CN103050704B - Porous conductive additive and preparation method thereof, lithium ion battery - Google Patents
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a porous conductive additive and a preparation method thereof. The porous conductive additive consists of graphene-based particles, having flaky particle shapes, the size distribution of 0.01-5 microns in a planar direction, the size distribution of 0.1-50 nanometers in a thickness direction, and through holes with the diameters of 1-1000 nanometers inside, with the porosity of 20-70%. The preparation method comprises the following steps of: dispersing a graphene-based material into a solvent to obtain a dispersion solution, adding a pore forming agent in a mass ratio of the pore forming agent to the graphene-based material of 0.1-1000, and performing ultrasonic treatment or mixing to obtain a uniform mixed solution; heating the mixed solution, removing the solvent, drying an obtained solid, and heating the solid in an oxygen-free protective atmosphere to obtain the porous conductive additive. The porous conductive additive has very high conductivity efficiency and can optimize a pore structure in an electrode and reduce ion conducting paths.
Description
Technical field
The present invention relates to secondary battery material and preparation method thereof, particularly relate to a kind of porous, electrically conductive additive and preparation method thereof, lithium ion battery.
Background technology
Along with secondary cell, if lithium ion battery is in the use in electric tool and new-energy automobile field, the power-performance of people to lithium ion battery proposes more and more higher requirement.Positive electrode due to lithium ion battery is inorganic semiconductor substantially, electronic conductivity is lower, in order to meet the instructions for use of lithium ion battery, in cell manufacturing process, in positive pole, usually add the good material of electric conductivity as conductive additive, according to the shape characteristic of current conductive additive, spherical conductive carbon black can be divided into, linear carbon nano-fiber, the electrically conductive graphite of CNT (carbon nano-tube) and sheet shape, the materials such as nanoscale twins graphite, these materials add the electronic conductivity that effectively can improve anode pole piece, but due to the material that above carbon-based conductive additive is all electrochemicaUy inert in positive pole, namely capacity can not be provided when lithium ion battery works, lithium ion battery weight can be caused on the contrary too much so add conductive additive too much, reduce its power density and energy density.And due to the high cost of partially conductive additive, battery manufacture cost when addition is excessive, also can be caused to increase.
The general principle of lithium ion battery work is that electronics enters into inside lithium ion cell by external circuit, and the electronic conduction network that the solid particle along inside is formed arrives at active material border, then with the lithium ion generation electrochemical reaction in electrolyte.After lithium ion near active material particle runs out of, the lithium ion at a distance in electrolyte needs to be diffused into reflecting point, to meet proceeding of electrochemical reaction.So concerning lithium ion battery, the transmittance process no less important of ion, in order to meet the high power performance of lithium ion battery, inside battery must have unobstructed ion transfer channels.Lithium ion is transmitted by electrolyte, so the pore structure of electrode interior (comprising porosity and hole tortuosity) directly can affect the transmission of lithium ion.Conductive additive add the pore structure that membership affects electrode interior to a great extent.First, conductive additive particle can occupy the hole of electrode interior, causes porosity, reduces the content of lithium ion in electrode; Meanwhile, flap-type conductive additive add the increase that also can cause hole tortuosity, delay the diffusion of lithium ion.
Summary of the invention
Technical problem to be solved by this invention is: make up above-mentioned the deficiencies in the prior art, proposes a kind of porous, electrically conductive additive and preparation method thereof, lithium ion battery.This porous, electrically conductive additive has very high electrical efficiency, and can optimize the pore structure in electrode, reduces the path of ionic conduction; Preparation method's technique is simple, and energy consumption is little, is applicable to very much the extensive preparation of technical grade.
Technical problem of the present invention is solved by following technical scheme:
A kind of porous, electrically conductive additive, it is graphene-based particle, the shape of particle of described graphene-based particle is sheet shape, particle distribution of sizes is in the in-plane direction between 0.01-5 μm, particle distribution of sizes is in a thickness direction between 0.1-50nm, inside particles is distributed with the through hole that diameter is 1-1000nm, and the porosity of described through hole is 20%-70%.
