CN104852049A - Modified soft carbon negative electrode material of lithium ion battery and preparation method thereof - Google Patents
Modified soft carbon negative electrode material of lithium ion battery and preparation method thereof Download PDFInfo
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- CN104852049A CN104852049A CN201410855276.8A CN201410855276A CN104852049A CN 104852049 A CN104852049 A CN 104852049A CN 201410855276 A CN201410855276 A CN 201410855276A CN 104852049 A CN104852049 A CN 104852049A
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- soft carbon
- lithium ion
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Abstract
The invention discloses a modified soft carbon negative electrode material of a lithium ion battery, which is characterized by doping graphene powder particles in soft carbon powder particles. Simultaneously, the load of the graphene powder particles is distributed in nanometer coating material coating on the surface layer of the soft carbon powder particles to form a nanometer conductive carbon layer. The preparation method comprises the steps as follows: mixing soft carbon raw material and graphene material and grinding the mixed material to 0.3-0.4 microns and then performing pre-burning; performing high-speed mixing for the pre-burned material and a conductive agent and a binder in solvent; performing heat treatment for the mixed soft carbon material under protective atmosphere after performing vacuum drying to obtain the modified soft carbon negative electrode material. The reversible specific capacity of the modified soft carbon negative electrode material prepared by the method is more than 360 mAh/g, while the efficiency is more than 85%. The modified soft carbon negative electrode material of the lithium ion battery has excellent fast lithium insertion/extraction capacity, and greatly improves rate capability and cycle performance.
Description
Technical field
The present invention relates to lithium ion battery negative material field, be specifically related to soft carbon negative pole material of a kind of novel high-capacity modification and preparation method thereof
Background technology
At present, commercial lithium-ion batteries negative material is mainly graphite-like material with carbon element, as Delanium, native graphite and carbonaceous mesophase spherules etc.But, graphite negative electrodes material, because its specific capacity lower (372mAh/g), high rate charge-discharge performance are not good and lithium deposits that the safety issue brought makes it more difficultly catch up with electronics miniaturization, the paces of the demand such as automobile-used and electric tool lithium ion battery is high-power, high power capacity, thus needs to research and develop the high-energy-density of alternative current graphite type material, high safety performance, long circulation life and can the Novel cathode material for lithium ion battery of high rate charge-discharge.
Soft carbon refers to easy graphited carbon, can graphited amorphous carbon under the high temperature more than 2500 DEG C.The degree of crystallinity (i.e. degree of graphitization) of soft carbon is low, crystallite dimension is little, interplanar distance (d002) is larger, good with the compatibility of electrolyte, output voltage is lower, thus there is cycle performance, high rate performance, security performance and high and low temperature advantage, therefore soft carbon is the power negative material preparing highly secure lithium ion dynamic battery negative pole great potential.The comparatively successful soft carbon negative pole material of power in the market, the main problem that there is first effect, capacity low (220mA/g), cannot enter the large-scale commercial stage, domestic association area is still in the pilot scale stage, not yet has the report that industrialization is correlated with.Therefore, the technical barrier that a kind of high power capacity, high first charge-discharge efficiency, the high rate performance simultaneously possessing excellence and cycle performance soft carbon class negative material are affiliated fields is developed.
Summary of the invention
For the deficiencies in the prior art, an object of the present invention is to provide the modification of a kind of novel high-capacity lithium ion battery soft carbon negative pole material, grapheme material simultaneously on the top layer coated one deck graphene-based high conductivity carbon coating layer of the soft carbon negative pole material of described modification owing to being doped with high conductivity in soft material with carbon element inside, therefore this kind of soft material with carbon element of modification has high power capacity and high first charge-discharge efficiency, possesses excellent high rate performance and cycle performance simultaneously.
The soft carbon negative pole material of a kind of lithium ion battery modification of the present invention, at soft carbon dust granule interior doped graphene powder particle, meanwhile, graphene powder Granular composite is carried in the nanometer clad material coating on described soft carbon dust particle top layer and forms conductive nano carbon-coating.Wherein, the particle diameter of described soft carbon dust particle is 1 ~ 30 μm.The thickness of described nanometer clad material coating is 10nm ~ 500nm, and content is 0.01 ~ 2wt%.
