that conductive network is destructurized.The reunion fasciculation in use takes place in novel conductive such as carbon nano-tube, carbon nano-fiber additive easily, and dispersiveness can not be well solved, and makes its use amount improve.Above defective causes the utilance of electrode active material and cyclical stability to descend easily.In order further to improve the performance of lithium ion battery, be necessary problem (Kuroda, S. such as the conductive additive of development of new solves stable circulation, and conductive structure is complete; Tobori, N.; Sakuraba, M.; Sato, Y.J.Power Sources 2003,119-121,924.).
Graphene is the novel carbon nano material with special two-dimentional monoatomic layer crystal structure characteristic, has special power, electricity, light, thermal characteristics, and Theoretical Calculation and experiment show to have superelevation electron mobility (20000cm under its room temperature 2/ (Vs)), quantum hall effect, little free track reciprocation, theoretical specific area is up to 2600m 2/ g also has high heat conductance (5000W/ (mK)) and outstanding mechanical property (high-modulus 1100GPa, high strength 125GPa) (Park, S.; Ruoff, R.S.NatureNanotechnology 2009,4, and 217).The sp of Graphene 2The conjugated that structure is formed and the surface exists has guaranteed ballistic Transport, compares with above-mentioned four kinds of conductive agent materials, makes Graphene have excellent conducting performance.Form with aforementioned conductive agent and active material in addition that some contact or the line contact is compared, face contacts has less contact impedance, helps the raising of electrode conductivuty.Compare with other conductive agents and to have remarkable advantages.
Graphene preparation method commonly used comprises that micromechanics peels off method (Novoselov, K.S.; Geim, A.K.; Morozov, S.V.; Jiang, D.; Y.Zhang, Dubonos, S.V.; Grigorieva, I.V.; Firsov, A.A.Science 2004,306, and 66.), organic synthesis method (Zhi, L.; M ü llen, K.Journal ofMaterials Chemistry.2008,18,1472.), vapour deposition process (Eizenberg, M.; Blakely, J.M.Surface Science 1970,82,228), solvent-thermal method (Nethravathi, C.; Rajamathi, M.Carbon 2008,46, and 1994), graphite oxide reducing process (Stankovich, S.et al.Carbon 2007,45,1558.).Among the above preparation method, micromechanics is peeled off with the organic synthesis method can obtain the higher thin layer Graphene of purity, but productive rate is lower; Vapour deposition process needs higher temperature, and energy consumption is higher; Solvent-thermal method uses methyl alcohol, and alkali metal is as reactant, and the course of reaction fail safe is relatively poor.Oxidizing process productive rate height but byproduct of reaction is more.
Still do not use at present Graphene to make up the bibliographical information of lithium ion battery negative material as electric conducting material.Therefore, be of very high actual application value for research and development new type lithium ion battery electrode material.
Summary of the invention:
The purpose of this invention is to provide a kind of lithium ion battery conducting material and its production and use with high aspect ratio and high conductivity.
A kind of lithium ion battery conducting material of the present invention is characterized in that: described lithium ion battery conducting material is the graphene nanometer sheet of toner powder darkly, and thickness is 1-10nm, and area is 1~5 μ m 2, tap density is 0.67~0.78g/cm 3, room-temperature conductivity is 950-1200S/cm.
The preparation method of the above-mentioned lithium ion battery conducting material of the present invention is graphite oxide Rapid Thermal plavini, specifically adopts the following step and condition:
A: the mass ratio according to 1: 9~11 takes by weighing graphite and potassium chlorate, earlier graphite is joined volume ratio and be in the mixed liquor of 2~2.5: 1 the concentrated sulfuric acid (mass concentration is 98%) and red fuming nitric acid (RFNA) (mass concentration is 65~67%), progressively add potassium chlorate (purpose that progressively adds potassium chlorate is to prevent that reaction is violent) then, carry out oxidation reaction, control reaction temperature is 0~4 ℃, react after 72~120 hours, (concentration can be 0.1~1mol/L) solution to use watery hydrochloric acid successively, deionized water cleans repeatedly that chloride ion does not detect and the pH value reaches neutrality to having, under 40 ℃ of conditions of vacuum, dry then, pulverize, obtain the graphite oxide powder;
B: the graphite oxide powder that steps A is obtained after 10~30 seconds rapid thermal treatment, obtains peelable graphite under 900~1050 ℃, air atmosphere;
C: the peelable graphite that step B is obtained is scattered in the absolute ethyl alcohol, placed under the ultrasonic wave condition of 100~400W power dispersion treatment 1~4 hour, ultrasonic wave is separated into routine techniques, obtain graphene suspension, vacuum and low temperature (baking temperature is preferably 40~60 ℃) drying obtains powdery graphite alkene nano-sheet lithium ion battery electric conducting material then.