Owing to adopting above technical scheme, conductive additive inherits all features of graphene-based material in electrical conductivity, such as " face-point " contact mode, excellent electronic conductivity etc., so have very high electrical efficiency, the positive pole diaphragm of secondary cell as lithium ion battery can be applied to, cathode membrane and other exist among the conduction system of electronic conductance and ionic conductance in conducting process simultaneously, the job requirement of secondary cell just can be met when conductive additive addition of the present invention is less, the inside particles of this conductive additive has some diameters to be the through hole of 1-1000nm simultaneously, transmission for ion provides new approach, compared with conventional conductive additive, ion can pass these through holes in transmittance process, porous, electrically conductive additive joins after in electrode can not produce larger obstruction to the transmittance process of ion, porous, electrically conductive additive has higher electronic conductivity and lower conductivity threshold simultaneously, can easily at the efficient electronic conduction network of electrode material Internal architecture, optimize the pore structure in electrode, decrease the path of ionic conduction.
Preferably, the effective resistivity of described porous, electrically conductive additive is not more than 5m Ω cm.
Preferably, the specific area of described conductive additive is 5-2600m
2/ g.
Preferably, described graphene-based particle is Graphene particle or their combination of graphene oxide particle, Graphene particle or functionalization.
A preparation method for above-mentioned porous, electrically conductive additive, comprises the following steps:
(1) by graphene-based dispersion of materials in a solvent, obtain the dispersion soln of graphene-based material, then add pore creating material, the mass ratio of pore creating material and graphene-based material is 0.1-1000, ultrasonic or stir after obtain uniform mixed solution;
(2) mixed solution that step (1) obtains is heated a period of time; heating-up temperature is 40-100 DEG C; time is 0.5-100 h; pore creating material is fully mixed with graphene-based material; then remove described solvent, by after the solid drying that obtains, under the protective atmosphere of anaerobic, heat 0.5-20 h; heating-up temperature is 400-1500 DEG C, thus obtains described porous, electrically conductive additive.
Can chemical reaction be there is and be etched in the metal ion in the carbon atom of graphene-based material surface and pore creating material, graphene-based material leaves a large amount of holes, by the control of each technological parameter, described conduction interpolation is made to have aforesaid feature, the method technique preparing this conductive additive is simple, energy consumption is little, is applicable to very much the extensive preparation of technical grade.
Preferably, the described graphene-based material described in step (1) is Graphene or their combination of graphene oxide, Graphene or functionalization.
Preferably, before mixed solution being heated in described step (2), also comprise: in the mixed solution that step (1) obtains, add alkali lye the pH of mixed solution is adjusted to alkaline pH=8-14, then add a certain amount of reducing agent, the mass ratio of reducing agent and graphene-based material is 0.5-10.
Preferably, described reducing agent is organic or inorganic reducing agent; Wherein organic reducing agent optimization citric acid, vitamin C, hydrazine hydrate, theophylline, ethylene glycol, aniline, phenol, toluene or acetaldehyde; The preferred divalent iron salt of inorganic reducing agent, halogen acids, lithium hydroxide, sodium borohydride, stannous salt, iron powder, zinc powder or aluminium powder.
Add the oxygen-containing functional group that reducing agent can reduce graphene-based material, improve the regularity of graphene-based material, thus improve graphene-based material and obtain electron conduction.
Preferably, the pore creating material described in step (1) is metallic salt or metal oxide.
Preferably, in described step (1), the mass ratio of pore creating material and graphene-based material is 1 ~ 100.
A kind of lithium ion battery, comprises positive pole, negative pole, electrolyte, barrier film, collector and battery case, is added with above-mentioned porous, electrically conductive additive in described positive pole and/or negative pole.
Porous, electrically conductive additive is that the transmission of lithium ion provides new approach, optimize the pore structure in electrode, decrease the path of ionic conduction, effectively can reduce the mass transfer polarization of inside battery, thus give the good high power performance of lithium ion battery and cycle performance, experiment proves to use the lithium ion battery of porous, electrically conductive additive to have good power-performance and energy characteristics.
Accompanying drawing explanation
Fig. 1 is the stereoscan photograph of the conductive additive in the embodiment of the present invention 3;
Fig. 2 is the transmission electron microscope photo of the conductive additive in the embodiment of the present invention 4.
Embodiment
Below in conjunction with preferred embodiment, the present invention is explained in detail.
