CN103050704A - Porous conductive additive and preparation method thereof, lithium ion battery - Google Patents
Porous conductive additive and preparation method thereof, lithium ion battery Download PDFInfo
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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, such as the use of lithium ion battery in electric tool and new-energy automobile field, people have proposed more and more higher requirement to the power-performance of lithium ion battery.Because the positive electrode of lithium ion battery is inorganic semiconductor substantially, electronic conductivity is lower, in order to satisfy the instructions for use of lithium ion battery, usually in the battery preparation process, in positive pole, add the good material of electric conductivity as conductive additive, shape characteristic according to present conductive additive, can be divided into spherical conductive carbon black, linear carbon nano-fiber, the electrically conductive graphite of CNT (carbon nano-tube) and sheet shape, the materials such as nanoscale twins graphite, the adding of these materials can the Effective Raise anode pole piece electronic conductivity, but because above carbon back conductive additive all is the material of electrochemistry inertia in positive pole, namely when working, lithium ion battery can not provide capacity, can cause on the contrary lithium ion battery weight too much so add too much conductive additive, reduce its power density and energy density.And because the high cost of partially conductive additive also can cause the battery manufacture cost to increase when addition is excessive.
The basic principle of lithium ion battery work is that electronics enters into inside lithium ion cell by external circuit, and the electronic conduction network that forms along the solid particle of inside arrives at the active material interface, then with electrolyte in lithium ion generation electrochemical reaction.After near the active material particle lithium ion ran out of, the lithium ion in the electrolyte need to be diffused into reflecting point at a distance, to satisfy proceeding of electrochemical reaction.So, concerning lithium ion battery, the transmittance process no less important of ion, in order to satisfy the high power performance of lithium ion battery, inside battery must have unobstructed ion transport passage.Lithium ion is by the electrolyte transmission, so the pore structure of electrode interior (comprising porosity and hole tortuosity) can directly affect the transmission of lithium ion.Conductive additive add the pore structure that affiliation affects electrode interior to a great extent.At first, the conductive additive particle can occupy the hole of electrode interior, causes porosity, has reduced the content of lithium ion in the electrode; Simultaneously, the adding of sheet type conductive additive also can cause the increase of hole tortuosity, delays the diffusion of lithium ion.
Summary of the invention
Technical problem to be solved by this invention is: remedy above-mentioned the deficiencies in the prior art, propose 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 the electrode, reduces the path of ionic conduction; Preparation method's technique is simple, and energy consumption is little, is fit 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 in the distribution of sizes on the in-plane between 0.01-5 μ m, particle in the distribution of sizes on the 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 has been inherited all features of graphene-based material aspect electrical conductivity, " face-point " contact mode for example, excellent electronic conductivity etc., so have very high electrical efficiency, can be applied to the anodal diaphragm of secondary cell such as lithium ion battery, cathode membrane and other exist in conducting process among the conduction system of electronic conductance and ionic conductance simultaneously, just can satisfy the job requirement of secondary cell when conductive additive addition of the present invention is less, some diameters are arranged is the through hole of 1-1000nm to the inside particles of this conductive additive simultaneously, for the transmission of ion provides new approach, compare with conventional conductive additive, ion can pass these through holes in transmittance process, after joining in the electrode, the porous, electrically conductive additive can not produce larger obstruction to the transmittance process of ion, the porous, electrically conductive additive has higher electronic conductivity and lower conductivity threshold simultaneously, can be at an easy rate at the efficient electronic conduction network of electrode material Internal architecture, optimized the pore structure in the electrode, the path of having reduced 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 the Graphene particle of graphene oxide particle, Graphene particle or functionalization or their combination.
A kind of preparation method of above-mentioned porous, electrically conductive additive may further comprise the steps:
(1) with graphene-based dispersion of materials in 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) the mixed solution heating a period of time that step (1) is obtained; heating-up temperature is 40-100 ℃; time is 0.5-100 h; so that pore creating material fully mixes with graphene-based material; then remove described solvent, behind the solid drying that obtains, heating 0.5-20 h under the protective atmosphere of anaerobic; heating-up temperature is 400-1500 ℃, thereby obtains described porous, electrically conductive additive.
Chemical reaction can occur and be etched in the carbon atom of graphene-based material surface and the metal ion in the pore creating material, stay a large amount of holes at graphene-based material, control by each technological parameter, so that adding, described conduction has aforesaid feature, the method technique for preparing this conductive additive is simple, energy consumption is little, is fit to very much the extensive preparation of technical grade.
Preferably, the described described graphene-based material of step (1) Graphene that is graphene oxide, Graphene or functionalization or their combination.
Preferably, in described step (2) with before the mixed solution heating, also comprise: interpolation alkali lye is adjusted to alkaline pH=8-14 with the pH of mixed solution in the mixed solution that step (1) obtains, 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 the 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.