The above-mentioned lithium ion battery conducting material of the present invention can be used as conductive agent and is used to prepare lithium ion cell electrode, it is characterized in that: graphene nanometer sheet lithium ion battery conducting material shared quality in electrode is 2~10%, negative or positive electrode active material powder quality is 80~88%, and all the other are binding agent.
Described negative or positive electrode active material and binding agent are in the present technology known material commonly used, as negative active core-shell material can be in native graphite, modified natural graphite, Delanium, mesophase pitch carbon microspheres, the graphitized carbon fiber a kind of.Binding agent can be Kynoar or polytetrafluoroethylene.
Use graphene nanometer sheet of the present invention to compare with acetylene black conductive agent commonly used under same amount as the lithium ion battery negative that electric conducting material makes up, the specific capacity of negative material improves 25~40%, and coulombic efficiency improves 10~15%.
Lithium ion battery conducting material, (thickness is 1~10nm, and area is 1~5 μ m to have high aspect ratio 2), the wettability that helps shortening the migration distance of lithium ion and improve electrolyte, thus the electrode high rate performance improved; Have in addition high conductance (950~1200S/cm), can guarantee that electrode active material has higher utilance and good cyclical stability.
The Graphene cost of the graphite oxide Rapid Thermal plavini preparation that the present invention adopts is low, and technology is simple, and is safe, energy consumption is low, is suitable for large-scale production.
Description of drawings:
The high-resolution-ration transmission electric-lens photo of the graphene conductive material that Fig. 1 makes for embodiment 1.
The Graphene surface has manyly by fold and pile up the silk shape feature that forms as can be seen from FIG., and thickness is 2-5nm.
Fig. 2 is the embodiment of the invention 9 Graphenes, Comparative Examples 4 acetylene blacks during as conductive agent, and the ion secondary battery cathode material lithium Delanium is respectively 0.2,0.5,0.8,1mA cm -2Current density under, the relation curve of discharge capacity and cycle-index.Adopt under the identical multiplying power Graphene of the present invention as the capacity of conductive agent and capability retention apparently higher than the electrode of acetylene black as conductive agent.
Embodiment:
Embodiment 1
A: (industrial lithium ion battery negative material, distribution of particles are 10~15 μ m, and specific area is 4m to take by weighing the 5.5g Delanium 2/ g, ash content is 4~6%), join in the mixed liquor of the concentrated sulfuric acid (concentration 98%) of 95mL0~4 ℃ and 47.5mL red fuming nitric acid (RFNA) (concentration is 65~67%), added 5 gram potassium chlorate subsequently every 5 minutes, amount to 55 grams, control reaction temperature is 0~4 ℃, and sustained response is after 90 hours, washes repeatedly until no chloride ion with deionized water with the watery hydrochloric acid of 0.1mol/L earlier to detect and the pH value reaches neutrality again.Obtain the graphite oxide powder after 40 ℃ of oven dry of vacuum.
B: the graphite oxide powder packed into put into the Muffle furnace rapid thermal treatment 20 seconds (promptly placing 20 seconds) of 1000 ℃ of air atmospheres behind the crucible, obtain peelable graphite.
C: use supersonic wave cleaning machine under 150W power, in absolute ethyl alcohol, the peelable graphite of dispersion treatment B step gained 1 hour obtains graphene suspension.After 40 ℃ of oven dry of vacuum, obtain the graphene conductive agent.Shown in the high-resolution-ration transmission electric-lens photo of accompanying drawing 1, the Graphene surface is that many thickness is 2~5nm by fold and pile up the silk shape feature that forms, and area is 1~2 μ m 2Recording tap density (down with) according to the method for GB/T21354-2008 is 0.67~0.70g/cm 3Recording room-temperature conductivity (down with) according to the method for GB/T11007-2008 is 1100~1200S cm -1
(industrial lithium ion battery negative material, distribution of particles are 10~15 μ m, and specific area is 4m to take by weighing the negative active core-shell material Delanium respectively 2/ g, ash content are 4~6%) 85mg, the graphene conductive agent 5mg that the C step obtains, Kynoar binding agent 10mg uses the N-methyl pyrrolidone to be solvent, with the mortar ground and mixed evenly after, be to film on the nickel foam of 1cm at diameter, thickness is 40~50 μ m.The N-methyl pyrrolidone was volatilized fully in dry 12 hours down for 120 ℃ in vacuum, use tablet press machine under 10MPa pressure, to obtain electrode slice.With Cellgard2400 is barrier film, is 1: 1 the ethylene carbonate and the LiPF of dimethyl carbonate and 1 molal weight with volume ratio 6Be electrolyte, metal lithium sheet is to electrode, finishes the simulated battery assembling, and recording in current density is 0.2mA/cm 2The time discharge capacity be 309mAh/g.