The invention provides a kind of porous, electrically conductive additive, in one embodiment, it is graphene-based particle, the shape of particle of described graphene-based particle is sheet shape, particle distribution of sizes is in the in-plane direction between 0.01-5 μm, particle distribution of sizes is in a thickness direction between 0.1-50nm, and inside particles is distributed with the through hole that diameter is 1-1000nm, and the porosity of through hole is 20%-70%.
Conductive additive is sheet shape, and the size on its thickness direction is less than on in-plane.
Preferably, the effective resistivity of described porous, electrically conductive additive is not more than 5m Ω cm.
Preferably, the specific area of described conductive additive is 5-2600m
2/ g.
Preferably, described graphene-based particle is Graphene particle or their combination of graphene oxide particle, Graphene particle or functionalization.
The present invention also provides a kind of preparation method of above-mentioned porous, electrically conductive additive, in one embodiment, comprises the following steps:
(1) by graphene-based dispersion of materials in solvent (preferred water), obtain the dispersion soln of graphene-based material, then add pore creating material, the mass ratio of pore creating material and graphene-based material is 0.1-1000, ultrasonic or stir after obtain uniform mixed solution;
(2) mixed solution that step (1) obtains is heated a period of time; heating-up temperature is 40-100 DEG C; time is 0.5-100 h; pore creating material is fully mixed with graphene-based material; then remove described solvent (as evaporation of solvent), by after solid (mixture of graphene-based material and the pore creating material) drying that obtains, under the protective atmosphere of anaerobic, (as nitrogen or argon gas) heats 0.5-20 h; heating-up temperature is 400-1500 DEG C, obtains described porous, electrically conductive additive.
Preferably, the described graphene-based material described in step (1) is Graphene or their combination of graphene oxide, Graphene or functionalization.
Preferably, before mixed solution being heated in described step (2), also comprise: in the mixed solution that step (1) obtains, add alkali lye the pH of mixed solution is adjusted to 8-14, then add a certain amount of reducing agent, the mass ratio of reducing agent and graphene-based material is 0.5-10; Preferably, described reducing agent is organic or inorganic reducing agent; Wherein organic reducing agent optimization citric acid, vitamin C, hydrazine hydrate, theophylline, ethylene glycol, aniline, phenol, toluene or acetaldehyde; The preferred divalent iron salt of inorganic reducing agent, halogen acids, lithium hydroxide, sodium borohydride, stannous salt, iron powder, zinc powder or aluminium powder.
Preferably, the pore creating material described in step (1) is metallic salt or metal oxide, as molysite, manganese salt, permanganate etc.
Preferably, in described step (1), the mass ratio of pore creating material and graphene-based material is 1 ~ 100.
The present invention also provides a kind of lithium ion battery, comprises positive pole, negative pole, electrolyte, barrier film, collector and battery case, is added with above-mentioned porous, electrically conductive additive in described positive pole and/or negative pole.
Wherein, the active material of positive pole comprises the cobalt acid lithium used in current commercialization battery, LiMn2O4, LiFePO4, rich lithium manganese, other positive electrode etc. used in 5V high voltage material and lithium ion battery, the active material of negative pole comprises traditional graphite type material, soft carbon/hard carbon, lithium titanate, other negative material etc. used in silicon and metal oxide materials and lithium ion battery, the barrier film simultaneously using traditional lithium-ion battery to use and electrolyte, this battery when conductive additive addition is little energy and power density higher than the battery with wide variety of conventional conductive additive.
Below by way of embodiment more specifically, the present invention will be described in detail.
embodiment 1
A kind of conductive additive, it is graphite oxide thiazolinyl particle, and shape of particle is sheet shape, is of a size of 1-3 μm in the in-plane direction, and specific area is 1300m
2/ g, is of a size of 0.5-5nm in a thickness direction, and the diameter of through hole is 1-800nm, and the porosity of through hole is 25%, and effective resistivity is 4.6 m Ω .cm.Its preparation method is as follows:
First 20g graphene oxide composite material is dispersed in water, obtains the dispersion soln of graphene oxide composite material; Add 20g Fe (NO
3)
3after ultrasonic disperse is even, add ammoniacal liquor and pH value of solution is adjusted to 8, then the citric acid of 50g is added, above-mentioned solution being heated 40 h at 80 DEG C, then evaporating except anhydrating, after solid (mixture of pore creating material and the graphene oxide composite material after the reducing) drying obtained, heat 3 h under an argon atmosphere, heating-up temperature is 800 DEG C, obtains the conductive additive with loose structure.