The preparation method of the soft carbon negative pole material of above-mentioned lithium ion battery modification that the present invention proposes, comprises the following steps:
Step one: be 0.1 ~ 2wt% according to grapheme material and soft carbon material rate, by soft carbon raw material and grapheme material mixing and stirring in a solvent, the granularity carrying out being ground to grapheme material and soft carbon raw material in sand mill all to reach after 0.3um ~ 4um in protective atmosphere between 300 ~ 1300 DEG C, pre-burning 1 ~ 24h, naturally cool to room temperature, obtain the soft material with carbon element after pre-burning;
Step 2: be (1 ~ 10) according to mass ratio by solvent, binding agent and conductive agent: (0.01 ~ 1): (0.01 ~ 1) mixes 1 ~ 10h in high-speed dispersing kettle;
Step 3: after 200-1000 mesh sieve that the soft material with carbon element after step one pre-burning is sieved, be 1:(1 ~ 10 according to the mass ratio of the soft material with carbon element after pre-burning and solvent, binding agent, conductive agent): (0.01 ~ 1): (0.01 ~ 1) dries 4 ~ 12h at 80 ~ 150 DEG C after joining in described high-speed dispersing kettle and stirring 1 ~ 10h in vacuum drying chamber, obtains powdery product;
Step 4: powder step 3 obtained puts into baking furnace after crossing 1000 mesh sieves, pass into between ramp to 600 ~ 1150 of 4-8 DEG C/min DEG C after protective gas, insulation 1 ~ 24h, naturally cools to room temperature, obtains the soft carbon negative pole material of modification.
Further, in step one, described soft carbon raw material is the combination of any one or at least two kinds in petroleum coke, petroleum needle coke, coal-based needle coke, non-graphitized carbonaceous mesophase spherules.
In step one and step 2, described solvent is the combination of any one or at least two kinds in water, ethanol, ether, acetone, methyl methacrylate, butyl acrylate, acrylic acid, isopropyl alcohol, butyl glycol ether, oxolane, benzene,toluene,xylene and dimethyl formamide.
In step 2, described binding agent is water-soluble or the material with adhesive property of organic solvent, comprising: the combination of any one or at least two kinds in sucrose, glucose, methylcellulose, polyvinyl alcohol, polyethylene glycol, phenolic resins, PVP, epoxy resin, polymethyl methacrylate, Kynoar and polyacrylonitrile.
In step 2, described conductive carbon material is one or more mixtures in grapheme material and SP, KS6, nickel-plating carbon nanotube, and wherein, grapheme material proportion is 30 ~ 50wt%.
Wherein, described protective atmosphere is one or more mixing in nitrogen, argon gas, neon, helium.
The soft material with carbon element of the modification that the present invention prepares is for the negative material of lithium ion battery.
The coated method of Graphene dopant conductive carbon material used due to the present invention has increased substantially the Lithium-ion embeding deintercalation speed of soft material with carbon element, make this kind material modifiedly to have high power capacity and high first charge-discharge efficiency, possess excellent high rate performance and cycle performance simultaneously.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the soft material with carbon element of modification that the embodiment of the present invention 1 prepares;
Fig. 2 is the partial enlarged drawing in Fig. 1;
Fig. 3 is the first charge-discharge curve chart of 2032 button cells of the soft material with carbon element making of modification that embodiment 1 prepares.
Embodiment
Tell about detailed process of the present invention by the following examples, provide embodiment to be convenience in order to understand, is never restriction the present invention.
Embodiment 1: the preparation of the soft carbon negative pole material of lithium ion battery modification
The mixing and stirring in methyl methacrylate solution by soft for 1000g carbon raw material and 10g grapheme material, carry out being ground to after granularity reaches 0.5um in sand mill, in protection nitrogen atmosphere between 800 DEG C, pre-burning 6h, naturally cools to room temperature.
Soft material with carbon element after pre-burning is crossed 500 mesh sieves mix 4h in high-speed dispersing kettle after and added in high-speed dispersing kettle by 4000g butyl acetate, 50g polymethyl methacrylate 20g Graphene, 20g carbon nickel-plating carbon nanotube, after stirring 2h, in vacuum drying chamber, dries 12h at 80 DEG C.Put into baking furnace after the powder of drying in vacuum drying oven is crossed 1000 mesh sieves, to be warming up between 1050 DEG C after passing into nitrogen atmosphere, insulation 24h, naturally cools to room temperature, obtains the soft carbon negative pole material of described modification;
Fig. 1 shows the SEM figure of the soft material with carbon element of modification that embodiment 1 prepares, and Fig. 2 is the partial enlarged drawing in Fig. 1, for checking the performance of the lithium ion battery negative material utilizing the present embodiment to prepare, using the soft carbon negative pole material of modification that obtains through the above-mentioned steps negative pole as lithium ion battery, using lithium sheet as positive pole, LiPF6-EC/DEC (1:1) is adopted to do electrolyte, assembling CR2032 type button cell, charging/discharging voltage is limited in 0-2.0V, current density 0.2C, 1C, 30C carries out discharge and recharge, test reversible capacity and first coulombic efficiency first, Fig. 3 is the first charge-discharge curve chart of 2032 button cells of the soft material with carbon element making of modification that embodiment 1 prepares, concrete test data is in table 1.