Embodiment 2
The preparation method of graphite oxide powder is with embodiment 1, the Muffle furnace rapid thermal treatment 10 seconds that the graphite oxide powder that the A step is obtained is packed into and put into 1000 ℃ of air atmospheres behind the crucible, obtain peelable graphite, use the probe ultrasonic cell disruptor under 400W power, in alcohol solvent, dispersion treatment obtained graphene suspension in 4 hours, obtained the graphene conductive agent behind 40 ℃ of vacuum dryings, the graphene nanometer sheet thickness that makes is 5~10nm, and area is 2~4 μ m 2Tap density is 0.74~0.78g/cm 3, room-temperature conductivity is 900~950S cm -1
The preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 294mAh/g.
Embodiment 3
Graphene conductive agent preparation method except that the A stage oxidation reaction time be 72 hours with embodiment 1, the graphene nanometer sheet thickness that makes is 7~9nm, area is 1~5 μ m 2Tap density is 0.76~0.77g/cm 3, room-temperature conductivity is 950~1150S cm -1
The preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 297mAh/g.
Embodiment 4
Graphene conductive agent preparation method except that the A stage oxidation reaction time be 120 hours with embodiment 1, the graphene nanometer sheet thickness that this method makes is 3~5nm, area is 1~2 μ m 2Tap density is 0.77~0.78g/cm 3, room-temperature conductivity is 900~950S cm -1
The preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 282mAh/g.
Embodiment 5
Graphene conductive agent preparation method except that the A stage oxidation reaction time be 900 ℃ with embodiment 1, the graphene nanometer sheet thickness that this method makes is 5~7nm, area is 3~5 μ m 2Tap density is 0.76~0.77g/cm 3, room-temperature conductivity is 950~1150S cm -1
The preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 294mAh/g.
Embodiment 6
Graphene conductive agent preparation method except that the A stage oxidation reaction time be 1050 ℃ with embodiment 1, the graphene nanometer sheet thickness that this method makes is 3~5nm, area is 1~2 μ m 2Tap density is 0.71~0.73g/cm 3, room-temperature conductivity is 1000~1100S cm -1
The preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 301mAh/g.
Embodiment 7
Graphene conductive agent preparation method takes by weighing negative active core-shell material Delanium 88mg respectively with embodiment 1, graphene conductive agent 2mg, and Kynoar (PVDF) binding agent 10mg, the preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 220mAh/g.
Embodiment 8
Graphene conductive agent preparation method takes by weighing negative active core-shell material Delanium 83mg respectively with embodiment 1, graphene conductive agent 7mg, and Kynoar (PVDF) binding agent 10mg, the preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 349mAh/g.
Embodiment 9
Graphene conductive agent preparation method takes by weighing negative active core-shell material Delanium 80mg respectively with embodiment 1, graphene conductive agent 10mg, and Kynoar (PVDF) binding agent 10mg, the preparation of electrode slice, the assembling of simulated battery and test are with embodiment 1.As shown in Figure 2: recording in current density is 0.2mol/cm 2, 0.5mA/cm 2, 0.8mA/cm 2, 1mA/cm 2The time discharge capacity be respectively 424mAh/g, 329mAh/g, 272mAh/g, 245mAh/g.
Embodiment 10
Graphene conductive agent preparation method takes by weighing negative active core-shell material native graphite 85mg respectively with embodiment 1, graphene conductive agent 5mg, and binding agent-Kynoar (PVDF) 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 312mAh/g.
Embodiment 11
Graphene conductive agent preparation method is with embodiment 1, and (particle diameter is 5-40 μ m, and average grain diameter is 10 μ m to take by weighing negative active core-shell material mesophase pitch carbon microspheres respectively; Density is 2.1gcm -3) 85mg, graphene conductive agent 5mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 325mAh/g.
Embodiment 12
Graphene conductive agent preparation method is with embodiment 1, and (density is 1.9gcm for diameter 5-7 μ m, average diameter 6 μ m to take by weighing the negative active core-shell material graphitized carbon fibre respectively -3) 85mg, graphene conductive agent 5mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 336mAh/g.
Comparative Examples 1
Take by weighing negative active core-shell material Delanium 85mg respectively, acetylene black conductive agent 5mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Must the discharge capacity when current density is 0.2mA/cm2 be 247mAh/g, be 80% of specific capacity under the identical graphene conductive agent consumption.