According to 5%(mass fraction) PVDF, 3%(mass fraction) porous, electrically conductive additive, 92%(mass fraction) LiFePO
4composition and ratio mixed pulp, be applied to the post-drying on aluminium foil, roll-in, cutting, reel, enter shell with scribbling together with the aluminium foil of graphite cathode, barrier film, then in glove box, inject electrolyte.Take out after sealing, carry out test after shelving 24 hours and obtain: be 128 mAh/g when positive electrode capacity is 132mAh/g, 10C during 5C electric discharge.
embodiment 2
a kind of conductive additive, it is the functionalization graphene base particle crossed with N doping vario-property, and shape of particle is sheet shape, is of a size of 0.8-3 μm in the in-plane direction, and specific area is 900m
2/ g, is of a size of 0.2-3nm in a thickness direction, and the diameter of through hole is 5-780nm, and the porosity of through hole is 35%, and effective resistivity is 4.3 m Ω .cm.Its preparation method is as follows:
First the functionalization graphene dispersion of materials crossed by 1.8g N doping vario-property, in water, obtains the dispersion soln of the functionalization graphene material crossed with N doping vario-property; Add 180g FeCl
3after ultrasonic 1h mixes, add ammoniacal liquor and pH value of solution is adjusted to 9, then the vitamin C of 18g is added, above-mentioned solution being heated 25h at 85 DEG C, then evaporating except anhydrating, after the solid that obtains (mixture of the grapheme material after pore creating material and reduction treatment) drying, heat 5 h in a nitrogen atmosphere, heating-up temperature is 1100 DEG C, obtains the conductive additive with loose structure.By 5%(mass fraction) PVDF, 2%(mass fraction) porous, electrically conductive additive, 93%(mass fraction) LiNi
1/3co
1/3mn
1/3o
2mixed pulp, be applied on aluminium foil dry, roll-in, reel with scribbling together with the aluminium foil of graphite cathode, barrier film, then in glove box, inject electrolyte.Shelve 24 hours after taking-up, carry out test and obtain: be 124 mAh/g when positive electrode capacity is 136mAh/g, 10C during 5C electric discharge.
embodiment 3
A kind of conductive additive, it is graphene-based particle, and shape of particle is sheet shape, is of a size of 0.5-4.3 μm in the in-plane direction, and specific area is 800m
2/ g, is of a size of 0.6-30nm in a thickness direction, and the diameter of through hole is 10-870nm, and the porosity of through hole is 40%, and effective resistivity is 4 m Ω .cm.Its preparation method is as follows:
First 2.5g grapheme material is dispersed in water, obtains the dispersion soln of grapheme material; Add 125g KMnO
4after ultrasonic 1h mixes, add ammoniacal liquor and pH value of solution is adjusted to 12, then adding the ethylene glycol of 20g, above-mentioned solution is heated 12 h at 90 DEG C, then evaporating except anhydrating, 6 h are heated under an argon atmosphere after the solid that obtains (grapheme material after pore creating material and reduction treatment) drying, heating-up temperature is 1300 DEG C, obtains the conductive additive with loose structure, and its stereoscan photograph as shown in Figure 1.
By 5%(mass fraction) PVDF, 1%(mass fraction) porous, electrically conductive additive, 94% (mass fraction) Delanium mixed pulp, be applied on Copper Foil dry, roll-in, and scribble LiFePO
4aluminium foil, the barrier film of positive pole reel together, then in glove box, inject electrolyte.Shelve 24 hours after taking-up, carry out test and obtain: be 260 mAh/g when capacity of negative plates is 300mAh/g, 10C during 5C electric discharge.