Embodiment 2: the preparation of the soft carbon negative pole material of lithium ion battery modification
The mixing and stirring in methyl methacrylate solution by soft for 1000g carbon raw material and 20g grapheme material, carry out being ground to after granularity reaches 0.5um in sand mill, in protection nitrogen atmosphere between 1000 DEG C, pre-burning 4h, naturally cools to room temperature.
After 2000g acrylic acid, 1000g isopropyl alcohol, 30g epoxy resin, 40g Graphene, 40gSP are mixed 8h in high-speed dispersing kettle, the soft material with carbon element after pre-burning being crossed 500 mesh sieves adds in high-speed dispersing kettle, dries 12h after stirring 4h in vacuum drying chamber at 120 DEG C.Put into baking furnace after the powder of drying in vacuum drying oven is crossed 1000 mesh sieves, to be warming up between 900 DEG C after passing into nitrogen atmosphere, insulation 18h, naturally cools to room temperature, obtains the soft carbon negative pole material of described modification.Concrete test data is in table 1.
Embodiment 3: the preparation of the soft carbon negative pole material of lithium ion battery modification
The mixing and stirring in butyl glycol ether solution by soft for 1000g carbon raw material and 10g grapheme material, carry out being ground to after granularity reaches 2um in sand mill, in protection nitrogen atmosphere between 600 DEG C, pre-burning 12h, naturally cools to room temperature.
After 3000g acetone, 10g PVP, 10g Graphene, 20gKS6 are mixed 10h in high-speed dispersing kettle, the soft material with carbon element after pre-burning being crossed 500 mesh sieves adds in high-speed dispersing kettle, dries 8h after stirring 8h in vacuum drying chamber at 120 DEG C.Put into baking furnace after the powder of drying in vacuum drying oven is crossed 1000 mesh sieves, to be warming up between 1200 DEG C after passing into nitrogen atmosphere, insulation 6h, naturally cools to room temperature, obtains the soft carbon negative pole material of described modification.Concrete test data is in table 1.
The electric performance test result table of table 1 embodiment 1-3
| Embodiment | Reversible capacity mAh/g first | Coulombic efficiency first | 30C/1C | 1C1000 week capability retention |
| 1 | 351.9 | 88.9％ | 96.5％ | 90.9％ |
| 2 | 385.8 | 91.15％ | 97.3％ | 88.7％ |
| 3 | 339.4 | 84.6％ | 92.1％ | 90.5％ |
From above test result, the soft carbon negative pole material of lithium ion battery modification utilizing the inventive method to prepare, capacity, first coulombic efficiency soft carbon products more in the market significantly improves first, has excellent quick lithium storage performance and cycle performance.In conjunction with high safety performance and the high and low temperature advantage of soft carbon itself, the soft carbon of modification of the present invention prepares the power negative material that highly secure lithium ion dynamic battery negative pole has competitiveness, and market potential is huge.
Give the alternative multiple concrete material of described soft carbon raw material, solvent, conductive agent and protective atmosphere in the preparation process in accordance with the present invention; adopt different selections can not produce the impact of essence to obtained soft material with carbon element; therefore, without the need to containing the embodiment of all various selections.
Although invention has been described by reference to the accompanying drawings above; but the present invention is not limited to above-mentioned embodiment; above-mentioned embodiment is only schematic; instead of it is restrictive; such as: those of ordinary skill in the art is under enlightenment of the present invention; when not departing from present inventive concept, can also make a lot of distortion, these all belong within protection of the present invention.
Claims (9)
1. the soft carbon negative pole material of lithium ion battery modification, it is characterized in that, at soft carbon dust granule interior doped graphene powder particle, meanwhile, graphene powder Granular composite is carried in the nanometer clad material coating on described soft carbon dust particle top layer and forms conductive nano carbon-coating.
2. the soft carbon negative pole material of lithium ion battery modification according to claim 1, is characterized in that, the particle diameter of described soft carbon dust particle is 1 ~ 30 μm.
3. the soft carbon negative pole material of lithium ion battery modification according to claim 1, is characterized in that, the thickness of described nanometer clad material coating is 10nm ~ 500nm, and content is 0.01 ~ 2wt%.