Comparative Examples 2
Take by weighing negative active core-shell material Delanium 88mg respectively, acetylene black conductive agent 2mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 216mAh/g, be 98% of specific capacity under the identical graphene conductive agent consumption.
Comparative Examples 3
Take by weighing negative active core-shell material Delanium 83mg respectively, acetylene black conductive agent 7mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 278mAh/g, be 79% of specific capacity under the identical graphene conductive agent consumption.
Comparative Examples 4
Take by weighing negative active core-shell material Delanium 80mg respectively, acetylene black conductive agent 10mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.As shown in Figure 2: recording in current density is 0.2mA/cm 2The time discharge capacity be 319mAh/g, be 75% of specific capacity under the identical graphene conductive agent consumption; In current density is 0.5mA/cm 2, 0.8mA/cm 2, 1mA/cm 2The time discharge capacity be respectively 285mAh/g, 229mAh/g, 182mAh/g, 86%, 84%, 74% when using Graphene as conductive agent for corresponding ratio.
Comparative Examples 5
Take by weighing negative active core-shell material native graphite 85mg respectively, acetylene black conductive agent 5mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 257mAh/g, be 79% of specific capacity under the identical graphene conductive agent consumption.
Comparative Examples 6
Take by weighing negative active core-shell material mesophase pitch carbon microspheres (specification is with embodiment 11) 85mg respectively, acetylene black conductive agent 5mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 224mAh/g, be 69% of specific capacity under the identical graphene conductive agent consumption.
Comparative Examples 7
Take by weighing negative active core-shell material graphitized carbon fibre (specification is with embodiment 12) 85mg respectively, acetylene black conductive agent 5mg, Kynoar (PVDF) binding agent 10mg, the assembling of simulated battery and test are with embodiment 1.Recording in current density is 0.2mA/cm 2The time discharge capacity be 252mAh/g, be 75% of specific capacity under the identical graphene conductive agent consumption.
Table 1 uses variety classes electric conducting material electrode of lithium cell chemical property relatively
Figure G2009102367851D0000101
The data of table 1 have provided the embodiment of the invention, the resulting different electric conducting materials of Comparative Examples, the different adding proportions of same conductive, the comparison of electrode of lithium cell chemical property under the different battery testing conditions of the identical adding proportion of same conductive, as can be seen, under identical adding proportion, use Graphene of the present invention to improve 25~40% than the specific capacity of using acetylene black as the reversible capacity of the lithium battery of electric conducting material, coulombic efficiency improves 10~15%, with the raising of adding proportion, Graphene as electric conducting material for lithium battery specific capacity and capability retention to improve effect more obvious.The graphene conductive material that the embodiment of the invention 1 obtains is to the performance improvement best results of lithium battery.

Claims (5)

1. lithium ion battery conducting material is characterized in that: described lithium ion battery conducting material is the graphene nanometer sheet of toner powder darkly, and thickness is 1~10nm, and area is 1~5 μ m 2, tap density is 0.67~0.78g/cm 3, room-temperature conductivity is 950~1200S/cm.
2. the preparation method of the described lithium ion battery conducting material of claim 1, adopt the following step and condition:
A: the mass ratio according to 1: 9~11 takes by weighing graphite and potassium chlorate, earlier graphite is joined volume ratio and be in the mixed liquor of 2~2.5: 1 the concentrated sulfuric acid and red fuming nitric acid (RFNA), progressively add potassium chlorate then, carry out oxidation reaction, control reaction temperature is 0~4 ℃, reacts after 72~120 hours, cleans repeatedly with dilute hydrochloric acid solution, deionized water successively that chloride ion does not detect and the pH value reaches neutrality to having, vacuum and low temperature oven dry then, pulverizing obtain the graphite oxide powder;
B: the graphite oxide powder that steps A is obtained after 10~30 seconds rapid thermal treatment, obtains peelable graphite under 900~1050 ℃, air atmosphere;
C: the peelable graphite that step B is obtained is scattered in the absolute ethyl alcohol, placed under the ultrasonic wave condition of 100~400W power dispersion treatment 1~4 hour, obtain graphene suspension, vacuum dehydrating at lower temperature obtains powdery graphite alkene nano-sheet lithium ion battery electric conducting material then.
3. according to the preparation method of the described lithium ion battery conducting material of claim 2, the mass concentration that it is characterized in that the described concentrated sulfuric acid of steps A is 98%, and the mass concentration of red fuming nitric acid (RFNA) is 65~67%, and the concentration of watery hydrochloric acid is 0.1mol/L~1mol/L.