The adding reducing agent can reduce the oxygen-containing functional group of graphene-based material, improves the regularity of graphene-based material, gets electron conduction thereby improve graphene-based material.
Preferably, the described pore creating material of step (1) is metallic salt or metal oxide.
Preferably, the mass ratio of pore creating material and graphene-based material is 1 ~ 100 in the described step (1).
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.
The porous, electrically conductive additive provides new approach for the transmission of lithium ion, optimized the pore structure in the electrode, reduced the path of ionic conduction, can effectively reduce the mass transfer polarization of inside battery, thereby give the good high power performance of lithium ion battery and cycle performance, experimental results show that and use the lithium ion battery of porous, electrically conductive additive to have good power-performance and energy characteristics.
Description of drawings
Fig. 1 is the stereoscan photograph of the conductive additive in the embodiment of the invention 3;
Fig. 2 is the transmission electron microscope photo of the conductive additive in the embodiment of the 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 in the distribution of sizes on the in-plane between 0.01-5 μ m, between 0.1-50nm, inside particles is distributed with the through hole that diameter is 1-1000nm to particle in the distribution of sizes on the thickness direction, 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 the 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 the Graphene particle of graphene oxide particle, Graphene particle or functionalization or their combination.
The present invention also provides a kind of preparation method of above-mentioned porous, electrically conductive additive, in one embodiment, may further comprise the steps:
(1) with 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) the mixed solution heating a period of time that step (1) is obtained; heating-up temperature is 40-100 ℃; time is 0.5-100 h; so that pore creating material fully mixes with graphene-based material; then remove described solvent (such as the evaporation desolventizing), after solid (mixture of graphene-based material and the pore creating material) drying that obtains, (such as nitrogen or argon gas) heating 0.5-20 h under the protective atmosphere of anaerobic; heating-up temperature is 400-1500 ℃, obtains described porous, electrically conductive additive.
Preferably, the described described graphene-based material of step (1) Graphene that is graphene oxide, Graphene or functionalization or their combination.
Preferably, in described step (2) with before the mixed solution heating, also comprise: interpolation alkali lye is adjusted to 8-14 with the pH of mixed solution in the mixed solution that step (1) obtains, and then adds a certain amount of reducing agent, and the mass ratio of reducing agent and graphene-based material is 0.5-10; Preferably, described reducing agent is the 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 described pore creating material of step (1) is metallic salt or metal oxide, such as molysite, manganese salt, permanganate etc.
Preferably, the mass ratio of pore creating material and graphene-based material is 1 ~ 100 in the described step (1).
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, anodal active material comprises employed cobalt acid lithium in the present commercialization battery, LiMn2O4, LiFePO4, rich lithium manganese, employed other positive electrode etc. in 5V high voltage material and the lithium ion battery, the active material of negative pole comprises traditional graphite type material, soft carbon/hard carbon, lithium titanate, employed other negative material etc. in silicon and metal oxide materials and the lithium ion battery, use simultaneously the employed barrier film of conventional lithium ion battery and electrolyte, this battery the conductive additive addition seldom the time energy and power density be higher than battery with the wide variety of conventional conductive additive.
Below the present invention will be described in detail by embodiment more specifically.
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 μ m on in-plane, and specific area is 1300m
2/ g is of a size of 0.5-5nm on thickness direction, 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:
At first with 20g graphene oxide dispersion of materials in water, obtain the dispersion soln of graphene oxide material; Add 20g Fe (NO
3)
3After ultrasonic being uniformly dispersed, add ammoniacal liquor pH value of solution is adjusted to 8, then the citric acid that adds 50g, at 80 ℃ of lower heating 40 h, then evaporation removes and anhydrates with mentioned solution, heats 3 h after the solid that obtains (mixture of the graphene oxide material after pore creating material and the reduction) is dry under argon gas atmosphere, heating-up temperature is 800 ℃, obtains having the conductive additive of loose structure.
According to the 5%(mass fraction) PVDF, 3%(mass fraction) porous, electrically conductive additive, 92%(mass fraction) LiFePO
4The composition and ratio mixed pulp, shell is reeled, entered to oven dry after being applied on the aluminium foil, roll-in, cutting with the aluminium foil that scribbles graphite cathode, barrier film, then inject electrolyte in glove box.Sealing is rear takes out, and shelves to test after 24 hours to obtain: positive electrode capacity is 132mAh/g during the 5C discharge, is 128 mAh/g during 10C.