embodiment 4
A kind of conductive additive, it is graphite oxide thiazolinyl particle, and shape of particle is sheet shape, is of a size of 0.6-4 μm in the in-plane direction, and specific area is 800m
2/ g, is of a size of 2-35nm in a thickness direction, and the diameter of through hole is 2-500nm, and the porosity of through hole is 50%, and effective resistivity is 4.2 m Ω .cm.Its preparation method is as follows:
First 15g graphene oxide composite material is dispersed in water, obtains the dispersion soln of grapheme material; Add 5g Co
3o
4after ultrasonic 1h mixes, add ammoniacal liquor and solution is adjusted to 12, then adding the hydrazine hydrate of 7.5 g, above-mentioned solution is added hot reflux 20h at 90 DEG C, then evaporating except anhydrating, 15 h are heated under an argon atmosphere after the solid that obtains (graphene oxide composite material after pore creating material and reduction treatment) drying, heating-up temperature is 850 DEG C, obtains the conductive additive with loose structure, and its transmission electron microscope photo as shown in Figure 2.
By 5% (mass fraction) PVDF, 1%(mass fraction) porous, electrically conductive additive, 94% (mass fraction) Delanium mixed pulp, be applied to oven dry, roll-in on Copper Foil, reel with scribbling together with the aluminium foil of LiFePO4 positive pole, barrier film, then in glove box, inject electrolyte.Shelve 24 hours after taking-up, carry out test and obtain: 260 mAh/g when capacity of negative plates is 300mAh/g, 10C during 5C electric discharge.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that specific embodiment of the invention is confined to these explanations.For general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, make some equivalent to substitute or obvious modification, and performance or purposes identical, all should be considered as belonging to protection scope of the present invention.
Claims (13)
1. a porous, electrically conductive additive, it is characterized in that: described porous, electrically conductive additive is graphene-based particle, the shape of particle of described graphene-based particle is sheet shape, particle distribution of sizes is in the in-plane direction between 0.01-5 μm, particle distribution of sizes is in a thickness direction between 0.1-50nm, inside particles is distributed with the through hole that diameter is 1-1000nm, and the porosity of described through hole is 20%-70%; Described porous, electrically conductive additive is obtained by following steps: (1) by graphene-based dispersion of materials in a solvent, obtain the dispersion soln of graphene-based material, then pore creating material is added, the mass ratio of pore creating material and graphene-based material is 0.1-1000, ultrasonic or stir after obtain uniform mixed solution; (2) mixed solution that step (1) obtains is heated a period of time; heating-up temperature is 40-100 DEG C; time is 0.5h-100h; pore creating material is fully mixed with graphene-based material; then described solvent is removed; by after the solid drying that obtains; 0.5-20h is heated under the protective atmosphere of anaerobic; heating-up temperature is 400-1500 DEG C; metal ion generation chemical reaction in the carbon atom of graphene-based material surface and pore creating material and being etched; graphene-based material leaves a large amount of holes, obtains described porous, electrically conductive additive.
2. porous, electrically conductive additive according to claim 1, is characterized in that: the effective resistivity of described porous, electrically conductive additive is not more than 5m Ω cm.
3. porous, electrically conductive additive according to claim 1, is characterized in that: the specific area of described conductive additive is 5-2600m
2/ g.
4. porous, electrically conductive additive according to claim 1, is characterized in that: described graphene-based particle is Graphene particle or their combination of Graphene particle or functionalization.
5. a preparation method for porous, electrically conductive additive, is characterized in that, comprises the following steps:
(1) by graphene-based dispersion of materials in a solvent, obtain the dispersion soln of graphene-based material, then add pore creating material, the mass ratio of pore creating material and graphene-based material is 0.1-1000, ultrasonic or stir after obtain uniform mixed solution;
(2) mixed solution that step (1) obtains is heated a period of time, heating-up temperature is 40-100 DEG C, time is 0.5h-100h, pore creating material is fully mixed with graphene-based material, then described solvent is removed, by after the solid drying that obtains, 0.5-20h is heated under the protective atmosphere of anaerobic, heating-up temperature is 400-1500 DEG C, metal ion generation chemical reaction in the carbon atom of graphene-based material surface and pore creating material and being etched, graphene-based material leaves a large amount of holes, obtain described porous, electrically conductive additive, described porous, electrically conductive additive is graphene-based particle, the shape of particle of described graphene-based particle is sheet shape, particle distribution of sizes is in the in-plane direction between 0.01-5 μm, particle distribution of sizes is in a thickness direction between 0.1-50nm, inside particles is distributed with the through hole that diameter is 1-1000nm, the porosity of described through hole is 20%-70%.