4. according to the preparation method of claim 2 or 3 described lithium ion battery conducting materials, the temperature that it is characterized in that vacuum dehydrating at lower temperature among the step C is 40 ℃~60 ℃.
5. the application of the described lithium ion battery conducting material of claim 1 in electrode preparation is characterized in that: graphene nanometer sheet lithium ion battery conducting material shared quality in electrode is 2~10%.
CN200910236785A 2009-10-30 2009-10-30 Lithium ion battery conducting material and preparation method and application thereof Pending CN101728535A (en)

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CN102142548A (en) * 2011-02-25 2011-08-03 浙江大学 Compound nano material of graphene and MoS2 and preparation method thereof
CN102142551B (en) * 2011-02-25 2014-02-19 浙江大学 Graphene nano sheet/MoS2 composite nano material and synthesis method thereof
CN102142549A (en) * 2011-02-25 2011-08-03 浙江大学 Graphene nano sheet and SnS2 composite nano material and synthesis method thereof
CN102153074A (en) * 2011-03-22 2011-08-17 西北大学 Method for preparing graphene with high specific surface area through low-temperature pyrolysis and expansion
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CN102891014B (en) * 2011-07-19 2016-06-01 国家纳米科学中心 Graphene electrodes active substance and method for making thereof and electrode material and electrode slice and application
CN102891014A (en) * 2011-07-19 2013-01-23 国家纳米科学中心 Grapheme electrode active material, preparation method of grapheme electrode active material, electrode material, electrode slice, and application of grapheme electrode active material
CN102354613A (en) * 2011-09-14 2012-02-15 中国第一汽车股份有限公司 Electrode material of supercapacitor and preparation method for electrode material
CN102340005A (en) * 2011-10-09 2012-02-01 上海大学 Preparation method of lithium manganous silicate/graphene composite lithium ion cathode material
CN102502609A (en) * 2011-11-10 2012-06-20 东华大学 Method for preparing graphene hollow microspheres for anisotropic conductive materials
CN102786048A (en) * 2012-08-22 2012-11-21 深圳市斯诺实业发展有限公司永丰县分公司 Method for preparing conductive additive for lithium ion batteries
CN103833009A (en) * 2012-11-23 2014-06-04 海洋王照明科技股份有限公司 Graphene, its preparation method, electrode slice and supercapacitor
US9959946B2 (en) 2012-12-03 2018-05-01 Boe Technology Group Co., Ltd. Conductive graphene-metal composite material, the production method of the same and use of the same
CN103000245A (en) * 2012-12-03 2013-03-27 京东方科技集团股份有限公司 Graphene metal hybrid electrode material and preparation method and applications thereof
CN103000245B (en) * 2012-12-03 2015-09-23 京东方科技集团股份有限公司 A kind of graphene metal hybrid electrode material, its preparation method, application and substrate
CN103232458A (en) * 2013-04-25 2013-08-07 大连理工大学 Method for preparing graphite phase carbon nitride material with monatomic layer structure
CN103387229A (en) * 2013-07-23 2013-11-13 哈尔滨工业大学 A preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell
CN103387229B (en) * 2013-07-23 2015-03-18 哈尔滨工业大学 A preparation method for porous graphene and a preparation method for a graphene-based aluminium-air cell
CN104795535A (en) * 2015-04-01 2015-07-22 广东烛光新能源科技有限公司 Electrochemical energy storing component and preparation method thereof
CN107615526A (en) * 2015-06-05 2018-01-19 罗伯特·博世有限公司 Sulphur carbon composite comprising micropore carbon nanosheet for lithium-sulfur cell and preparation method thereof
CN107615526B (en) * 2015-06-05 2021-01-12 罗伯特·博世有限公司 Sulfur-carbon composite material comprising microporous carbon nanoplatelets for lithium-sulfur batteries and method for preparing same
CN109817382A (en) * 2017-11-21 2019-05-28 山东欧铂新材料有限公司 A kind of preparation method of high-stability graphene electrocondution slurry
CN111542953A (en) * 2018-01-26 2020-08-14 株式会社Lg化学 Conductive agent, slurry for forming electrode including the same, electrode, and lithium secondary battery manufactured using the same
CN110322986A (en) * 2018-03-29 2019-10-11 山东欧铂新材料有限公司 A kind of preparation method of high fluidity graphene conductive slurry
CN110322986B (en) * 2018-03-29 2021-06-29 山东欧铂新材料有限公司 Preparation method of high-fluidity graphene conductive paste
CN114730881A (en) * 2019-11-29 2022-07-08 日本黑铅工业株式会社 Conductive agent for electrode of lithium ion battery, composition for electrode, and electrode

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Application publication date: 20100609