Embodiment 2
A kind of conductive additive, its functionalization graphene base particle for crossing with the N doping vario-property, shape of particle is sheet shape, is of a size of 0.8-3 μ m on in-plane, and specific area is 900m
2/ g is of a size of 0.2-3nm on thickness direction, 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:
The functionalization graphene dispersion of materials of at first 1.8g being crossed with the N doping vario-property obtains the dispersion soln of the functionalization graphene material crossed with the N doping vario-property in water; Add 180g FeCl
3After ultrasonic 1h mixes, add ammoniacal liquor pH value of solution is adjusted to 9, then the vitamin C that adds 18g, at 85 ℃ of lower heating 25h, then evaporation is heated 5 h except anhydrating after the solid that obtains (mixture of the grapheme material after pore creating material is processed with reduction) is dry under nitrogen atmosphere with mentioned solution, heating-up temperature is 1100 ℃, obtains having the conductive additive of loose structure.With the 5%(mass fraction) PVDF, 2%(mass fraction) porous, electrically conductive additive, 93%(mass fraction) LiNi
1/3Co
1/3Mn
1/3O
2Mixed pulp is applied to oven dry, roll-in on the aluminium foil, reels with the aluminium foil that scribbles graphite cathode, barrier film, then injects electrolyte in glove box.Shelved after the taking-up 24 hours, and tested obtaining: positive electrode capacity is 136mAh/g during the 5C discharge, is 124 mAh/g during 10C.
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 μ m on in-plane, and specific area is 800m
2/ g is of a size of 0.6-30nm on thickness direction, 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:
At first the 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 pH value of solution is adjusted to 12, then the ethylene glycol that adds 20g, at 90 ℃ of lower heating 12 h, then evaporation is except anhydrating with mentioned solution, under argon gas atmosphere, heat 6 h after the solid that obtains (grapheme material after pore creating material is processed with reduction) is dry, heating-up temperature is 1300 ℃, obtains having the conductive additive of loose structure, and its stereoscan photograph as shown in Figure 1.
With the 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 the Copper Foil, and scribble LiFePO
4Anodal aluminium foil, barrier film are reeled together, then inject electrolyte in glove box.Shelved after the taking-up 24 hours, and tested obtaining: capacity of negative plates is 300mAh/g during the 5C discharge, is 260 mAh/g during 10C.
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 μ m on in-plane, and specific area is 800m
2/ g is of a size of 2-35nm on thickness direction, 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:
At first with 15g graphene oxide dispersion of materials in water, obtain the dispersion soln of grapheme material; Add 5g Co
3O
4After ultrasonic 1h mixes, add ammoniacal liquor solution is adjusted to 12, then the hydrazine hydrate that adds 7.5 g adds hot reflux 20h with mentioned solution under 90 ℃, then evaporation is except anhydrating, under argon gas atmosphere, heat 15 h after the solid that obtains (the graphene oxide material after pore creating material is processed with reduction) is dry, heating-up temperature is 850 ℃, obtains having the conductive additive of loose structure, and its transmission electron microscope photo as shown in Figure 2.
With 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 the Copper Foil, reel with the aluminium foil that scribbles the LiFePO4 positive pole, barrier film, then in glove box, inject electrolyte.Shelved after the taking-up 24 hours, and tested obtaining: capacity of negative plates is 300mAh/g during the 5C discharge, 260 mAh/g during 10C.
Above content is in conjunction with concrete preferred implementation further description made for the present invention, can not assert that implementation of the present invention is confined to these explanations.For the general technical staff of the technical field of the invention, without departing from the inventive concept of the premise, make some being equal to substitute or obvious modification, and performance or purposes are identical, all should be considered as belonging to protection scope of the present invention.
Claims (10)
1. 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 in the distribution of sizes on the in-plane between 0.01-5 μ m, particle in the distribution of sizes on the 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%.
2. described porous, electrically conductive additive according to claim 1, it is characterized in that: the effective resistivity of described porous, electrically conductive additive is not more than 5m Ω cm.
3. described porous, electrically conductive additive according to claim 1, it is characterized in that: the specific area of described conductive additive is 5-2600m
2/ g.
4. described lithium ion battery porous, electrically conductive additive according to claim 1, it is characterized in that: described graphene-based particle is the Graphene particle of graphene oxide particle, Graphene particle or functionalization or their combination.
5. the preparation method of the described porous, electrically conductive additive of claim 1 ~ 4 any one is characterized in that, may further comprise the steps:
(1) with graphene-based dispersion of materials in 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) the mixed solution heating a period of time that step (1) is obtained; heating-up temperature is 40-100 ℃; time is 0.5h-100 h; so that pore creating material fully mixes with graphene-based material; then remove described solvent, behind the solid drying that obtains, heating 0.5-20 h under the protective atmosphere of anaerobic; heating-up temperature is 400-1500 ℃, obtains described porous, electrically conductive additive.