6. the preparation method of porous, electrically conductive additive according to claim 5, is characterized in that, the described graphene-based material described in step (1) is Graphene or their combination of Graphene or functionalization.
7. the preparation method of the porous, electrically conductive additive according to claim 5 or 6, it is characterized in that: before in described step (2), mixed solution being heated, also comprise: in the mixed solution that step (1) obtains, add alkali lye the pH of mixed solution is adjusted to 8-14, then add a certain amount of reducing agent, the mass ratio of reducing agent and graphene-based material is 0.5-10.
8. the preparation method of porous, electrically conductive additive according to claim 7, is characterized in that: described reducing agent is organic or inorganic reducing agent.
9. the preparation method of porous, electrically conductive additive according to claim 8, is characterized in that: described organic reducing agent is citric acid, vitamin C, hydrazine hydrate, theophylline, ethylene glycol, aniline, phenol, toluene or acetaldehyde.
10. the preparation method of porous, electrically conductive additive according to claim 8, is characterized in that: described inorganic reducing agent is divalent iron salt, halogen acids, lithium hydroxide, sodium borohydride, stannous salt, iron powder, zinc powder or aluminium powder.
The preparation method of 11. porous, electrically conductive additives according to claim 8, is characterized in that: the pore creating material described in step (1) is metallic salt or metal oxide.
The preparation method of 12. porous, electrically conductive additives according to claim 5 or 6, is characterized in that: in described step (1), the mass ratio of pore creating material and graphene-based material is 1 ~ 100.
13. 1 kinds of lithium ion batteries, comprise positive pole, negative pole, electrolyte, barrier film, collector and battery case, it is characterized in that: in described positive pole and/or negative pole, be added with porous, electrically conductive additive according to claim 1.
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| CN201210582083.0A CN103050704B (en) | 2012-12-28 | 2012-12-28 | Porous conductive additive and preparation method thereof, lithium ion battery |
| HK13106687.0A HK1179761A1 (en) | 2012-12-28 | 2013-06-05 | Porous electrically conductive additive and method thereof, lithium ion battery |
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| TW201515994A (en) * | 2013-10-28 | 2015-05-01 | Enerage Inc | Nano-graphene hollow particles and manufacturing method thereof |
| CN103570011B (en) * | 2013-10-28 | 2015-10-07 | 复旦大学 | A kind of preparation method of porous graphene material of nitrogen-phosphor codoping |
| CN103663438B (en) * | 2013-11-18 | 2016-01-27 | 南京久和纳米科技有限公司 | A kind of preparation method of porous graphene |
| CN103787326B (en) * | 2014-03-06 | 2015-06-17 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
| US10654721B2 (en) * | 2015-09-18 | 2020-05-19 | Toray Industries, Inc. | Graphene dispersion, process for producing same, process for producing particles of graphene/active material composite, and process for producing electrode paste |
| KR102160710B1 (en) | 2017-07-04 | 2020-09-28 | 주식회사 엘지화학 | Electrode and Lithium Secondary Battery Comprising the Same |
| CN107482222A (en) * | 2017-09-05 | 2017-12-15 | 深圳市比克动力电池有限公司 | Combined conductive agent, electrodes of lithium-ion batteries and lithium ion battery |
| CN108470625A (en) * | 2018-01-29 | 2018-08-31 | 广东明路电力电子有限公司 | Micropore conduction sheet electrodes and its processing technology |
| CN108306007B (en) * | 2018-01-31 | 2021-04-06 | 天津大学 | Method for improving negative electrode surface loading capacity of nano silicon of lithium ion battery by adopting sulfur template and hydrogen peroxide activation |
| CN109575745A (en) * | 2018-10-29 | 2019-04-05 | 徐冬 | A kind of earthing material conductive anti-corrosion coating and preparation method thereof |
| CN109728300B (en) * | 2018-12-27 | 2020-09-29 | 宁波杉元石墨烯科技有限公司 | Lithium battery conductive slurry containing different-defect graphene and preparation method thereof |
| CN112054205A (en) * | 2020-09-28 | 2020-12-08 | 成都玉龙化工有限公司 | Conductive additive and preparation method thereof |
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