4. a preparation method for the soft carbon negative pole material of lithium ion battery modification as claimed in claim 1, comprises the following steps:
Step one: be 0.1 ~ 2wt% according to grapheme material and soft carbon material rate, by soft carbon raw material and grapheme material mixing and stirring in a solvent, the granularity carrying out being ground to grapheme material and soft carbon raw material in sand mill all to reach after 0.3um ~ 4um in protective atmosphere between 300 ~ 1300 DEG C, pre-burning 1 ~ 24h, naturally cool to room temperature, obtain the soft material with carbon element after pre-burning;
Step 2: be (1 ~ 10) according to mass ratio by solvent, binding agent and conductive agent: (0.01 ~ 1): (0.01 ~ 1) mixes 1 ~ 10h in high-speed dispersing kettle;
Step 3: after 200-1000 mesh sieve that the soft material with carbon element after step one pre-burning is sieved, be 1:(1 ~ 10 according to the mass ratio of the soft material with carbon element after pre-burning and solvent, binding agent, conductive agent): (0.01 ~ 1): (0.01 ~ 1) dries 4 ~ 12h at 80 ~ 150 DEG C after joining in described high-speed dispersing kettle and stirring 1 ~ 10h in vacuum drying chamber, obtains powdery product;
Step 4: powder step 3 obtained puts into baking furnace after crossing 1000 mesh sieves, pass into between ramp to 600 ~ 1150 of 4-8 DEG C/min DEG C after protective gas, insulation 1 ~ 24h, naturally cools to room temperature, obtains the soft carbon negative pole material of modification.
5. the preparation method of the soft carbon negative pole material of lithium ion battery modification according to claim 4, in step one, described soft carbon raw material is the combination of any one or at least two kinds in petroleum coke, petroleum needle coke, coal-based needle coke, non-graphitized carbonaceous mesophase spherules.
6. the preparation method of the soft carbon negative pole material of lithium ion battery modification according to claim 4, in step one and step 2, described solvent is the combination of any one or at least two kinds in water, ethanol, ether, acetone, methyl methacrylate, butyl acrylate, acrylic acid, isopropyl alcohol, butyl glycol ether, oxolane, benzene,toluene,xylene and dimethyl formamide.
7. the preparation method of the soft carbon negative pole material of lithium ion battery modification according to claim 4, in step 2, described binding agent is water-soluble or the material with adhesive property of organic solvent, comprising: the combination of any one or at least two kinds in sucrose, glucose, methylcellulose, polyvinyl alcohol, polyethylene glycol, phenolic resins, PVP, epoxy resin, polymethyl methacrylate, Kynoar and polyacrylonitrile.
8. the preparation method of the soft carbon negative pole material of lithium ion battery modification according to claim 4, in step 2, described conductive agent is one or more mixtures in grapheme material and SP, KS6, nickel-plating carbon nanotube, and wherein, grapheme material proportion is 30 ~ 50wt%.
9. the preparation method of the soft carbon negative pole material of lithium ion battery modification according to claim 4, wherein, described protective atmosphere is one or more mixing in nitrogen, argon gas, neon, helium.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107293697A (en) * | 2017-07-26 | 2017-10-24 | 大连宏光锂业股份有限公司 | A kind of power-type lithium ion battery negative material production method |
| CN110429278A (en) * | 2019-07-10 | 2019-11-08 | 中盐安徽红四方锂电有限公司 | A kind of negative electrode slurry and preparation method thereof for low temp lithium ion battery |
| CN110521028A (en) * | 2018-03-22 | 2019-11-29 | Tdk株式会社 | Cathode and lithium ion secondary battery |
| CN110581275A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | Graphene/soft carbon negative electrode material of lithium ion battery, preparation method of graphene/soft carbon negative electrode material and lithium ion battery |
| CN116022783A (en) * | 2023-01-09 | 2023-04-28 | 南阳天成新能源科技有限公司 | Modified graphite negative electrode material and preparation method and application thereof |
-
2014
- 2014-12-31 CN CN201410855276.8A patent/CN104852049A/en active Pending
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107293697A (en) * | 2017-07-26 | 2017-10-24 | 大连宏光锂业股份有限公司 | A kind of power-type lithium ion battery negative material production method |
| CN107293697B (en) * | 2017-07-26 | 2019-07-12 | 大连宏光锂业股份有限公司 | A kind of power-type lithium ion battery negative electrode material production method |
| CN110521028A (en) * | 2018-03-22 | 2019-11-29 | Tdk株式会社 | Cathode and lithium ion secondary battery |
| CN110521028B (en) * | 2018-03-22 | 2022-07-01 | Tdk株式会社 | Negative electrode and lithium ion secondary battery |
| CN110581275A (en) * | 2018-06-07 | 2019-12-17 | 山东欧铂新材料有限公司 | Graphene/soft carbon negative electrode material of lithium ion battery, preparation method of graphene/soft carbon negative electrode material and lithium ion battery |
| CN110429278A (en) * | 2019-07-10 | 2019-11-08 | 中盐安徽红四方锂电有限公司 | A kind of negative electrode slurry and preparation method thereof for low temp lithium ion battery |
| CN116022783A (en) * | 2023-01-09 | 2023-04-28 | 南阳天成新能源科技有限公司 | Modified graphite negative electrode material and preparation method and application thereof |
| CN116022783B (en) * | 2023-01-09 | 2023-08-08 | 南阳天成新能源科技有限公司 | Modified graphite negative electrode material and preparation method and application thereof |
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Application publication date: 20150819 |