6. the preparation method of porous, electrically conductive additive according to claim 5 is characterized in that, the Graphene that the described described graphene-based material of step (1) is graphene oxide, Graphene or functionalization or their combination.
7. according to claim 5 or the preparation method of 6 described porous, electrically conductive additives, it is characterized in that: in described step (2) with before the mixed solution heating, also comprise: interpolation alkali lye is adjusted to 8-14 with the pH of mixed solution in the mixed solution that step (1) obtains, then add a certain amount of reducing agent, the mass ratio of reducing agent and graphene-based material is 0.5-10.
8. according to claim 5 or the preparation method of 6 described porous, electrically conductive additives, it is characterized in that: described reducing agent is the 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; The described pore creating material of step (1) is metallic salt or metal oxide.
9. it is characterized in that according to claim 5 or the preparation method of 6 described porous, electrically conductive additives: the mass ratio of pore creating material and graphene-based material is 1 ~ 100 in the described step (1).
10. a lithium ion battery comprises positive pole, negative pole, electrolyte, barrier film, collector and battery case, it is characterized in that: be added with porous, electrically conductive additive claimed in claim 1 in described positive pole and/or negative pole.
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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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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570011A (en) * | 2013-10-28 | 2014-02-12 | 复旦大学 | Method for preparing nitrogen and phosphorus codoped porous graphene material |
| CN103663438A (en) * | 2013-11-18 | 2014-03-26 | 南京久和纳米科技有限公司 | Preparation method of porous graphene |
| CN103787326A (en) * | 2014-03-06 | 2014-05-14 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
| CN104555994A (en) * | 2013-10-28 | 2015-04-29 | 安炬科技股份有限公司 | Hollow nano-graphene particles and method for making the same |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102515151A (en) * | 2011-12-22 | 2012-06-27 | 哈尔滨工程大学 | Porous graphene with stratified columnar support structure and its preparation method |
| CN102544502A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery |
| CN102583337A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Preparation method for graphene material with porous structure |
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
-
2012
- 2012-12-28 CN CN201210582083.0A patent/CN103050704B/en active Active
-
2013
- 2013-06-05 HK HK13106687.0A patent/HK1179761A1/en not_active IP Right Cessation
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102544502A (en) * | 2010-12-09 | 2012-07-04 | 中国科学院宁波材料技术与工程研究所 | Anode and cathode conductive additive for secondary lithium battery, method for preparing conductive additive, and method for preparing secondary lithium battery |
| CN102115069A (en) * | 2010-12-20 | 2011-07-06 | 中国石油大学(北京) | Graphene with porous structure and preparation method of graphene |
| CN102757036A (en) * | 2011-04-26 | 2012-10-31 | 海洋王照明科技股份有限公司 | Preparation method of porous graphene |
| CN102515151A (en) * | 2011-12-22 | 2012-06-27 | 哈尔滨工程大学 | Porous graphene with stratified columnar support structure and its preparation method |
| CN102583337A (en) * | 2012-01-20 | 2012-07-18 | 中国科学院上海硅酸盐研究所 | Preparation method for graphene material with porous structure |
Cited By (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103570011A (en) * | 2013-10-28 | 2014-02-12 | 复旦大学 | Method for preparing nitrogen and phosphorus codoped porous graphene material |
| CN104555994A (en) * | 2013-10-28 | 2015-04-29 | 安炬科技股份有限公司 | Hollow nano-graphene particles and method for making the same |
| 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 |
| CN103663438A (en) * | 2013-11-18 | 2014-03-26 | 南京久和纳米科技有限公司 | Preparation method of porous graphene |
| 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 |
| CN103787326A (en) * | 2014-03-06 | 2014-05-14 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
| CN103787326B (en) * | 2014-03-06 | 2015-06-17 | 南开大学 | Preparation method of grapheme material with three-dimensional network structure |
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| CN110800135A (en) * | 2017-07-04 | 2020-02-14 | 株式会社Lg化学 | Electrode and lithium secondary battery comprising the same |
| US11424441B2 (en) | 2017-07-04 | 2022-08-23 | Lg Energy Solution, Ltd. | Electrode and lithium secondary battery comprising same |
| CN110800135B (en) * | 2017-07-04 | 2022-08-30 | 株式会社Lg新能源 | 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 |
| CN108306007A (en) * | 2018-01-31 | 2018-07-20 | 天津大学 | The method that lithium ion cell nano silicium cathode face carrying capacity is improved using sulphur template and Activation of Hydrogen Peroxide Solution |
| 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 |
| CN109728300A (en) * | 2018-12-27 | 2019-05-07 | 宁波杉元石墨烯科技有限公司 | A kind of lithium battery electrocondution slurry and preparation method thereof containing different defect graphenes |
| 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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| HK1179761A1 (en) | 2013-10-04 |
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